1 Au PT

ISSN 1463-9262
Cutting-edge research for a greener sustainable future

CRITICAL REVIEW
Robert J. Davis et al.
Selective oxidation of alcohols and aldehydes over supported metal
nanoparticles
www.rsc.org/greenchem Volume 15 | Number 1 | January 2013 | Pages 1268
Green Chemistry
CRITICAL REVIEW
Cite this: Green Chem., 2013, 15, 17
Received 11th September 2012,
Accepted 12th October 2012
DOI: 10.1039/c2gc36441g
www.rsc.org/greenchem
Selective oxidation of alcohols and aldehydes over
supported metal nanoparticles
Sara E. Davis, Matthew S. Ide and Robert J. Davis*
Oxidation is a key reaction in organic synthesis and will likely play a signicant role in the development
of value-added chemicals from biomass. The application of heterogeneous catalysis and molecular
oxygen to oxidation reactions oers a green alternative to traditional, toxic chemical oxidants. However,
making comparisons of catalyst performance (reaction rate, product selectivity) between reports in the
literature is dicult because of inconsistencies in the ways results are reported. Herein, we examine the
literature on supported metal catalysts for the oxidation of molecules of interest in biomass conversion
( primary alcohols, polyols, 5-hydroxymethylfurfural, and various sugars). Reaction rates are calculated
and compared in a consistent manner and recommendations for avoiding common pitfalls in kinetic
investigations are made.
1. Introduction
The diminishing supply of oil has heightened interest in the
development of more sustainable alternatives to petroleum-
derived fuels and chemicals. Although much attention is paid
to the transportation and energy sectors of the economy, 5%
of current consumption of crude oil is used for the production
of chemicals.
1
Renewable resources such as solar and wind
power can meet some of the worlds energy demands, but
replacements for petroleum-derived chemicals require a
source of carbon atoms, such as biomass. The U.S. National
Renewable Energy Laboratory (NREL) describes a biorefinery
for the conversion of biomass to produce fuels, power, and
chemicals that is analogous to the contemporary petroleum
refinery.
2
A major challenge to the development of a bio-
refinery, and thus the biorenewable chemicals industry, is
identifying key intermediates and platform chemicals. While
todays petroleum refinery benefits from years of optimization
and a well-defined set of platform chemicals for the pro-
duction of value-added chemicals, the implementation of the
biorefinery is still under development.
In 2004, the US Department of Energy (DOE) sought to
identify the molecules with the greatest potential for use as
value added chemicals from biomass.
3,4
In the years since the
DOE report, the literature involving the production and trans-
formation of these chemicals has grown substantially. While a
consensus on the key intermediates that will be utilized in a
biorefinery has yet to be reached, common reactions such as
oxidation, reduction and dehydration will undoubtedly play a
role in their development. As the oxidation of alcohols to their
corresponding ketones, aldehydes, and/or carboxylic acids is
one of the most important transformations in organic syn-
thesis, reviews of the transformations of alcohols by bio-
catalysts
5
and heterogeneous photocatalysts
6
were recently
published. The use of Au catalysts for selective oxidation re-
actions of sugars and alcohols was also recently discussed.
7
In the current review, we focus on the selective oxidation of
alcohols (and aldehydes) over supported metal catalysts,
because of the ease of recovery of heterogeneous catalysts from
the products and their potential for recyclability. In particular,
this critical review aims to classify reaction rates on a common
basis (the turnover frequency, TOF) so that catalyst perform-
ance (rate and selectivity) can be compared in a consistent
manner.
We have chosen to examine the oxidation of several classes
of alcohols, including monoalcohols, 5-hydroxymethylfurfural
(HMF), and polyols. The monoalcohols ethanol, octanol,
benzyl alcohol, and cinnamyl alcohol, have been used pri-
marily as model alcohols to test for oxidative activity and selec-
tivity over a wide variety of supported metals and reaction
conditions. The oxidation of HMF to 2,5-furan dicarboxylic
acid (FDCA) was highlighted by the DOE as a target reaction to
produce a monomer for use in polyethyleneterephthalate
(PET)-like plastics because HMF can be produced from
glucose.
4
The polyol glycerol is a byproduct of the transesterifi-
cation of vegetable oil and animal fats into bio-diesel. While
glycerol can be utilized in pharmaceutical and cosmetic
applications, bio-diesel production provides low purity gly-
cerol. The oxidation of glycerol to fine chemicals, such as
Department of Chemical Engineering, University of Virginia, 102 Engineers Way,
Charlottesville, VA 22904-4741, USA. E-mail: rjd4f@virginia.edu;
Fax: +1 434-982-2658; Tel: +1 434-924-6284
This journal is The Royal Society of Chemistry 2013 Green Chem., 2013, 15, 1745 | 17
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dihydroxyacetone (DHA), glyceric acid (GA), and tartronic acid
(TA), might also help oset the cost of bio-diesel production.
8
Finally, the direct oxidation of glucose and other simple
sugars to acids for use as additives in food and beverages was
examined. The oxidation of sugars is also interesting because,
in aqueous solution, sugars exist in equilibrium between their
ring-opened aldose form and their ring-closed cyclic form.
9
As the depth of the literature on selective oxidation grows,
the wide variety of reaction conditions, catalyst characteristics,
and methods for rate calculations make comparing the conver-
sion, selectivity, and kinetic results dicult. Perhaps the most
problematic area involves the rate, as the literature generally
does not report turnover frequency calculations in a consistent
way. It is our belief that the most useful form of the turnover
frequency (TOF) is reported at a low level of conversion, before
substantial deactivation of the catalyst takes place, and is
based on the amount of surface metal available to the sub-
strate (eqn (1)).
TOF
moles of substrate converted
moles of surface metal time
1
Therefore, in this review, we discuss the literature that has
reported turnover frequency values in this way, or has reported
enough information for us to calculate the turnover frequency
ourselves, so that various catalysts for oxidation reactions can
be compared. Because many of the reactions included in this
review are not simple one step oxidations but are sequential
reactions, we emphasize the importance of comparing product
selectivity at equal levels of conversion.
2. Alcohol oxidation mechanism
The oxidation of a primary alcohol proceeds first to an alde-
hyde and subsequently to a carboxylic acid, as outlined in
Fig. 1. The oxidation of an alcohol to an aldehyde over a
heterogeneous catalyst likely occurs in three steps: first, the
alcohol adsorbs on the metal surface, producing an adsorbed
metal alkoxide. Second, -hydride elimination occurs to
produce a carbonyl species and a metal hydride. Last, the
metalhydride is oxidized by dioxygen to regenerate the metal
surface. The oxidation of an aldehyde to carboxylic acid is
believed to proceed through a geminal diol intermediate.
2.1 Metalalkoxide formation
As mentioned above, the mechanism of primary alcohol oxi-
dation to aldehyde over a supported metal catalyst likely
begins with the formation of a metal alkoxide;
1015
however,
the nature of the metal or the nature of substrates adsorbed
on the metal may influence its formation. In the case of benzyl
alcohol and Ru/Al
2
O
3
or Ru(OH)
x
/Fe
3
O
4
catalysts, a Rualkoxide
has been hypothesized to form via ligand exchange between
RuOH and the alcohol, producing a Rualkoxide and a water
molecule.
16
In other work with Ru and Pd catalysts, activation
of the OH bond in benzyl alcohol on the metal surface is pro-
posed, yielding a metalalkoxide and a metalhydride.
11,12,15,17
The selective oxidation of primary alcohols over secondary
alcohols was demonstrated for benzyl alcohol and phenyletha-
nol oxidation over Ru catalysts.
10,14
These results are consist-
ent with formation of a metal alkoxide intermediate, as the
formation of this species is well known for the selective oxi-
dation of primary alcohols.
10,16,18,19
In a seeming contra-
diction, Mori et al. report similar reaction rates for benzyl
alcohol and 1-phenylethanol oxidation over a Pd catalyst, yet
propose the same metal alkoxide intermediate.
11
Further
support for metal alkoxide formation was derived from 2-pro-
panol oxidation with O
2
over Ru/Al
2
O
3
. Production of H
2
O and
acetone were monitored during the reaction and revealed a
1 : 1 molar ratio.
10,18
Similarly, the uptake of O
2
was monitored
during benzyl alcohol oxidation, and a 1 : 2 molar ratio of O
2
to aldehyde was observed.
11,14,15,18
These studies demonstrate
that simple dehydrogenation of alcohol to aldehyde does not
take place.
2.2 -Hydride elimination
A -hydride elimination is widely accepted as the second step
of alcohol oxidation over metal catalysts, producing a carbonyl
group and a metalhydride.
1012,14,15,18,20,21
The Hammett methodology has been employed by a few
groups to probe the mechanism of benzyl alcohol oxidation
and to confirm the -hydride elimination step.
10,13
Comparing
the rates of para-substituted benzyl alcohols over Ru catalysts
yielded a Hammett value of 0.461, which indicates the for-
mation of a carbocation-type intermediate due to hydride
abstraction from the Rualkoxide.
10
Similarly, a Hammett
value of 1.10 was found over a Au catalyst, indicating that a
similar mechanism operates despite the higher oxygen cover-
age on Ru than on Au.
13
The hydride abstraction step was also confirmed through
the incorporation of deuterium in the -position of the
alcohol. The deuterated alcohol should react significantly
slower than the non-deuterated alcohol and the kinetic isotope
eect was found to be 1.82. Transfer hydrogenation was noted
in a mixture of acetophenone and 2-propanol with a Ru cata-
lyst, further supporting the formation of a RuH species.
10
Interestingly, the -hydride elimination step has been pro-
posed as the likely rate-determining step in alcohol
oxidation.
10,11,14,15
2.3 Oxidation of metalhydride and regeneration of catalyst
surface
The third step in alcohol oxidation to aldehyde is the oxidation
of the metalhydride species generated from the -hydride
elimination step to regenerate either the metalhydroxide
10,14
or metal surface.
11,12,15
The oxidation of the metalhydride Fig. 1 General oxidation scheme for primary alcohol oxidation to acid.
Critical Review Green Chemistry
18 | Green Chem., 2013, 15, 1745 This journal is The Royal Society of Chemistry 2013
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likely proceeds through a peroxide intermediate to yield a
water molecule and one half of an O
2
molecule.
11
2.4 Oxidation of aldehyde to carboxylic acid
It is well known in organic chemistry that aldehydes in H
2
O
undergo reversible hydration to geminal diols and that the rate
of hydration is accelerated at elevated pH. The geminal diol
will likely adsorb to a metal surface to form a metal alkoxide,
which will undergo -hydride elimination to form a carboxylic
acid.
22
2.5 Illustrative example: ethanol and glycerol oxidation
The oxidation of an alcohol to an acid over supported Au and
Pt was investigated both experimentally and computationally
with density functional theory (DFT).
23
Specifically, the oxi-
dation of ethanol to acetic acid and glycerol to glyceric acid
over Au and Pt in an aqueous solvent requires dioxygen. In
addition, Au requires added base for the reaction to proceed at
low temperature whereas the rate of reaction over Pt is signifi-
cantly increased with the addition of base. The roles of dioxy-
gen and the hydroxide (high pH) in the oxidation mechanism
were explored to elucidate the most likely steps in alcohol oxi-
dation. Since ethanol (alcohol) and glycerol ( polyol) are oxi-
dized by the same mechanism, it is likely that the mechanism
can be extended to most alcohol oxidations.
Table 1 (Steps 1 and 2) compares the energetics of the first
step of ethanol oxidation to form a metal alkoxide via the
initial deprotonation of the alcohol. The deprotonation of an
alcohol can occur in solution, where it is controlled by the
solution pH and pK
a
of the alcohol, or it can occur on a metal
surface where the deprotonation forms a metal alkoxide.
While the intrinsic barrier for deprotonation of the alcohol on
a metal surface is high (Step 1), the presence of a surface
bound hydroxide decreases the activation energy significantly
(Step 2). The activation energy over a Au(111) surface decreases
from 204 kJ mol
1
over the bare metal surface to 22 kJ mol
1
over one containing adsorbed hydroxide. Thus, adsorbed
hydroxide enhances the deprotonation of an alcohol similar to
that in basic solution. It is important to note that Step 1 forms
a metalhydride bond, while Step 2 results in the formation of
adsorbed water.
After the formation of the metalalkoxide, a -hydride elimi-
nation can similarly happen on the metal surface alone or be
facilitated by surface bound hydroxide. While the energy of
activation is again lower over Au(111) with an adsorbed hydroxide
(Step 4) compared to just the bare metal (Step 3), the dier-
ence in activation energy is not as significant as the initial
alcohol deprotonation step. In addition, the -hydride elimi-
nation has similar activation energies over Pt(111) alone and
with an adsorbed hydroxide. Once the -hydride elimination
has been completed, an adsorbed aldehyde is formed on the
surface.
The aldehyde can undergo reversible hydration to a
geminal diol in the solution phase. Under basic conditions,
the aldehyde can also react over the metal surface with hydro-
xide to form an adsorbed diol intermediate (Step 5). A second
-hydride elimination of the geminal diol can form a car-
boxylic acid over the metal surface (Step 6) or be facilitated by
adsorbed hydroxide (Step 7). At this point, O
2
does not play a
role in the mechanism, yet O
2
is required for the oxidation to
proceed. Consistent with the above mechanism, when
18
O
2
was used to oxidize ethanol or glycerol, only unlabeled acetic
acid and glyceric acid were produced, regardless of whether
the catalyst could easily dissociate
18
O
2
, such as Pt and Pd, or
not, such as Au. However, when H
2
18
O was used,
18
O appeared
in the products. The appearance of
18
O in the product when
using H
2
18
O is strong experimental evidence that aqueous-
phase alcohol oxidation most likely proceeds through the
alkoxy intermediate of the geminal diol which can undergo
-hydride elimination on the metal surface to produce the car-
boxylic acid.
Because the dissociation of O
2
on the Au surface is unlikely
(105 kJ mol
1
) and most metal surfaces, such as Pt and Pd, are
likely inhibited by water and hydroxide adsorbed on the
surface, O
2
might adsorb associatively on the surface. Experi-
mental evidence of peroxide production formation during the
reaction suggests that the associatively adsorbed oxygen is
reduced by electrons on the metal catalyst before dissociation
into hydroxide.
24
The energetics of O
2
reduction, summarized
in Table 2, show a low barrier of 16 kJ mol
1
over Au(111) (Step 1).
The adsorbed peroxide can then react with water or decom-
pose on the surface. The dissociation of peroxide into atomic
oxygen and hydroxide on Au(111) (Step 2), however, is less
likely energetically compared to the formation of hydrogen
peroxide and hydroxide (Step 3), which is consistent with
experimental results in which peroxide formation is reported
Table 1 Reaction energies and activation barriers for ethanol oxidation calculated over Au(111) and Pt(111) in water
Step # Step
Au(111) Pt(111)
H
RXN
E
ACT
H
RXN
E
ACT
1 CH
3
CH
2
OH* + * CH
3
CH
2
O* + H* +196 204 +98 116
2 CH
3
CH
2
OH* + OH* CH
3
CH
2
O* + H
2
O* +13 22 5 18
3 CH
3
CH
2
O* + * CH
3
CHO* + H* 40 46 62 15
4 CH
3
CH
2
O* + OH* CH
3
CHO* + H
2
O* 222 12 165 24
5 CH
3
CHO* + OH* CH
3
CHOOH* + * 33 5 5 5
6 CH
3
CHOOH* + * CH
3
COOH* + H* 151 21 154 13
7 CH
3
CHOOH* + OH* CH
3
COOH* + H
2
O* 334 29 258 17
The * represents a catalytic site on the surface. All values in kJ mol
1
.
23
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over supported Au.
24
The last step closes the catalytic cycle by
removing excess electrons from the metal surface via adsorbed
hydroxide reacting with any metal hydrides found on the
metal surface (Step 5). Thus, the role of associatively adsorbed
oxygen is ultimately to remove electrons from the metal
surface, oxidize metalhydride bonds, and regenerate
hydroxide ions.
It is important to note that hydroxide ions are not con-
served during the reaction. Hydroxide ions are reacted during
the oxidation of glycerol to glyceric acid and some are used to
neutralize the acid product. While the reduction of O
2
can
regenerate some of the hydroxide ions (Table 2, Step 1), about
0.6 mole of hydroxide was consumed for every mole of glycerol
converted, after the hydroxide used to neutralize the acid
products was accounted for.
25
2.6 Illustrative example. HMF oxidation
The oxidation of 5-hydroxymethylfurfural (HMF) involves both
the oxidation of an aldehyde and an alcohol. The oxidation to
monoacid hydroxymethylfurancarboxylic acid (HFCA) and
diacid 2,5-furandicarboxylic acid (FDCA) at ambient temp-
eratures over Pt and Au catalysts requires both a base (typically
NaOH) and gaseous dioxygen and the roles of both base and
O
2
in the mechanism were elucidated recently.
26
Similar to the
glycerol study,
23
isotopically-labeled H
2
18
O and
18
O
2
were
employed to discern the source of oxygen atoms inserted into
the products. To ensure that the incorporation of labeled
oxygen was due to the mechanism of reaction and not due to
oxygen scrambling in solution, control experiments under
reaction conditions were conducted. No oxygen scrambling
between H
2
18
O and the products HFCA and FDCA was
detected.
The majority product of HMF oxidation was found pre-
viously to be aected by the catalyst type and ratio of NaOH:
HMF.
26
Thus, three dierent scenarios for HMF oxidation were
examined in that study: oxidation to FDCA over Pt, oxidation
to HFCA over Au with a relatively low concentration of NaOH
(NaOH: HMF 2 : 1), and oxidation to FDCA over Au with a rela-
tively high concentration of NaOH (NaOH: HMF 20 : 1). In all
of these studies, the incorporation of
18
O was found in the
product when the reaction was conducted with H
2
18
O, but no
incorporation of
18
O was seen in reactions utilizing
18
O
2
.
In the case of a Au catalyst with low NaOH concentration, two
18
O atoms were incorporated in the product, HFCA, when the
reaction was run in H
2
18
O, presumably both in the acid group.
In the case of Au with a high concentration of NaOH and in
the case of the Pt-catalyzed reaction, four
18
O atoms were
incorporated in the diacid product, FDCA, when the reaction
was run in H
2
18
O. Thus, in all cases, oxygen insertion in the
acid products occurred through H
2
18
O. The proposed mecha-
nism can be seen in Fig. 2.
In step one, the aldehyde side chain of HMF undergoes
reversible hydration in solution to a geminal diol through the
nucleophilic addition of a hydroxide ion to the carbonyl and
proton transfer from H
2
O to the alkoxy ion intermediate. The
second step is a dehydrogenation of the geminal diol to form a
carboxylic acid, likely facilitated by hydroxyl ions on the metal
surface, as indicated in the previous section. This step pro-
duces two molecules of water and deposits two electrons on
the metal surface. In the third step, the hydroxymethyl group
is dehydrogenated to an aldehyde. It is believed that base
deprotonates the alcohol group, likely in solution, to form an
alkoxy intermediate.
23
Subsequently, hydroxide ions on the
metal surface facilitate the activation of the CH bond in the
hydroxymethyl group to form an aldehyde, producing two
molecules of water and depositing two additional electrons on
the metal surface. In step four, this aldehyde undergoes the
same reversible hydration to a geminal diol as seen in step
one. Finally, a dehydrogenation step produces the second car-
boxylic acid (step five), depositing two more electrons on the
metal surface, analogous to step two. In total, six electrons are
deposited on the metal catalyst surface.
Though the isotopic labeling studies indicate that oxygen
atoms from dioxygen are not directly incorporated in the acid
products, it is essential for the oxidation of HMF to FDCA. It
was proposed in the ethanol and glycerol oxidation mecha-
nism that O
2
is an electron scavenger, removing excess elec-
trons from the metal surface by undergoing the oxygen
reduction reaction to peroxide and hydroxide ions.
23,26
A test
also revealed peroxide in solution during HMF oxidation reac-
tions; therefore, it is believed that the role of O
2
in HMF oxi-
dation is to scavenge electrons from the metal catalyst surface,
regenerating hydroxide ions and closing the catalytic cycle.
26
This mechanism is completely consistent with that described
for ethanol and glycerol oxidation.
3. Alcohol oxidation review
3.1 Ethanol
Production of ethanol from biomass has been the investigated
thoroughly due to the application of ethanol as a liquid fuel.
Much of the literature focuses on electro-oxidation of ethanol
in fuel cells, or on oxide materials as catalysts for ethanol oxi-
dation, which is beyond the scope of this review. The oxidation
of ethanol can lead to acetic acid, an important industrial
chemical in the production of synthetic fibers and fabrics, as
well as a chemical reagent in the production of vinyl acetate.
Consistent with other alcohol oxidation reactions and the
mechanism discussed earlier, the first oxidation product is
Table 2 The role of O
2
in oxidation of alcohols. Activation barriers calculated
over Au(111) and Pt(111) in water
Step # Step
Au(111) Pt(111)
E
ACT
E
ACT
1 O
2
* + H
2
O* OOH* + OH* 16 18
2 OOH* + * O* + OH* 83 52
3 OOH* + H
2
O* H
2
O
2
* + OH* 48 41
4 H
2
O
2
* + * OH* + OH* 71 29
5 OH* + H* H
2
O* + * 39 30
The * represents a catalytic site on the surface.
23
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acetaldehyde and the second oxidation product is acetic acid.
The general oxidation scheme for ethanol oxidation is seen in
Fig. 3.
Zope et al. reported on the oxidation of ethanol over sup-
ported Au and Pt catalysts, both in presence and absence of
added NaOH.
23
The group found the turnover frequencies over
Au to be an order of magnitude higher than those over
Pt when a 2 : 1 ratio of NaOH: ethanol was used. In the
absence of NaOH, the Au catalysts were inactive for ethanol
oxidation at 333 K, whereas Pt/C displayed some activity. The
turnover frequencies for ethanol oxidation are summarized in
Table 3.
Jorgensen et al.
27
investigated the oxidation of aqueous
ethanol over Au/TiO
2
catalysts at temperatures between 363
and 473 K, and a yield of 95% acetic acid was reached. Prelimi-
nary investigations over Au/C did not demonstrate nearly as
high a conversion of ethanol or selectivity to acetic acid.
Although attempts were made to recycle the catalyst, a signifi-
cant decrease in activity was noted, likely due to Au particle
aggregation (spent catalyst Au size 57 nm; unused 36 nm).
The intermediates and byproducts noted in this reaction were
acetaldehyde, CO
2
, and ethyl acetate. The reaction profile
shows that the oxidation of ethanol proceeds through
acetaldehyde before reaching acetic acid. Using acetaldehyde
as the reactant demonstrated a rapid oxidation to acetic acid
(acetic acid yield 98%); thus, it was determined that the de-
hydrogenation of ethanol was the rate determining step.
Because extending the reaction time showed no degradation of
acetic acid, formation of CO
2
likely occurred via over-oxidation
of an intermediate species. One proposed intermediate forms
by the adsorption of ethanol to the catalyst surface and can be
either oxidized/dehydrogenated to acetaldehyde or cleaved to
produce CO
2
. An attempt was made to increase the yield of
ethyl acetate by varying the concentration of ethanol and a
maximum selectivity to ethyl acetate (50%) was seen at concen-
trations between 80100% ethanol, indicating that water has a
significant limiting eect on the production of ethyl acetate
from ethanol.
At moderate temperature and pressure (423 K and 0.6 MPa
O
2
), the selective oxidation of aqueous ethanol into acetic acid
with 90% yield was demonstrated by Christensen et al.
28
Fig. 3 Reaction scheme for ethanol oxidation.
Table 3 Turnover frequencies and reaction conditions for ethanol oxidation
a
Catalyst
Particle
size (nm) T (K)
Pressure
(kPa) Solvent
TOF
(s
1
) Reference
Au/C 20 333 1035 H
2
O + 2 eq.
NaOH
0.30 23
Au/TiO
2
3.4 333 1035 H
2
O + 2 eq.
NaOH
0.46 23
Pt/C 2.3 333 1035 H
2
O + 2 eq.
NaOH
0.04 23
Pt/C 2.3 333 1035 H
2
O 0.01 23
a
All reactions were performed in batch mode with O
2
as oxidant.
Fig. 2 Proposed HMF oxidation mechanism, adapted from ref. 26.
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Ethanol concentrations corresponding to those obtained
during fermentation were utilized. Comparing the yields from
Au/MgAl
2
O
4
(conversion 97%, selectivity 86%), Pt/MgAl
2
O
4
(conversion 93%, selectivity 65%), and Pd/MgAl
2
O
4
(conversion
82%, selectivity 20%) at the same reaction conditions, the
highest yield was obtained over the Au catalyst. No signs of sin-
tering were seen for the Au catalyst ( particle size 36 nm) over
the course of the reaction (30 h). Under optimized conditions
(453 K and 3.5 MPa O
2
), 92% yield of acetic acid was obtained
after 8 h. Increasing the reaction temperature resulted in both
increased conversion of ethanol and selectivity to acetic
acid.
27,28
Gold catalysts are among the most eective of the sup-
ported metal nanoparticle catalysts for ethanol oxidation,
though much of the literature seems to be focused on metal
oxides or electrocatalysts for this transformation. The number
of reports of initial TOF is limited, and most reports on
ethanol oxidation are at too high conversion to calculate initial
rate.
3.2 Octanol
Octanol is often used as a probe molecule to determine the
eectiveness of a catalyst in the oxidation of alkanols. The
general reaction scheme for octanol oxidation is seen in Fig. 4.
Low reactivity is characteristic of octanol. Accordingly, there is
an abundance of low conversion results in the literature,
which facilitates the calculation of initial reaction rate.
Both primary and secondary octanols are investigated fre-
quently, and the rates of 1-octanol oxidation are summarized
in Table 4. The highest rate was obtained over bimetallic cata-
lysts containing Au and either Pt or Pd (0.3 s
1
for PdAu/C and
0.2 s
1
for PtAu/C) in H
2
O solvent with 4 equivalents of NaOH
at 323 K.
29
Under the same conditions, but in absence of
added base, the rates of oxidation were an order of magnitude
lower for both bimetallic catalysts. An experiment utilizing a
AuPd bimetallic catalyst in water with 1-equivalent NaOH
exhibited a TOF of 0.06 s
1
, higher than the base-free case but
lower than the experiment with higher NaOH concentration.
30
Additionally, Au monometallic catalysts were inactive for
1-octanol oxidation without addition of base in both water and
toluene solvents.
29,30
Thus, the role of base in octanol oxi-
dation over bimetallic PdAu and PtAu catalyst is significant.
The role of base is also significant in oxidation over monome-
tallic Au catalysts; in the absence of added base, the Au catalyst
was virtually inactive, though some activity was realized with
the addition of 4 : 1 NaOH: substrate. Interestingly, the
addition of base to the reaction mixture over Pt and Pd mono-
metallic catalysts had no significant eect on the reaction rate.
Aside from the bimetallic catalysts, the rates shown in Table 4
are similar to each other and it would seem that the intrinsic
TOF of 1-octanol oxidation in water at temperatures 323 K
373 K over Au, Pt, and Pd metals is on the order of 0.01 s
1
.
Dimitratos et al. have speculated that NaOH facilitates the
first step of oxidation, H abstraction, which Au alone is unable
to catalyze at low temperature.
30
Moreover, the addition of
Fig. 4 Reaction scheme for octanol oxidation.
Table 4 Turnover frequencies and reaction conditions for 1-octanol oxidation
a
Catalyst Particle size (nm) T (K) Pressure (kPa) Solvent TOF (s
1
) Reference
Au/CeO
2
Not reported 373 200 None 0.007 31
Au/C Not reported 323 310 H
2
O + 4 eq. NaOH 0.05 29
Pd/C Not reported 323 310 H
2
O + 4 eq. NaOH 0.007 29
Pd/C Not reported 323 310 H
2
O 0.007 29
Pt/C Not reported 323 310 H
2
O + 4 eq. NaOH 0.008 29
Pt/C Not reported 323 310 H
2
O 0.008 29
PdAu/C Not reported 323 310 H
2
O + 4 eq. NaOH 0.3 29
PtAu/C Not reported 323 310 H
2
O + 4 eq. NaOH 0.2 29
PdAu/C Not reported 323 310 H
2
O 0.01 29
PtAu/C Not reported 323 310 H
2
O 0.02 29
0.73%Au0.27%Pd/C 3.4 333 155 H
2
O 0.02 30
0.73%Au0.27%Pd/C 3.4 333 155 H
2
O + 1 eq. NaOH 0.06 30
a
2
as oxidant.
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NaOH favors formation of Na-carboxylate, which is more
stable than metal-carboxylate. Thus, the products are thought
to desorb from the metal surface so the catalytic cycle can con-
tinue uninhibited.
The addition of NaOH can enhance the reaction rate, but
also aects the product selectivity, presumably because of the
sequential nature of the oxidation reaction. In the case of a
PdAu/C catalyst, 17% conversion of aqueous 1-octanol with
70% selectivity to the aldehyde was realized after 8 h at 323 K
without base; adding 4 equivalents of NaOH without changing
the other conditions shifted the selectivity toward the acid
(98% selectivity) with 93% conversion in just 4 h.
29
Under the
same conditions but with the monometallic Pd/C catalyst, at
2% conversion of 1-octanol the selectivity to the aldehyde was
70% in absence of NaOH, but with 4 equivalents of NaOH, the
reaction was 97% selective to the acid at 2% conversion. The
trend continued over Pt and PtAu catalysts.
Prati et al. also noted a negligible eect of O
2
pressure on
1-octanol reaction rate. Increasing the reaction temperature
enhanced activity but resulted in a decrease in selectivity to
aldehyde.
29
In addition to 1-octanol, secondary octanols have also been
investigated. For example, the rates of oxidation of neat
3-octanol over some supported catalysts are reported in
Table 5. The highest rates for 3-octanol oxidation were
obtained over Au catalysts supported on nanocrystalline CeO
2
.
Both supported Au catalysts in Table 5 exhibited high selec-
tivity to the ketone product (99 and 97%, respectively). Table 5
also presents a comparative study of Au/CeO
2
and Pd/CeO
2
demonstrating the enhanced activity of Au (TOF
Au
= 2.92 s
1
compared to TOF
Pd
= 0.09 s
1
at 333 K), although supporting
Pd on apatite improved its activity. The oxidation of 2-octanol
was investigated over supported Ru(OH)
x
and Pd catalysts in
toluene and trifluorotoluene, respectively
11,14
and both metals
were shown to be active for this oxidation.
The literature investigating octanol oxidation highlights the
superior activity (rate) of Au catalysts over Pd catalysts for
alcohol oxidation, typically exhibiting a TOF an order of mag-
nitude greater. The role of additional homogenous base is sig-
nificant in reactions utilizing bimetallic Pt or Pd and Au
catalysts or Au monometallic catalysts. The role of base is
apparently much less important in reactions utilizing mono-
metallic Pt or Pd catalysts.
3.3 Benzyl alcohol oxidation
Benzyl alcohol is often used as a model alcohol to test for cata-
lyst reactivity. While the literature is extensive on this topic,
quality rate data obtained at low conversion is lacking. The
popularity of benzyl alcohol as a probe molecule results from
its extremely high reactivity and the limited number of side
products (the intermediate benzaldehyde is a non-enolizable
structure).
31
Like other alcohols, benzyl alcohol oxidation pro-
ceeds through an aldehyde intermediate to the acid final
product, as depicted in Fig. 5. Typical metal catalysts for
benzyl alcohol oxidation are Pt, Pd, and Au.
3.3.1 Palladium catalysts. Nanoparticles of Pd have been
supported on a variety of materials, including hydroxyapatite
(HAP),
11
carbon,
11,30
Al
2
O
3
,
11
SiO
2
,
11
pumice,
34
and SiO
2
Al
2
O
3
mixed oxide.
15
Table 6 shows the turnover frequency results
from selected works that provided appropriate information.
It is interesting to note that the TOFs vary by an order of
magnitude from 0.19 s
1
to 2.8 s
1
over a fairly narrow range
of experimental conditions.
The role of the support for Pd catalysts was investigated by
Mori et al.
11
and Chen et al.
15
Mori et al. found that benzyl
alcohol conversion and the benzaldehyde selectivity depended
on support, with the hydroxyapatite (HAP)-supported catalyst
having the highest conversion (99%) and selectivity to alde-
hyde (99%). The other supports examined (Al
2
O
3
, SiO
2
, and C)
produced the aldehyde with less than 50% selectivity; the most
selective was Pd/SiO
2
(47%) though the conversion was only
71%. The highest conversion was achieved over Pd/Al
2
O
3
,
though the selectivity was the lowest (38%). The Pd/C pro-
duced the lowest conversion (46%) and low selectivity (42%).
Unfortunately, the reaction rates over these catalysts were not Fig. 5 Reaction scheme for benzyl alcohol oxidation.
Table 5 Turnover frequencies and reaction conditions for 3-octanol oxidation
a
Catalyst
Particle
size (nm) T (K)
Pressure
(kPa) Solvent
TOF
(s
1
) Reference
Au/CeO
2
4.5 353 101.3 None 0.54 32
Au/CeO
2
4.5 393 Flowing None 2.92 33
Pd/CeO
2
6 393 Flowing None 0.09 33
Pd/Apatite 7.5 393 Flowing None 0.74 33
a
2
as oxidant.
Table 6 Turnover frequencies and reaction conditions for benzyl alcohol oxidation over Pd catalysts
a
1
) Reference
Pd/C 2.9 363 101.3 Trifluorotoluene 0.19 11
Pd/pumice Not reported 333 202.6 Acetonitrile 2.8 34
Pd/SiO
2
Al
2
O
3
4.3 353 Flowing None 2.5 15
a
All reactions were performed in batch mode.
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given, so no conclusions can be drawn about the eect of
support on reaction rate.
Chen et al. probed the eect of Pd particle size on BA oxi-
dation by varying the ratio of SiO
2
: Al
2
O
3
in a mixed oxide
support to tune the size of Pd particles in the range
2.210 nm.
15
Decreasing the SiO
2
: Al
2
O
3
ratio resulted in a
decrease in the size of the Pd nanoparticles, due to the
relative strength of interactions of the Pd precursor with
the support. Though varying the SiO
2
: Al
2
O
3
ratio changed the
relative acidity of the support, the variation in activity
correlated only to Pd nanoparticle size. A maximum TOF was
found at a mean metal particle size of 3.64.3 nm, suggesting
that BA oxidation over Pd might be structure sensitive,
which was also noted by Mori et al.
11
in their work over Pd
supported on HAP. The optimized catalysts (Pd particle sizes
of 4.3 nm and 3.6 nm) demonstrated high TOF (2.53 s
1
and
2.45 s
1
, respectively) as well has high selectivity to the alde-
hyde (98% selectivity with 73% conversion and 98% selectivity
with 99% conversion, respectively, in 10 h) in solvent-free
conditions.
Uozumi et al. utilized a novel support, an amphiphilic
resin, in the oxidation of aqueous alcohols.
35
The resin is
highly hydrophobic in its pores, so organic molecules can
diuse from the aqueous media into the matrix where the
anchored Pd nanoparticles catalyze the oxidation. A mixture of
catalyst and benzyl alcohol was refluxed in water under atmos-
pheric pressure of dioxygen to give 97% yield of the aldehyde
product after 1.5 h. The high selectivity to the aldehyde in
aqueous medium is interesting particularly because sequential
oxidation to the carboxylic acid readily occurs in water. Appar-
ently the hydrophobic nature of the resin prevents the conver-
sion of the aldehyde in water over Pd.
The eect of solvent was investigated by Mori et al.
11
and
Villa et al.
36
Mori found the most eective solvent to be tri-
fluorotoluene (99% conversion in 1 h), although 1,2-diethoxy-
ethane aorded 65% conversion under the same conditions.
Aprotic polar solvents were not eective at all, which the
authors hypothesized may be due to the coordination of het-
eroatoms to Pd(II) pre-catalysts, preventing their reduction to
Pd
0
. The oxidation of BA in aqueous NaOAc over Pd/HAP
resulted in 90% yield of aldehyde and 10% yield of benzoic
acid at 383 K in an O
2
atmosphere after 24 h, which is unusual
given the typical sequential oxidation of aldehyde to carboxylic
acid in high pH solution.
The investigation of role of solvent by Villa et al. used Pd on
activated carbon (AC) or on carbon nanotubes (CNT).
36
An increased rate of reaction was noted in neat alcohol (TOF
0.83 s
1
) as opposed to a mixture of 80% water and 20%
alcohol (TOF 0.023 s
1
) over Pd/AC catalyst, though the
product distribution remained unchanged. The rate of reaction
was higher in cyclohexane than in water. It is important to
note that the leaching of Pd from the support into the liquid
was extensive in this study, 28% for Pd/AC and 25% for
Pd/CNTs.
From these results, it appears that the support material for
Pd nanoparticles can have a substantial eect on the product
selectivity. Interestingly, the appropriate choice of support can
suppress the sequential oxidation of aldehyde to carboxylic
acid in aqueous solution. Nevertheless, it seems that the
intrinsic turnover rate for benzyl alcohol oxidation over Pd
catalysts at modest temperatures (<373 K) is on the order of 2 s
1
.
3.3.2 Au catalysts. The eects of support, added base, and
metal particle size have been investigated thoroughly for BA
oxidation over Au catalysts. Table 7 shows the calculated TOFs
for BA oxidation over a variety of Au catalysts, but the values
span two orders of magnitude. The critical role of added base
in Au catalysis can be discerned from the oxidation rates in
Table 7. With the exception of the first entry (which was at the
lowest temperature), the TOF associated with base-free con-
ditions is generally an order of magnitude lower than the TOF
obtained in high-pH conditions. The rates for BA oxidation
over the Au foil catalysts are on the same order of magnitude
as those for glycerol and HMF oxidation (to be discussed
later), as well as over Pd catalysts for benzyl alcohol oxidation.
Much of the literature on alcohol oxidation over Au catalysts
describes results obtained in the presence of a homogeneous
base. As Table 7 shows, added base can greatly enhance the
reaction rate. Buonerba et al.
37
supported Au nanoparticles on
block copolymers and used the resulting catalysts in the oxi-
dation of benzyl alcohol in a water and chloroform solvent
with added KOH. They attained >99% conversion of benzyl
alcohol and 97% selectivity to the aldehyde product after 6 h
at mild conditions (308 K, 100 kPa O
2
). Over longer reaction
times (>24 h), further oxidation of benzaldehyde was not
Table 7 Turnover frequencies and reaction conditions for benzyl alcohol oxidation over Au catalysts
a
1
) Reference
Au on block co-polymers 9.5 308 100 1 : 1 H
2
O: chloroform with KOH
(1 : 1 KOH: substrate)
0.04 37
Au/CeO
2
4.5 373 200 None 0.042 31
Au foil n/a 333 500 H
2
O + 0.6 M NaOH 2.8 38
Au foil n/a 363 500 Toluene + equimolar K
2
CO
3
2.8 38
Au foil n/a 363 500 Heptane + equimolar K
2
CO
3
4.4 38
2
CO
3
2.8 38
2
CO
3
5.7 38
Au/MgO 3.3 453 Unknown Trifluorotoluene 0.13 39
Au/HT 3.1 393 Flowing
b
Toluene 0.22 21
a
b
Ar atmosphere.
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observed; the performance of these materials is in stark con-
trast to other reports which showed partial or complete oxi-
dation to benzoic acid in aqueous media or in the presence of
base.
22,38,40,41
The authors ascribed this dierence to the
temperature (407 K) and the hydrophobic nature of the
polymer phase in conjunction with the chloroform solvent,
similar to what Uozumi and Nakao proposed in their Pd/resin
catalysts.
35
Thus, a support material may inhibit oxidation of
aldehyde to acid in high pH aqueous media. However, the
influence of the base might also be limited by the hydrophobic
support.
Very recently, Guo et al. reported successful aerobic oxi-
dation of benzyl alcohol over unsupported bulk Au.
38
The oxi-
dation of BA was performed in aqueous NaOH, and the
distribution of products was a function of the reaction temp-
erature and concentration of NaOH. For benzyl alcohol oxi-
dation at 333 K, the major product was the ester, benzyl
benzoate, for lower concentrations of base (0.6 M NaOH) and
the acid, benzoic acid, at higher concentrations (1.2 M NaOH).
Increasing the temperature to 363 K resulted in a majority of
the aldehyde product over the range of NaOH concentrations.
Investigation of other solvents revealed that bulk Au was
inert in trifluorotoluene but active for BA oxidation in heptane
and in toluene, producing the aldehyde as the majority
product. The authors hypothesize that the -electrons in BA
enhance interactions with Au, facilitating the oxidation. They
found that the -activation for the CH
2
OH group by the
phenyl group in BA is critical for oxidation over bulk Au. No
oxidation occurred in the presence of inert gas, demonstrating
the importance of O
2
as oxidant in this case, in contrast to pre-
vious work on BA oxidation over supported Au.
21,42
Increasing
the temperature increased the conversion of BA in heptane
solvent, whereas conversion decreased with increasing temp-
erature in water solvent. The authors suggested that the oxi-
dation in aqueous NaOH may be favored by H
2
O
2
produced
during the reaction and that the H
2
O
2
may decompose readily
at the higher temperatures. At the lower temperature, H
2
O
2
was readily detected, whereas at the higher temperature it was
not. No peroxide was detected when heptane was the solvent.
Previous work proposed that, in organic solvent, the role of O
2
was to remove the hydride from the Au surface, or, in aqueous
NaOH, that O
2
regenerated catalytic sites by removing elec-
trons from the surface and in the process regenerating hydrox-
ide ions.
23
As an alternative to adding homogenous base, some groups
investigated solid bases as catalyst supports. The eect of acid
and base sites on the support in Au catalysis for BA oxidation
has been investigated in the absence of additional homo-
geneous base.
21,31,41
In summary, low conversion of benzyl
alcohol was observed after 3 h (maximum conversion 7%, over
Au/Fe
2
O
3
), which is typical of oxidation reactions in the
absence of homogeneous base. Selective oxidation to benz-
aldehyde was achieved over Au on SiO
2
, CeO
2
, and TiO
2
, with
the best results obtained with Au/CeO
2
(3.4% conversion,
100% selectivity to aldehyde after 3 h at 373 K and 200 kPa
O
2
). The lowest conversion was seen over Au/TiO
2
(0.65%
conversion in 3 h; 100% selectivity to aldehyde). The Fe
2
O
3
and C supported catalysts were the only samples to form the
ester product (selectivity to benzyl benzoate 12% and 10%,
respectively); the authors hypothesized that ester formation is
related to the acid sites on the catalyst surface. Indeed, temp-
erature programmed desorption of NH
3
revealed the strongest
acidic sites on Au/Fe
2
O
3
, and addition of a small amount of
HCl to a reaction with Au/SiO
2
supported this hypothesis.
Villa et al. examined the role of base sites on product selec-
tivity in cyclohexane solvent in the absence of homogeneous
base and found a correlation between basicity of the support
and catalyst activity.
41
Gold catalysts supported on nanosized
NiO (35 nm) were more active by an order of magnitude than
Au on commercial micrometer sized NiO (55% conversion vs.
6% conversion, in 6 h), likely due to both an increase in basi-
city of the support (basicity per square meter of nNiO:
0.21 mmol g
1
; of commercial NiO: 0.12 mmol g
1
) and also a
cooperative eect of metal and support.
An inverse relationship between the basicity of the support
and the selectivity to aldehyde formation was also noted. The
more basic nanosized support showed decreased selectivity to
aldehyde (66%) compared to the less basic microsized support
(selectivity to aldehyde 75%); the increased basicity enhanced
sequential oxidation to acid products. The basicity of the
support, however, was not the only factor responsible for the
activity, as MgO was more basic than nNiO (basic site density
0.42 mmol g
1
) but was a much less active support for Au (7%
conversion vs. 55%). Investigation via CO adsorption and IR
spectroscopy revealed that Au/nNiO did not adsorb CO mole-
cules but Au/TiO
2
did, indicating a change in the electronic
properties of Au.
Finally, Fang et al. investigated amphoteric materials and
the eects of their acidity/basicity on BA oxidation in p-xylene
solvent at 393 K in the absence of an oxidant.
21
Gold nano-
particles of a similar size were supported on a variety of
materials to compare support eects. After 1 h of reaction
time, Au/Al
2
O
3
, Au/MgO, Au/HAP, and Au/hydrotalcite (HT)
catalysts demonstrated BA conversion of about 2030%; the
selectivity to the aldehyde over each catalyst was compared at
this conversion. The Au/Al
2
O
3
catalyst showed the highest con-
version (32%) but the lowest aldehyde selectivity (18%),
whereas Au/MgO showed the highest selectivity (99%) but the
lowest conversion (20%). The Au/HT exhibited similar selectiv-
ity to the Au/MgO, but at approximately 10% higher conver-
sion. Temperature programmed desorption (TPD) of NH
3
and
CO
2
revealed that Au/HT and Au/MgO possessed higher con-
centrations of basic sites than the other catalysts. It was also
shown that Au/HT had both strong acid and strong base sites,
Au/SiO
2
had neither acid nor base sites, and Au/MgO had only
strong base sites. The catalysts with neither acid nor base sites
were almost inactive, whereas the catalyst with the highest
acidity and basicity (Au/HT) had the highest conversion of
alcohol and selectivity to aldehyde. Moreover, a catalyst with
stronger basicity in the absence of acidity (Au/MgO) had
higher selectivity to aldehyde, but a catalyst with strong acidity
(Au/Al
2
O
3
) was more active. This is in direct contrast with Villa
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et al., who saw a lower selectivity to aldehyde over catalysts
with more base sites because of sequential oxidation to car-
boxylic acid. It should be noted, however, that the work of
Fang et al. was in absence of an oxidant so the other products
present were toluene and benzene rather than other oxidation
products. The role of O
2
in conjunction with catalyst support
may be significant with respect to product selectivity.
The eect of particle size of Au on BA oxidation was exam-
ined by Boronat et al.
39
using MgO as a support and by Fang
et al. using HT as support.
21
In general, the smaller the par-
ticle diameter, the higher the TOF. Thus, the groups concluded
that alcohol dehydrogenation on Au is a structure-sensitive
reaction, which was also supported by DFT calculations.
39
Interestingly, a maximum TOF for Au on MgO was observed
for a particle size of 3.3 nm (0.09 s
1
) while Au/MgO with a
smaller particle size (1.9 nm) exhibited lower activity (0.03 s
1
).
39
The trend is reminiscent of the trend noted by Chen et al.
15
who saw an optimum ratio of edge and corner sites to terrace
sites in the oxidation of BA over Pd nanoparticles. Others have
also noticed structure sensitivity for alcohol oxidation.
11,15,43
In summary, the oxidation of benzyl alcohol exhibited the
highest rates (5 s
1
) over Au catalysts in the presence of homo-
geneous base. Although the oxidation of alcohol to aldehyde
to acid is greatly accelerated by the presence of homogeneous
base, the sequential oxidation of aldehyde to acid may be
inhibited through careful selection of the solvent and catalyst
support. The incorporation of acid sites and/or basic sites on
catalyst support can influence the product selectivity of the
overall reaction.
3.3.3 AuPt and AuPd bimetallic catalysts. Alloying of
multiple metals has the potential to enhance reaction rate,
alter product selectivity, and/or help slow or prevent catalyst
deactivation. In one report, the alloying of Pd and Au pre-
vented the leaching of Pd from the catalyst support.
36
Syn-
thesis of bimetallic catalysts for benzyl alcohol oxidation is
focused on Au, Pt, Pd, and Ag catalysts. The rates of oxidation
over these bimetallic catalysts are summarized from selected
studies in Table 8.
Enache et al. noted a very high TOF for BA oxidation
(24 s
1
) at mild conditions (373 K, 0.1 MPa O
2
) over a bimetal-
lic AuPd/TiO
2
catalyst.
45
Although the addition of Au to Pd
nanoparticles improved the selectivity to aldehyde (92% at
75% conversion for bimetallic, 54% selectivity at 51% conver-
sion for monometallic Pd), the initial rate of the bimetallic
catalyst was lower than that of the monometallic Pd. This indi-
cates that the TOF for the monometallic Pd catalyst (not
reported) was greater than 24 s
1
, which is much higher than
any other reports for Pd catalysts for BA oxidation.
Microscopy and XPS showed that the nanocrystals were
made up of an Au-rich core with a Pd-rich shell; the enhance-
ment of activity may be due to Au altering the electronic struc-
ture of Pd.
45
Pure Au and Pd catalysts did not retain high
selectivity to the aldehyde at high conversion, whereas the
bimetallic catalyst did (selectivity 96% at 100% conversion).
Bimetallic catalysts were also synthesized on Al
2
O
3
and Fe
2
O
3
,
though the selectivity to the aldehyde was lower (87% at 83%
conversion on Al
2
O
3
, 67% at 63% conversion on Fe
2
O
3
) poss-
ibly due to acid sites on the support promoting ester
formation.
Meenakshisundaram et al. also synthesized bimetallic Au
Pd/TiO
2
catalysts for BA oxidation, and found that the initial
rate of BA oxidation was an order of magnitude higher over the
bimetallic catalyst than over the monometallic Pd catalyst,
which showed a rate an order of magnitude higher than the
monometallic Au catalyst.
44
This contrasts the report above, in
which the bimetallic demonstrated a rate between those of the
Pd and Au monometallic catalysts.
45
Meenakshisundaram
et al.s materials were found to be homogeneous alloys rather
than the shell-and-core configuration of Enache et al. This
group also looked at the reaction under inert pressure and
found that the reaction rates were an order of magnitude lower
than in the presence of O
2
. Moreover, the selectivity to alde-
hyde was 50% with toluene making up the balance. By com-
paring results from the monometallic catalysts, it appears that
all of the activity of the bimetallic alloys to produce aldehyde
under inert pressure was due to the Pd metal and the Au metal
did not contribute to the activity.
Dimitratos et al.
30
saw an enhancement of the reaction rate
over Au, Pd, and AuPt and AuPd bimetallic catalysts sup-
ported on C when water was used as solvent in place of
toluene, in all cases. The Au catalysts were inert in H
2
O and
toluene. However, it is important to note that no homogeneous
base was added to the reaction so this is not surprising, par-
ticularly at such moderate temperatures (333 K). The highest
activity was reached over 0.73%Au0.27%Pd/C catalyst in
toluene (96% conversion, 94% selectivity to aldehyde in 3 h).
The reaction rate of BA oxidation over AuPd bimetallics
was found to be zero order in O
2
pressure in the range
Table 8 Turnover frequencies and reaction conditions for benzyl alcohol oxidation over bimetallic AuPt and AuPd catalysts
a
1
) Reference
AuPd/TiO
2
4 353 100 None 1.6 44
AuPd/TiO
2
4 353 100 He None 0.24 44
0.73% Au0.27% Pd/C 3.4 333 155 Toluene 0.15 30
0.73% Au0.27% Pd/C 3.4 333 155 H
2
O 0.01 30
0.6% Au0.4% Pt/C 3.2 333 155 Toluene 0.004 30
0.6% Au0.4% Pt/C 3.2 333 155 H
2
O 0.05 30
2.5% Au2.5% Pd/C Not reported 433 100 None 24 45
a
All reactions performed in batch mode with O
2
as oxidant.
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1003000 kPa,
44,45
though a direct dependence was noted in
pressures up to 100 kPa.
44
In summary, the bimetallic catalysts discussed in this
review, with the exception of that of Enache et al.,
45
do not
demonstrate enhanced reaction rates for benzyl alcohol oxi-
dation when compared to their monometallic counterparts. In
fact, the highest rate for an Au-containing bimetallic catalyst
was 1.6 s
1
, which is lower than the highest rate reported for a
monometallic Au catalyst (5 s
1
). Although there does not
seem to be an obvious synergistic eect on rate, alloying two
metals for alcohol oxidation catalysts has been shown to
inhibit the leaching of metal (Pd) from the support or to
prevent catalyst deactivation.
30
3.3.4 Other metal catalysts. Other metals or metal com-
pounds have been investigated as catalysts for benzyl alcohol
oxidation, including Ag and Co
3
O
4
. These materials are
common dehydrogenation catalysts and are more economically
attractive than Au or Pd. Ruthenium catalysts have also been
investigated to a limited extent.
Beier et al. investigated a number of supported Ag catalysts
for the oxidation of alcohols by utilizing a screening method.
46
The supports for the Ag particles were SiO
2
, Al
2
O
3
, Celite,
CeO
2
, kaolin, MgO, and activated carbon. Although, Ag/SiO
2
and CeO
2
were nearly inactive (conversion <10%), a physical
mixture of the two was very active for benzyl alcohol oxidation
(conversion up to 45%). The catalytic activity and product dis-
tribution were found to be a function of the weight loading of
Ag on SiO
2
. Apparently, the selectivity to aldehyde was
improved at higher Ag weight loadings, (a 20 wt% Ag/SiO
2
cata-
lyst produced >95% selectivity to aldehyde with 20% conver-
sion). The ratio of CeO
2
: Ag/SiO
2
was also investigated, and at
higher loadings of CeO
2
, a higher selectivity to the aldehyde
was also achieved. Leaching of Ag and CeO
2
were ruled out via
ICP analysis of the filtered reaction mixture and hot filtration
tests confirming no continued reaction after the catalyst was
removed. A soluble cerium source in addition to Ag/SiO
2
did
not enhance the activity. The work suggests that the CeO
2
adsorbs both water and benzaldehyde, thus preventing their
adsorption and deactivation of the Ag surface, a phenomenon
also noted as a problem by Zotova et al. over Ru catalysts.
47
The eect of the calcination temperature of Ag catalysts was
also shown to influence activity.
46
Calcination of Ag above
773 K reduced both activity and selectivity. Silver-oxygen
species in mostly metallic silver particles reportedly played an
important role and were greatly aected by the pretreatment
temperature. Liotta et al. noted similar results on their Ag/
pumice catalyst.
34
Although the Ag catalysts required O
2
to be catalytically
active, the authors surmised that the role of CeO
2
may be to
act as an oxygen reservoir, reversibly storing oxygen.
46
In this
scenario, benzyl alcohol adsorbs on the silver surface where it
is dehydrogenated to benzaldehyde. The CeO
2
activates O
2
,
which can react with hydrogen produced from benzyl alcohol
dehydrogenation and thus regenerate the Ag surface.
The work of Liotta et al. also investigated the use of Ag for
BA oxidation, both in monometallic form and as a bimetallic
with Pd, on a pumice support.
34
The Pd monometallic catalyst
was the most active, with the bimetallic catalyst having a TOF
ten times lower than the Pd, and the Ag monometallic catalyst
another order of magnitude lower than the bimetallic. The
selectivity to the aldehyde product was 95% in all cases.
A physical mixture of the two monometallic catalysts resulted
in a rate higher than the sum of the rates for the monometallic
catalysts used independently, suggesting a synergy between
Pd
0
and Ag
0
in the reactor. The lower activity of the bimetallic
catalyst calcined at 773 K may be due to the presence of PdO.
Although EXAFS indicated the presence of alloyed PdAg, alloy-
ing did not seem to be necessary as the physical mixture of the
two metals was adequate for enhanced activity. The authors
suggested that the oxidative dehydrogenation mechanism, in
which the substrate is dehydrogenated on the metal surface
and oxygen removes the hydrogen to regenerate the site, can
explain this observation. The Pd can activate the alcohol while
the Ag can activate the O
2
. Close proximity of the two com-
ponents allows for the activated oxygen to hop to the Pd.
The importance of the role of O
2
was confirmed by testing
reactions under inert atmospheres. The reaction rate over both
monometallic catalysts was much slower in the absence of O
2
.
Mitsudome et al.
42
used Ag nanoparticles (mean diameter =
3.3 nm) supported on hydrotalcite in the absence of oxidant
for high yield of benzaldehyde after 10 h (>99% conversion BA,
90% selectivity to aldehyde) at moderate conditions (403 K,
Ar atmosphere). In this way, the over-oxidation to carboxylic
acid was avoided, and the only byproduct was H
2
.
The literature for supported nanoparticle ruthenium cata-
lysts is somewhat sparse, which is perhaps an indication of its
ineectiveness for this particular reaction. Indeed, low ratios
of substrate to Ru (1040 mole substrate per mole metal) are
characteristic of many studies. However, the oxidation of
benzyl alcohol to aldehyde was possible over Ru on a variety of
supports, including Al
2
O
3
,
10,47
carbon nanotubes (CNT),
12
and
Fe
3
O
4
.
14
High selectivity to benzaldehyde (>99%) with high
conversion of benzyl alcohol (>99%) was seen at moderate
temperatures (356363 K) over Ru supported on Al
2
O
3
in tri-
fluorotoluene
10,16
and toluene,
47
as well as over Ru supported
on Fe
3
O
4
in toluene.
14
Much of the work used toluene
12,14,47
and trifluorotoluene
10
as solvent, though ethanol, water, and
mixtures of toluene and water
12
have also been investigated.
Unfortunately, none of those studies provided sucient infor-
mation to calculate an initial TOF for BA oxidation.
The eect of O
2
pressure was also studied over Ru, and a
five-fold increase in O
2
pressure from 500 kPa to 2500 kPa sig-
nificantly enhanced the reaction rate. In contrast, Yamaguchi
et al.
18
found no eect of O
2
pressure on reaction rate, though
the range of pressures in this case (20300 kPa) may not have
been large enough to note the eect.
A study of the eect of solvent system was conducted by
Yang et al.,
12
who utilized novel Ru catalysts supported on
carbon nanotubes (CNTs). Three dierent solvents were tested
(water, toluene, and ethanol). Although the reaction in water
solvent demonstrated the highest conversion, the major
product was the acid. The reaction carried out in ethanol
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resulted in 100% selectivity to the aldehyde, but only 50% con-
version of the substrate. The optimized solvent system of 2 : 1
toluene : water exhibited 98% conversion of benzyl alcohol and
100% selectivity to benzaldehyde after 3 h at mild conditions
(358 K and 0.1 MPa O
2
). The authors suggested that the
Ru/CNTs stabilized the emulsion of toluene and water by
decreasing the interfacial tension, while also providing a
higher interfacial surface area for the oxidation of alcohol to
take place. Not only did the oxidation occur at a faster rate in
water, but BA also had a higher solubility in water than in
toluene. The role of toluene was to selectively extract the alde-
hyde (which is more soluble in toluene than in water), thus
preventing over-oxidation to carboxylic acid.
Alternatively, Zhu et al. investigated the use of various
cobalt oxides supported on activated carbon for BA oxidation
in the absence of promoters or base.
48
Testing of cobalt oxide
on a variety of high-surface-area supports verified that high
surface area is advantageous to the activity of cobalt oxide, but
also demonstrated a synergistic eect on the conversion of
benzyl alcohol over cobalt oxide supported on activated
carbon. The group proposed that the activated carbon oers
the sites for dioxygen adsorption/activation, whereas Co
3
O
4
catalyzes the dehydrogenation reaction.
Although explored to a lesser extent than Au and Pd, Ru, Ag
and Co
3
O
4
catalysts oer interesting options for benzyl alcohol
oxidation catalysts.
3.4 Cinnamyl alcohol
Cinnamyl alcohol (CA) oxidation is often used together with
benzyl alcohol as a model reaction for alcohol oxidation. Like
benzyl alcohol, CA is highly reactive; however, the CvC bond
in cinnamyl alcohol can undergo side reactions such as hydro-
genation and hydrogenolysis, which add a degree of complex-
ity. The general oxidation scheme for CA oxidation is shown in
Fig. 6. Because many studies investigating the oxidation of
both BA and CA, the reaction conditions here are similar to
those in the previous section. Commonly used catalysts are Au,
Pd, and Ru, and the solvents are generally xylene, toluene, and
water. The TOF values for cinnamyl alcohol oxidation at temp-
eratures less than 373 K range from 0.17 s
1
to 4.4 s
1
, which
is of the same order of magnitude as those for benzyl alcohol
oxidation. The highest rate was found over Au bulk foil with
added homogeneous base. It should be noted that the rate for
Pd/hydroxyapatite is not reported on the table and would likely
be much higher than that of Pd/SiO
2
; however, insucient
information was provided to calculate an initial rate for CA oxi-
dation over Pd/HAP (Table 9).
11
There are multiple reports of aldehyde production in the
presence of basic aqueous solutions over Au and Pd cata-
lysts.
11,37,38
In one instance, Au supported on block co-poly-
mers in a 50% H
2
O50% chloroform solution with
1 : 1 KOH: CA produced 99% conversion of CA with 95% selec-
tivity to aldehyde in 6 h at 273 K.
37
Similarly, the Pd/HAP
system was eective for 90% conversion of CA with 98% selec-
tivity to aldehyde in aqueous NaOAc in 24 h at 383 K.
11
Unsup-
ported bulk Au with 1 : 1 K
2
CO
3
: CA produced similar results,
70% conversion of CA with 100% selectivity to aldehyde,
though the solvent was heptane and therefore the high alde-
hyde selectivity is not surprising. Likewise, Au/CeO
2
could
convert CA with 73% selectivity to aldehyde (66% conversion)
in the absence of solvent and base; using water and Na
2
CO
3
as
the solvent system resulted in >99% conversion and 98% selec-
tivity to the expected carboxylic acid.
32
The choice of solvent
appears to be critical in the bulk Au case, as CA oxidation did
not proceed in trifluorotoluene, toluene, or acetophenone. It
should be noted that BA oxidation did proceed in heptane and
toluene under the same conditions.
38
An influence of solvent was also observed over Pd, Pt, Au
Pt, and AuPd catalysts supported on C. For example, the CA
oxidation rates over all of these catalysts were higher in water
rather than in toluene without added base. The Au mono-
metallic catalyst was inactive in both solvents. Bimetallic
0.73 wt% Au0.27 wt% Pd/C produced the highest conversion
and selectivity to aldehyde in both toluene (conversion 72%,
selectivity to aldehyde 85%) and water (conversion 95%, selectiv-
ity to aldehyde 83%) at 333 K, whereas Pd and Pt monometallic
Fig. 6 Reaction scheme for cinnamyl alcohol oxidation.
Table 9 Turnover frequencies and reaction conditions for cinnamyl alcohol oxidation
a
1
) Reference
Pd/SiO
2
4.7 363 101.3 Toluene 0.20 11
2
CO
3
4.4 38
0.73% Au0.27% Pd/C 3.4 333 155 Toluene 0.17 30
0.73% Au0.27% Pd/C 3.4 333 155 H
2
O 0.22 30
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catalysts both exhibited poor conversion (36% and 27%,
respectively) but relatively high selectivity to aldehyde (86%
and 100%, respectively) in H
2
O at 333 K.
A Pd/HAP catalyst was likewise eective in toluene solvent
in the absence of added base (91% conversion, 87% selectivity
to the aldehyde) at a slightly lower temperature (363 K).
11
The
Pd/C catalyst was nearly as eective (90% conversion, 68%
selectivity). Other supported Pd catalysts, under the same con-
ditions, were less eective; Pd/Al
2
O
3
converted 83% CA with
only 66% selectivity to aldehyde and Pd/SiO
2
produced only
31% conversion with 30% selectivity to the aldehyde.
Similar to what was observed during BA oxidation, a physi-
cal mixture of Ag/SiO
2
and CeO
2
had high activity for CA oxi-
dation (98% conversion in 2 h for BA vs. 83% conversion in 3 h
for CA).
46
Likewise, a magnetically-separable Ru(OH)
x
/Fe
3
O
4
catalyst active for BA oxidation was also active for CA oxidation
in toluene without addition of base (95% conversion, >99%
selectivity to aldehyde in 1.5 h at 378 K).
14
Ruthenium sup-
ported on carbon was also found to be active for CA oxidation
in toluene, with a 79% yield of the aldehyde after 24 h at
343 K.
17
The investigation of cinnamyl alcohol oxidation highlights
the importance of solvent choice in alcohol oxidation with
regards to product selectivity and catalyst activity. As with BA
oxidation, the product selectivity is greatly influenced by the
solvent as well as the nature of the catalyst support. As in other
alcohol oxidations, the Au catalyst features the highest oxi-
dation rate at modest temperature, <373 K (on the same order
of magnitude as BA oxidation, ca. 4 s
1
), though the solvent
and pH of solution must be carefully monitored.
3.5 5-Hydroxymethylfurfural oxidation
Oxidation of 5-hydroxymethylfurfural is an interesting and
complicated reaction because the substrate HMF is not stable
in water at high pH,
4952
subject to conversion via the
Cannizzaro reaction and other degradation pathways.
However, under most conditions, a high pH is necessary for its
oxidation. There has been a push to find a base-free oxidation
route, for both economic and environmental benefits, despite
the extremely low solubility of the common target product,
2,5-furandicarboxylic acid (FDCA), in neutral water.
53
The
base-free oxidation of HMF utilizing Au on hydrotalcite (HT)
as a solid base support was reported recently;
54
however, other
work demonstrated the likely leaching of this solid base
material into solution as a stoichiometric replacement for
homogenous base.
25
This is a good demonstration of the
complexity and technical barriers to base-free HMF oxidation
at present.
As described in Section 2.1.5, the oxidation of HMF into
FDCA encompasses two steps: aldehyde oxidation and alcohol
oxidation. It is generally believed that the alcohol oxidation is
the slow step in this oxidation.
51,52,55
The main intermediates
in HMF oxidation are seen in Fig. 7. The di-aldehyde inter-
mediate, 2,5-diformylfuran, is rarely seen in solution at high
pH, probably because of the high reactivity of the aldehyde in
aqueous media. The most commonly seen intermediate is the
acidalcohol product, 5-hydroxymethyl-2-furancarboxylic acid
(HFCA), which results from oxidation of the aldehyde moiety
to acid.
3.5.1 HMF oxidation in methanol. Although water is a
common solvent used during HMF oxidation, some studies
investigated the reaction in methanol, which often forms the
ester products of the corresponding acids shown in Fig. 7.
56
A
major advantage of converting HMF in methanol compared to
water is the solubility of the final product. The solubility of the
diacid product, FDCA, is low in water at neutral pH,
53,57
whereas the ester of the diacid is readily soluble in many
common solvents. An early study of HMF oxidation in
methanol was reported by Taarning et al. using Au/TiO
2
as the
catalyst.
56
The oxidation reaction was optimized at 403 K and
400 kPa of O
2
in the presence of 8% sodium methoxide as a
base to enhance the reaction rate. These optimized conditions
produced a 98% yield of diester in 3 h, with the main inter-
mediate being 5-hydroxymethylmethylfuroate (HMMF). Lower-
ing the temperature to 295 K resulted in approximately 95%
yield of HMMF after 3 h, since the oxidation reaction appa-
rently stopped after formation of the intermediate. A rate of
HMF oxidation can be calculated at 10% conversion based on
their work, and it is given in Table 10.
Casanova et al.
58
explored the reaction over Au/CeO
2
at a
similar temperature (403 K) but at higher pressure (1000 kPa)
and without addition of base, in an attempt to improve the
recyclability of catalysts for this reaction. The primary inter-
mediate in that case was the ester of HFCA, and the final
product diester was formed in 99% yield after 5 h. They pro-
posed that the rate limiting step in the sequence is the oxi-
dation of the alcohol side chain to an aldehyde, which is
analogous to the presumed rate limiting step during HMF oxi-
dation in aqueous solution.
The eect of support on reaction rate and product selecti-
vity was also investigated. The TOFs were calculated from
initial rates (at 0.25 h) of both HMF disappearance and of
Fig. 7 Commonly observed intermediates in HMF oxidation.
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diester formation. However, the TOFs were based on total
metal rather than on surface metal, so the values have been
recalculated and presented in Table 10. It should be noted that
production of diester is the result of subsequent oxidation
steps that are presumably slower than the initial oxidation of
HMF. According to Table 10, Au/C had the highest rate of HMF
oxidation but, relative to the other catalysts in the study,
demonstrated low final yield of the diester product. On the
other hand, Au/CeO
2
had the highest activity of the group for
the formation of diester product (99% yield in 5 h). An experi-
ment with Au/CeO
2
in the absence of O
2
yielded large amounts
of the acetal product and 3.8% of the monoester product,
which suggests that CeO
2
acts as an oxygen donor. When non-
nanometric ceria was used as support, the activity of the cata-
lyst was significantly reduced, in agreement with results from
CeO
2
-based catalysts for benzyl alcohol oxidation.
32
The eect of temperature was also investigated in the range
353 K403 K over the Au/CeO
2
and yielded an overall activation
energy of 34 kJ mol
1
. Although other alcohols, such as
ethanol and butanol, were also tested for the oxidation-esterifi-
cation, methanol was the most suitable.
58
The eect of water
was probed, and a negative eect on the initial reaction rate
was noted. In fact, when 20% water was loaded, the reaction
did not even reach completion. Interestingly, no trace of car-
boxylic acid was noted, possibly because of the presence of a
Lewis acid site on the catalyst support aiding in the rapid reac-
tion of any formed carboxylic acid to methyl ester.
3.5.2 HMF oxidation in aqueous solutions. In aqueous
solutions, HMF oxidation has been thoroughly investigated over
Pt, Pd, and Au catalysts and some recent work has also looked
at AuCu bimetallics and Ru(OH) catalysts.
26,4952,5457,5961
The eects of added base concentration, temperature, dioxy-
gen pressure, and catalyst composition have been studied. In
general, the oxidation of HMF at moderate temperatures
(295368 K) over Au and Pt catalysts requires the addition of a
homogeneous base, though a consensus has not been reached
in the literature about the amount of homogenous base that
should be employed. The degradation of HMF in presence of
base is of concern, and most researchers seek to find a
balance between high enough concentration of base to allow
the oxidation to proceed at a reasonable rate but low enough
to limit degradation. The work of Davis et al. showed that the
intermediate HFCA is much more stable in NaOH than is
HMF, so rapid oxidation of HMF to HFCA, through the use of
a high catalyst loading, can allow for higher concentrations
of NaOH to be employed to facilitate the subsequent oxidation
of HFCA to FDCA.
49
The work of Davis et al. also showed that the activity of Au
catalysts for HMF oxidation was an order of magnitude higher
than either Pt or Pd catalysts. The selectivity to the desired
diacid, however, was much higher over the Pt and Pd catalysts.
At their standard conditions of 295 K and 690 kPa O
2
and
2 equivalents NaOH, the major product over Pt and Pd catalysts
was FDCA (selectivity of 79% and 71%, respectively) while the
major product over the Au catalysts was HFCA (selectivity of
92% over Au/TiO
2
catalyst). Gorbanev et al., however, demon-
strated high selectivity to FDCA over Au catalysts in water by
increasing the amount of catalyst and NaOH (20 equivalents).
52
Over a Au/TiO
2
catalyst, Gorbanev et al. investigated the
eect of NaOH concentration and demonstrated that at 303 K
and 2000 kPa O
2
, the selectivity to diacid did not change in the
range 520 equivalents NaOH.
52
Below 5 equivalents, the selec-
tivity shifted more toward the mono-acid HFCA. In the
absence of base at the same conditions, only 13% conversion
of HMF was seen, with the majority product HFCA (yield 12%)
and little FDCA (selectivity 1%).
Casanova et al.
58
and Pasini et al.
50
also varied the amount
of NaOH to determine the eect of base on product selectivity.
Casanova et al. found that using 4 equivalents of NaOH in the
presence of Au/CeO
2
produced a 96% yield of diacid in 5 h,
while 2 equivalents aorded 96% yield in 20 h.
51
Using just
1 equivalent of NaOH resulted in only 20% yield in 14 h (76%
yield of HFCA) and the oxidation did not proceed further.
Pasini et al. found that, in the presence of AuCu/TiO
2
or
Au/TiO
2
, the product selectivity was influenced by amount of
NaOH in the range of 14 equivalents.
50
Increasing the NaOH
concentration in the range 410 equivalents did not change
product selectivity. The work also showed that using 20 equi-
valents of NaOH in the absence of catalyst resulted in com-
plete degradation of HMF after 2.5 h.
Table 10 Turnover frequencies and reaction conditions for 5-hydroxymethylfurfural oxidation
a
1
) Reference
Au/TiO
2
2.6
b
295 100 Methanol + 8% Sodium Methoxide 0.14 56
Au/CeO
2
3.5 403 1000 Methanol 0.31 58
Au/Fe
2
O
3
3.5 403 1000 Methanol 0.12 58
Au/TiO
2
3.5 403 1000 Methanol 0.30 58
Au/C 3.5 403 1000 Methanol 0.47 58
AuCu/TiO
2
4.4 368 1000 Water + 4 : 1 NaOH: HMF 0.18 50
Au/TiO
2
2.6 295 690 Water + 2 : 1 NaOH: HMF 1.6 49
Au/C 10.5 295 690 Water + 2 : 1 NaOH: HMF 5.0 49
Au/C 3.0 295 690 Water + 2 : 1 NaOH: HMF 2.3 49
Pt/C 2.5 295 690 Water + 2 : 1 NaOH: HMF 0.08 49
Pd/C 3.3 295 690 Water + 2 : 1 NaOH: HMF 0.15 49
Au/TiO
2
2.6 295 2000 Water + 2 : 1 NaOH: HMF 1.2 49
Au/TiO
2
2.6 295 3000 Water + 2 : 1 NaOH: HMF 1.4 49
a
b
Not given; estimated from data from World Gold Council standard catalyst.
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The role of O
2
pressure in HMF oxidation over Au/TiO
2
cata-
lysts was investigated by Gorbanev et al.
52
and Davis et al.
49
Over the range 690 kPa to 3000 kPa, no appreciable dierence
in the rate of HMF oxidation was noted. In contrast, Vinke
et al., reported that reaction rate over Pt/Al
2
O
3
was first order
with respect to O
2
pressure; however, this assertion is made
without showing any data.
61
The eect of O
2
pressure on product selectivity was investi-
gated by Pasini et al.,
50
Davis et al.
49
and Gorbanev et al.
52
over
Au catalysts. A positive correlation between O
2
pressure and
selectivity to diacid was noted. A control experiment conducted
by Gorbanev et al. in the absence of O
2
but in the presence of
catalyst and 20 equivalents of NaOH found full conversion of
HMF after 18 h, with 51% yield of HFCA and the balance com-
prised of decomposition products. This demonstrates the
necessity of dioxygen in this reaction to prevent undesirable
side reactions in the highly basic solution.
52
Lilga et al., used a flow reactor to investigate the acid/base
nature of the medium on HMF oxidation over Pt/Al
2
O
3
,
Pt/ZrO
2
, and Pt/SiO
2
catalysts.
57
Under basic conditions
(Na
2
CO
3
) at 373 K and 1035 kPa air, complete conversion of
HMF to FDCA was observed. However, however, the selectivity
shifted to FCA after 2 h of operating at 100% conversion of
HMF, which might be attributed to adsorption of products
onto the catalyst. Successive experiments in batch reactors
report the same phenomenon, yet the original activity could be
returned by washing the catalyst with hot water.
57
In neutral
conditions, the reaction was substantially slower but the down-
stream separations were easier.
57
Product inhibition was
apparently much higher than that in the basic conditions,
likely because of the low solubility of the reaction products in
neutral solution. It was noted that inorganic supports
adsorbed less of the products, which also correlated with the
surface area of the supports.
Acidic conditions were achieved through addition of acetic
acid.
57
While the solubility of FDCA is limited in neutral feeds,
the solubility in 40% acetic acid and 60% water is twice that in
100% water. At 373 K and with air as the oxidant, the dialde-
hyde (DFF) is the major product, though at higher tempera-
tures and with O
2
as the oxidant, 100% conversion and 85%
selectivity to FDCA was realized.
Verdeguer et al. investigated PtPb/C catalysts and found
that hydroxyl bases were more eective than carbonate bases
at promoting the reaction.
55
Vinke et al. found the rate of HMF
oxidation over Pt/Al
2
O
3
to be independent of pH between 811,
but at lower pH values, the rate was lower.
61
It is quite clear that the oxidation of HMF in basic aqueous
solution is facile over metal catalysts at room tempera-
ture.
26,49,50,56,57,61
Increasing the temperature, however, can
reduce the reaction time or change the product selectivity. For
example, Pasini et al. showed that at 333 K over AuCu/TiO
2
catalysts, the major product was the monoacid HFCA.
50
Raising the temperature by just 20 K shifted the selectivity
toward the diacid FDCA, and raising the temperature an
additional 15 K produced 99% yield of FDCA. This is consist-
ent with a rapid oxidation of HMF to HFCA and a slow
oxidation of HFCA to FDCA. Vinke et al. found the observed
activation energy to be 37.2 kJ mol
1
over Pt catalysts,
61
which
is similar to the value found over Au catalysts in MeOH solvent
(34 kJ mol
1
).
58
Casanova et al. varied the temperature between 298 and
403 K and found a positive eect on conversion over their
Au/TiO
2
catalysts, as expected. However, higher temperatures
caused the formation of some undesired byproducts (degra-
dation products).
51
Attempted reuse of the catalyst revealed
significant deactivation, which was attributed to the buildup
of 2.5 wt% C during the reaction. Extensive washing of the
spent catalyst did not improve activity. The researchers
claimed that the used catalyst was still able to oxidize the
alcohol group, but its ability to oxidize the aldehyde group was
diminished. This was confirmed by carrying out a reaction
with HFCA and a used catalyst; the reaction was completed in
4 h, yielding 93% FDCA. Since the catalyst can be used to
oxidize the aldehyde at 298 K without loss of activity, a new
reaction protocol was established wherein the first oxidation
step of HMF to HFCA was conducted at 298 K, and then the
temperature was raised to 403 K to allow for complete and
ecient oxidation to the diacid product while limiting catalyst
deactivation. With this method, the spent catalyst could be
successfully reused 3 times.
A possible promotional role of the support (Fe
2
O
3
, C, CeO
2
and TiO
2
) on Au nanoparticles was examined by Casanova
et al.
51
The Au/CeO
2
and Au/TiO
2
supported catalysts showed
the best activity (over Au/TiO
2
, 84% selectivity to diacid after
8 h; over Au/CeO
2
, 96% selectivity to diacid after 5 h), while
Au/Fe
2
O
3
and Au/C produced lower yields of FDCA. Highlight-
ing the important collaborative eect of CeO
2
and Au, the Au
on nanoparticulate CeO
2
reached high yields of FDCA in half
the time of the Au on non-nanoparticulate CeO
2
. The reductive
pretreatment of the catalyst was shown to increase the activity,
likely because it increases amount of Ce
3+
, which has been
shown previously to be important in catalyst activity.
32
Monometallic Au and Cu catalysts, as well as bimetallic Au
Cu/TiO
2
catalysts, were synthesized by Pasini et al.
50
Interest-
ingly, the reaction with Cu/TiO
2
produced no FDCA whereas
the bimetallic AuCu yielded twice the FDCA yield of the
monometallic Au catalysts, demonstrating a synergistic eect
of alloying the two metals. The optimum metal loading was
found to be 1.5 wt% and the preparation method played a role
in catalyst activity. Catalysts synthesized from preformed Au
Cu sols supported on TiO
2
were more active than those syn-
thesized by post-deposition of a Au sol onto a monometallic
Cu/TiO
2
catalyst. This may be indicative of the promotional
activity of Cu, or because Cu aids the dispersion of Au. The
bimetallic catalyst was able to be recycled 5 times without
losing activity, whereas the Au monometallic catalyst lost
activity after just 1 recycle, highlighting the beneficial eect of
alloying Cu with Au.
Pasini et al. also found an eect of pretreatment on catalyst
performance.
50
The calcined catalyst produced a higher yield
of HFCA and a lower yield of FDCA (92% and 8%, respectively)
than did the uncalcined catalyst (69% yield HFCA and 31%
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yield FDCA). In addition, the particle size of the calcined cata-
lyst was larger than the uncalcined (6 nm compared to 4.4 nm,
respectively). From this information, the group hypothesizes
that the HFCA oxidation may be more sensitive to size of metal
nanoparticles than is the HMF oxidation.
3.6 Glycerol oxidation
The oxidation of glycerol by heterogeneous catalysts has both
economic and academic appeal. Glycerol is a major byproduct
of biodiesel synthesis via transesterification of triglycerides
with alcohols. Glycerol oxidation to high value fine chemicals,
such as glyceric acid, tartronic acid, or dihydroxyacetone,
could help bio-diesel economics become more competitive
compared to diesel produced from non-renewable resources.
Academic interest in oxidative upgrading of glycerol stems
from glycerol being a model polyol with three hydroxyl groups,
two primary and one secondary. Fig. 8 shows a reaction
scheme of the major glycerol oxidation products. Glycerol oxi-
dation is a sequential reaction that can follow multiple paths.
The oxidation of a primary or secondary alcohol of glycerol
produces glyceraldehyde or dihydroxyacetone, respectively.
These two products are often in equilibrium in aqueous sol-
ution, depending on the pH. Glyceraldehyde can be sequen-
tially oxidized to an acid, glyceric acid, and both
glyceraldehyde and dihydroxyacetone can be oxidized to an
alpha-keto acid product, hydroxypyruvic acid. The sequential
oxidation of the primary alcohol of glyceric acid typically pro-
duces tartronic acid. Many authors have also reported that
glycerol oxidation products can undergo carbon cleavage to
form two carbon acids such as glycolic acid and oxalic acid,
24
which necessarily means that one carbon products can also be
formed.
62
The rate and selectivity of glycerol oxidation depends on
the choice of catalyst and the reaction conditions. As the selec-
tivity during glycerol oxidation strongly depends on the pH of
the solution, this discussion will focus on the influence of
reaction conditions of oxidation on supported Au, Pt, and
Pd catalyst performance.
3.6.1 Monometallic catalysts. Research on supported Au
catalysts for the oxidation of glycerol has increased signifi-
cantly over the past decade. Carretin et al. first published the
remarkable activity and selectivity of a 1% Au/C catalyst for the
oxidation of glycerol to glyceric acid in the presence of base.
63
After addition of NaOH to the reaction medium, the Au catalyst
reportedly had 100% selectivity to glyceric acid at 56% conver-
sion of glycerol, whereas without the addition of NaOH there
was no glycerol conversion over the Au catalyst. Basic con-
ditions favor the initial deprotonation of the alcohol group
either on the Au surface or in solution whereas this is unlikely
on the Au alone in neutral or acidic solution, which is consist-
ent with the mechanistic description of alcohol oxidation
described earlier.
23
Additional experiments by Carretin et al.
showed an increase in conversion with increasing concen-
trations of base and increasing dioxygen pressure. Since the
rate depended on O
2
pressure, it was not clear if the kinetics
were limited by mass transfer of the oxygen to the catalyst or
the rate of electron removal from the metal to the oxygen.
It is known that the rate of glycerol oxidation over sup-
ported Au catalysts is enhanced by the addition of base,
64
but
a true rate of oxidation is dicult to discern from the litera-
ture. While the reaction conditions aect the rate of reaction,
the initial TOF reported in the literature based on the available
Au surface metal can vary by almost three orders of magnitude
from 0.2 to 17 s
1
. The true rate of reaction, in the absence of
external and internal mass transfer limitations, is most likely
found at the higher bound of reported TOFs. Thus, selected
examples of glycerol oxidation with supported Au catalysts are
reported in Table 11.
The initial TOF for glycerol oxidation over well-dispersed
supported Au catalysts at 333 K, presumably in the absence of
mass transfer limitations, appears most frequently between
the values of 26 s
1
. Four dierent research labs have pro-
duced initial rates within this range and the supported Au cat-
alysts vary in synthesis procedure, support type, and Au weight
percent. In addition, a wide range of Au loadings in the reactor
were utilized, with glycerol to Au ratios ranging from 2000
65
to
over 50 000.
24
It is noteworthy that several of the authors of the
higher glycerol oxidation rates have addressed the external
mass transfer limitations of O
2
23,6569
and one addressed
internal mass transfer limitations as well.
67
The two highest rates for glycerol oxidation were 17 s
1
by a
0.5% Au/C catalyst with a glycerol to Au ratio of 50 000
24
and
6.1 s
1
by a 0.8% Au/C catalyst with a glycerol to Au ratio of
8000, both at 333 K.
23
Both authors calculated the maximum
O
2
transfer rate for their semi-batch reactor configuration and
purposely chose catalyst loadings in the reactor to ensure gly-
cerol oxidation rates fell below the maximum rate of dioxygen
transfer. The oxidation of sodium sulfite to sodium sulfate by
Fig. 8 Commonly observed glycerol oxidation products. Dotted lines represent
possible carbon cleavage of three carbon products to form two carbon
products.
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O
2
was used to calculate the maximum oxygen diusion rate
into the liquid phase at 298 K. In addition, the authors used
two dierent titania-supported catalysts and reported that for
a 1.47% Au/TiO
2
the TOF was 4.1 s
1 64
and over 1.8% Au/TiO
2
it was 4.9 s
1
.
23
Interestingly, the 0.8% Au/C catalyst investi-
gated had a particle size approximately three times larger than
both Au/TiO
2
catalysts at 10.5 nm, yet still had an initial TOF
of 6.1 s
1
.
An accurate initial rate can be determined regardless of
reaction conditions as long as they are not mass transfer
limited. Demirel et al. investigated a semi-batch process in
which the pH was controlled at 12 by the addition of NaOH
and the dioxygen pressure was only 100 kPa.
67
Instead of
increasing the dioxygen pressure, the loading of Au in the
reactor was limited to ensure there were no external mass
transfer limitations. An initial TOF of 5 s
1
was reported with a
1% Au/C catalyst. The external and internal mass transfer
limitations of glycerol oxidation were subsequently modeled
by Demirel et al. and shown to fall within the gasliquid and
liquidsolid criterion established by Chaudhari et al. for liquid
phase reactions of fine chemicals.
68,70
The kinetic modeling of
glycerol oxidation was fitted with the LangmuirHinshelwood
mechanism and suggested that only the adsorption of glycerol,
glyceric acid, and tartronic acid is relevant and that oxalic acid
is most likely the product of glycolic oxidation. In addition,
an initial rate was calculated for the 1% Au/C catalyst to
be 4.8 s
1
.
A good example of an initial rate that is limited by external
mass transfer of O
2
was presented by Rodrigues et al. for
glycerol oxidation over a 0.59% Au/C catalyst.
65
An increase in
the dioxygen pressure from 300 to 1000 kPa resulted in an
increase in the initial rate from 1.3 to 3.4 s
1
. In addition, they
noticed that modification of the carbon support to increase
the number of oxygenated acid groups six-fold severely
decreased the initial rate of reaction, while carbon supports
with a low content of oxygenated surface groups all had a simi-
larly higher initial rate.
Finally, Ketchie et al. illustrated that bulk Au powder can
catalyze glycerol oxidation at a rate of 2.5 s
1
in the presence
of base at 333 K.
66
Even very large 20 nm and 40 nm sized par-
ticles of Au on carbon supports had oxidation rates of 2.3 and
2.2 s
1
, respectively. All evidence in the literature shows that a
good guideline for the initial TOF of a well dispersed sup-
ported Au catalyst is on the order of magnitude of 1 s
1
at
333 K and O
2
pressure that does not introduce mass transfer
limitations.
Table 11 Turnover frequencies and reaction conditions for glycerol oxidation
Catalyst Size (nm) T (K) pO
2
(kPa) NaOH: Glycerol (mol : mol) TOF (s
1
) Reference
0.5% Au/C 7.3 333 1000 2 17 24
0.8% Au/C 10.5 333 1100 2 6.1 23
1% Au/C 4.3 333 100 pH = 12 5.0
a
67
1.8% Au/TiO
2
(WGC) 3.5 333 1100 2 4.9 23
1% Au/C 3.7 333 1000 2 4.8
a
68
1.47% Au/TiO
2
3.7 333 1000 2 4.1 64
0.75% Au/C 3.7 333 1000 2 3.9
a
69
0.59% Au/C 6.8 333 1000 2 3.4
a
65
0.6% Au/C 7.7 333 500 2 2.6
a
71
Au powder 333 1000 2 2.5 66
0.4% Au/MWCNT 5.5 333 300 2 1.7
a
72
1% Au/C 2.5 323 300 4 0.8
a
73
1% Au/TiO
2
3.8 363 100 4 0.7
a
74
1% Au/C 3.5 323 300 4 0.7
a
75
1.1% Au/C 13.3 333 500 2 0.5
a
71
1.5% Au/TiO
2
(WGC) 4 323 300 4 0.2
a
76
3% Pd/C 3 333 1100 2 2.2 23
3% Pt/C 2.3 333 1100 2 1.6 23
0.5% Pt/CS 5 343 1000 0.8 1.2
a
77
2.9% Pd/C 2.9 333 1000 2 1 24
1.28% Pd/C 5.6 323 300 4 0.4
a
78
1% Pt/TiO
2
2.5 363 100 4 0.3
a
74
0.5% Pt/C 3.8 333 300 2 0.3
a
79
1% Pt/C 2.5 323 300 4 0.3
a
80
0.65% Pd/C 2 333 300 2 0.09
a
65, 79
5% Pt/C 2.3 333 300 2 0.06
a
81
1% Pd/TiO
2
3 363 100 4 0.008
a
74
5% Pt/MWNTs 6.7 333 Flow 0 0.6
a
82
5% Pt/MWNTs 2.1 333 Flow 0 0.5
a
83
5% Pt/C 3.6 398 Flow pH = 4 0.2
a
84
5% Pt/C 3.2 333 Flow 0 0.2
a
85
3% Pt/C 3.2 333 Flow 0 0.1
a
83
3% Pt/C 2.3 333 1100 0 0.06 23
5% Pt/C 5 343 500 pH = 7 0.05 86
3% Pd/C 3 333 1100 0 0.004 23
a
TOF calculated or re-calculated based on available surface metal.
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If the initial rate of supported Au catalysts is on the order of
magnitude of 1 s
1
, the question of why there are many
examples of authors reporting lower initial rates is raised. We
suspect that, in the case of supported Au catalysts, low rates
can be explained by diusion limitations of O
2
and rapid deac-
tivation of the catalyst.
Demirel-Gulen et al. determined that the initial rate of reac-
tion over a 0.75 wt% Au/C catalyst increased from 2 to 6 s
1
as
the ratio of NaOH to glycerol increased from 1 to 4.
69
No con-
version was realized in the absence of NaOH. Thus, the initial
rate was still the same order of magnitude as long as there was
a high level of base. The eect of temperature on the initial
rate of reaction is summarized in Table 12. The temperature
was found to influence the initial rate of reaction by an order
of magnitude over the range 298373 K. The rate followed a
typical Arrhenius relationship with temperature with an appa-
rent activation energy of 50 5 kJ mol
1
. At 298 K the initial
TOF for glycerol oxidation was calculated to be about 0.5 s
1
,
but even at a temperature of 313 K the initial TOF was already
1.5 s
1
, which is comparable to other initial rates reported.
The selectivity of the glycerol oxidation reaction over sup-
ported Au catalysts in the presence of base is primarily to gly-
ceric acid and tartronic acid. Cleavage of the three carbon
acids can result in two carbon acids, glycolic acid and oxalic
acid. The two carbon products are typically produced by clea-
vage of three carbon glycerol oxidation products, presumably
with hydrogen peroxide formed as a byproduct.
24
Oxidation of
tartronic acid can also produce mesoxalic acid. Selectivity is
dicult to compare between papers because it depends not
only on level of conversion but also whether the reaction is
mass transfer limited.
Gil et al. determined that the selectivity can change signifi-
cantly when the reaction is not run in the kinetic regime as
seen in Table 13.
71
The TOF of 2.6 s
1
at a glycerol : Au ratio of
3500 was not mass transfer limited and had a selectivity to gly-
ceric acid of 20.2% with a 1.1% Au/C catalyst with 13.3 nm Au
particles at 30% conversion. However, a clearly mass transfer
limited TOF of 0.5 s
1
at a glycerol : Au ratio of 1000 has a
selectivity to glyceric acid of 8.5%. In addition, one can see a
higher selectivity to the diacid, tartronic acid, at higher catalyst
loadings. Thus, selectivity comparisons require not only equiv-
alent levels of conversion, but also results free from transport
limitations.
In most cases, the selectivity of supported Au catalysts in
the presence of base is typically toward monoacids, with a min-
ority of diacid products. Although 100% selectivity to mono-
acids has been reported,
63
the diacid product is the
subsequent oxidation of the monoacid. Thus, the conversion
and the amount of Au loaded in the reactor can play a major
role in determining the concentration of diacid. Still, the
highest reported selectivity to tartronic acid is only 44% over a
1% Au/TiO
2
catalyst after 4 h at 393 K.
87
Gold catalysts have
diculty producing the diacid in high yield because of inhi-
bition by strongly adsorbed ketone intermediates and conden-
sation products in addition to cleavage and over-oxidation
reactions, as noted earlier.
88
Significant amounts of one
carbon products, such as carbon dioxide (in the solution as
carbonate) and formic acid can also be observed depending on
the temperature of the reaction.
89
Even selectivity to dihydroxy-
acetone in basic solutions was reported over MWCNT-sup-
ported Au catalysts at very low conversions of glycerol.
65
The initial rate of glycerol oxidation over supported Pt and
Pd catalysts has also been investigated, although less
thoroughly than supported Au catalysts. Table 11 provides the
initial TOF of a few examples of Pt and Pd catalyzed glycerol
oxidation reactions. Glycerol oxidation over Pt and Pd is slower
than over Au, even in the presence of base. However, as dis-
cussed earlier, the glycerol oxidation mechanism is likely to be
similar over the dierent metals. Carrettin et al. investigated
the role of the type of basic promoter on glycerol oxidation
with a 5% Pt/C catalyst.
81
Sodium hydroxide (NaOH) was deter-
mined to promote the highest conversion when compared to
other alkali metal hydroxides. One major advantage of using
supported Pt and Pd catalysts is that oxidation is possible even
without base. Also, the selectivity during glycerol oxidation can
be significantly dierent at acidic and basic conditions.
However, a major disadvantage of Pt and Pd catalysts is that
they can deactivate quickly under certain reaction conditions.
Table 12 Inuence of temperature on glycerol oxidation turnover frequencies
a
T (K) TOF (s
1
)
298 0.5
313 1.5
333 3.9
353 6.7
373 11.5
a
Reaction conditions: 1.5 M glycerol, NaOH: glycerol = 2 (mol : mol),
glycerol : Au = 3500 (mol : mol), 1000 kPa O
2
. Catalyst 1 wt% Au/C. TOF
calculated by author. Ref. 69.
Table 13 Turnover frequencies and product selectivities for glycerol oxidation over Au/C
a
Selectivity
Glycerol : Au (mol : mol) TOF
b
(s
1
) Glyceric acid Glycolic acid Tartronic acid Oxalic acid Mesoxalic acid Hydroxypyruvic acid
3500 2.6 20.2 39.4 9.1 8.6 17.8 4.9
2000 0.95 18.6 40.6 15.1 5.0 13.3 7.4
1000 0.5 8.5 46.9 19.9 4.8 12.7 7.1
a
Reaction conditions: 0.3 M glycerol, NaOH: Glycerol = 2 (mol : mol), 500 kPa O
2
, 333 K. Catalyst: 1.1 wt% Au/C (particle size 13.3 nm).
Selectivities reported at 30% conversion. Ref. 71.
b
TOF re-calculated based on available surface metal.
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The noble nature of Au prevents substrates, including oxygen,
from adsorbing strongly to the surface. Deactivation of the Pt
and Pd catalysts can be caused by over-oxidation of the metal
to form oxides on the surface and by poisoning of the surface
with acid products, byproducts, or cleavage products.
90
The initial rate of reaction for supported Pt catalyst in the
presence of base was observed both by Zope et al.
23
at 333 K
and Huang et al.
77
at 343 K to be on the order of 1 s
1
.
Huang et al. noted that the TOF was sensitive to the dioxygen
pressure, decreasing to about 0.4 s
1
at a pressure of 300 kPa.
Zope et al. and Ketchie et al. reported TOFs for Pd/C catalysts
of 1 s
1
and 2.2 s
1
, respectively, in the presence of base at
333 K. Interestingly, while Pt and Pd exhibit a slower oxidation
rate of glycerol than Au in the presence of base, the order of
magnitude is similar. The inhibition of the Pt and Pd catalysts
by more strongly adsorbed reactants and products compared
to the more inert Au, might explain the slightly lower rate.
The majority of examples cited in Table 11, however, have
initial rates significantly below 1 s
1
. A TOF of 0.3 s
1
was cal-
culated over a 1% Pt/TiO
2
catalyst, a 0.5% Pt/C catalyst, and a
1% Pt/C catalyst.
65,74,80
Dimitratos et al. reported an initial rate
of 0.4 s
1
over a 1.28% Pd/C catalyst
78
and Rodrigues et al.
found an initial rate of approximately 0.09 s
1
with a 0.65%
Pd/C catalyst.
65
It is possible that rapid deactivation could play
a role in the low initial rate, but a second reason might be
mass transfer limitations of O
2
at low pressure and high cata-
lyst loading used in the study. For example, Shen et al. was
able to form lactic acid ( presumably a solution-mediated reac-
tion) by limiting the amount of available dioxygen at increased
temperature, but also had a low TOF of 0.008 s
1
over a 1%
Pd/TiO
2
catalyst.
74
In the absence of base, the TOF for glycerol oxidation is
about 0.5 s
1
as observed by Liang et al. over 5% Pt/MWNT.
83
Again, this value could be influenced by rapid deactivation. It
has been suggested that over-oxidation can form metal oxides
on the surface that are not active for oxidation and that bypro-
ducts, intermediates, or acids can strongly adsorb on the
metal surface. Gao et al. observed quick deactivation with the
rate of reaction dropping in half from 0.6 s
1
at 20 min to
approximately 0.3 s
1
at 60 min in the absence of base over 5%
Pt/MWNT.
82
The TOF of 0.06 s
1
reported by Zope at 5 h over
1% Pt/C, even at the low conversion of 5%, is probably
measured after too long to accurately gauge the initial rate of
reaction without interference from deactivation.
23
Villa et al. tested both 1% Pt/C and 1% Pt/H-mordenite, but
did not report the reaction profile or an estimation of particle
size, thus no TOF could be calculated.
62
Villa did note that the
Pt/H-mordenite catalyst had a lower selectivity to one-carbon
products. However, the conversion was significantly higher for
the Pt/C catalyst, 78% compared to 20% for the Pt/H-morde-
nite; thus the dierence in selectivity could just be a result of
over-oxidation of the glyceric and tartronic acid at higher
conversions.
Villa et al. reported very low activity for a 1% Pd/C catalyst
in base-free glycerol oxidation at 373 K with a conversion
similar to Au at about 5%.
62
It is unknown what the blank con-
version is at 373 K, but it is noted that no conversion with Au
and Pd was seen at 323 K. This is consistent with the low TOF
reported by Zope et al. of 0.004 s
1
for 3% Pd/C in the absence
of base.
23
Either Pd deactivates very quickly without base or it
is relatively inactive for glycerol oxidation in water.
Bianchi et al. reports a TOF based on the total metal
loading of 0.32 s
1
at 323 K, 304 kPa O
2
, NaOH: glycerol = 4,
and glycerol : Pd = 500, but does not report an estimation of
the particle size for Pd.
73
Similarly, Dimitratos et al. calculated
a TOF based on total metal loading of 0.09 s
1
, but does not
report an estimation of particle size.
78
However, these con-
ditions are identical to those reported by Bianchi et al.
Without knowing the dispersion of the catalyst it is dicult to
assess the catalysts and determine whether the dierence in
TOF is due to particle size variations or external mass transfer
limitations.
3.6.2 Bimetallic catalysts. A major topic of current
research on glycerol oxidation is the performance of bimetallic
catalysts. Since the rate over a supported Au catalyst is gen-
erally between 26 s
1
at 333 K (without mass transfer limit-
ations of dioxygen) and the rate over supported Pt and Pd
catalysts about 1 s
1
, one can now compare the rates of bi-
metallic catalysts against the monometallic analogues.
Table 14 shows some selected examples of alloyed catalysts.
Ketchie et al. reported that a bimetallic AuPd/C catalyst
had a TOF of 7 s
1
which is fairly typical of Au catalysts, but
with increased selectivity to glyceric acid.
24
Palladium appar-
ently accelerated the decomposition of H
2
O
2
, which prevented
cleavage of glyceric acid and tartronic acid to two and one
carbon products. Other bimetallic AuPd catalysts synthesized
with slightly less and more Au were of about the same rate
while maintaining the same selectivity at 50% conversion.
Table 14 Turnover frequencies and reaction conditions for glycerol oxidation over selected bimetallic catalysts
2
(kPa) NaOH: glycerol (mol : mol) TOF (s
1
) Reference
2.8% Pd2.2Au%/C 4.4 333 1000 2 7 24
0.6% Au0.35% Pd/C 2.6 323 300 4 1.3
a
73
1% (1 : 1 AuPd)/C 3.7 323 300 4 1.9
a
78, 80, 91
1% (1 : 1 AuPt)/C 2.5 323 300 4 0.6
a
80
0.96% Au1.71% Pd/C 6.1 323 300 4 1.6 78
1% (6Au : 4Pt)/H-Mordenite 4 373 300 0 0.2 62
1% AuPd(1 : 3)/MgO 4.1 333 300 0 0.04 92
1% AuPt(1 : 3)/MgO 4 333 300 0 0.12 92
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Bianchi et al. saw similar results with AuPd/C catalysts,
reporting that glyceric acid was not over-oxidized to tartronic
acid. However, the opposite trend was noticed for rate as the
AuPd alloy had a faster reaction rate with a TOF of 1.3 s
1
than just the monometallic Au which had a TOF of 0.8 s
1
.
The low initial rate of the monometallic Au catalyst, however,
hints at possible artifacts in the results. In addition, a AuPt/C
catalyst was synthesized that did see oxidation to tartronic
acid and glycolic acid. Since the particle size was not
reported, however, a direct comparison of TOF is not is
possible.
73
A bimetallic AuPd catalyst was also synthesized by Dimitra-
tos et al. and showed no significant eect on activity of glycerol
oxidation compared to a monometallic catalyst (TOF =
1.6 s
1
).
78
As the particle size of the bimetallic catalyst
increased the TOF decreased and the selectivity to glyceric acid
increased. Most likely the activity and selectivity were linked
since less over-oxidation products were produced (glycolic and
tartronic acid) on the larger particles. In a separate paper, a
rate increase of a factor of five is reported for a 1% (AuPd)/C
compared to a 1% Au/C catalyst, but an estimation of the par-
ticle size was not reported.
91
Prati et al. reported that a 1% Au/C catalyst had a TOF of
approximately 0.7 s
1
, based on the available surface metal.
75
A bimetallic catalyst synthesized by deposition of Ru on the
Au/C catalyst (Ru@(Au/C)) using the sol method showed
enhanced conversion of glycerol of 99% compared to 73% over
the monometallic Au/C catalyst after 1 h, but it is dicult to
perform a quantitative rate comparison of such high levels of
conversion. The authors noted a progressive segregation of the
metals on the catalyst surface, which would make an initial
rate of greater importance.
Villa et al. reported a TOF of 0.28 s
1
over a 1% Pd/C catalyst
and of 0.22 s
1
over a 1% Au/C catalyst at 323 K and 300 kPa
O
2
with NaOH: glycerol of 4.
93
The monometallic Pd and Au
catalysts were compared to bimetallic PdAu catalysts of
dierent molar ratios it was determined that the highest TOF
(1.2 s
1
) was found at a bimetallic ratio of 90%Au10%Pd/C,
but an estimation of particle size was not reported. This is a
significant increase in the rate of reaction for the bimetallic
catalyst even though the amount of available surface metal for
the reaction is uncertain. However, if a particle size between
two to four nanometers is assumed, the TOF value would
appear to be similar to that seen for monometallic Au catalysts
in other work.
A PdAu/C catalyst was explored in the absence of base for
glycerol oxidation by Prati et al.
89
A higher conversion of
11.9% for the 1% 1 : 1 PdAu/C catalyst, compared to 3% con-
version for the monometallic 5% Pd/C catalyst, was reported
after 1 h at 353 K and 300 kPa O
2
. If a TOF is calculated a the
total metal basis after 1 h, the 1% Pd/C catalyst has a TOF of
0.004 s
1
and the bimetallic AuPd/C catalyst has a rate of
0.017 s
1
. The authors speculated that the alloy prevented irre-
versible adsorption of byproducts and thus the deactivation of
the Pd, which is the active metal in the absence of base. The
same bimetallic phenomena was not observed for a 1% (1 : 1)
PtAu/C that had a TOF of 0.08 s
1
, while the 5% Pt/C catalyst
had a TOF of 0.07 s
1
calculated on a total metal basis.
In the absence of base at the relatively higher temperature
of 373 K, Villa et al. observed only 5% conversion of glycerol
and 70% selectivity to glyceric acid over a 1% Au/H-mordenite
catalyst.
62
While it is interesting that the supported Au catalyst
had any activity at all without base, a 1% (Au : Pt 6 : 4)/H-mor-
denite catalyst had a 70% conversion and 83% selectivity to
glyceric acid. Although comparing the selectivities is not
appropriate because of the dierent levels of conversion, the
significant increase in activity at the same reaction conditions
is noteworthy. A TOF calculated at the 70% conversion, which
is admittedly high for an initial rate, is approximately 0.2 s
1
without base for the bimetallic catalyst. A monometallic Pt/H-
mordenite catalyst only had 20% conversion and 79% selectiv-
ity to glyceric acid.
Brett et al. also investigated the eect of bimetallic AuPt
and AuPd on an MgO support at 333 K and 300 kPa O
2
in the
absence of added base.
92
No monometallic catalysts were
tested. While the particle size was similar between the two
catalysts, the PtAu bimetallic was significantly more active
with a TOF of 0.12 s
1
. This is similar to the initial activity
Villa et al. observed for the bimetallic alloy on the H-mordenite
support. The low rate of reaction is consistent with the idea
that Mg was not likely acting as a sacrificial base, which was
confirmed by elemental analysis.
An interesting application of bimetallic catalysts was
reported by Hirasawa et al., who alloyed Pd and Ag on carbon
by co-impregnation.
94
An increase in conversion from 2.8% for
the monometallic 1% Pd/C to 6.7% for the 1% 1 : 1 PdAg/C
catalyst was reported at 353 K and 300 kPa O
2
in the absence
of base. In addition, the amount of CO chemisorbed did not
vary significantly (<20%) for the monometallic and bimetallic
catalysts which led the authors to suggest that the two catalysts
have similar metal particle sizes. The researchers speculate
that the increase in conversion is due to Ag preventing deacti-
vation of the active Pd catalyst. A physical mixture of Pd/C and
Ag/C did not aect the overall conversion. In addition, the
selectivity to dihydroxyacetone increased from 66.1% to 74.6%,
although these selectivities were reported at dierent conver-
sion levels. Liang et al. also attempted to alloy Cu into Pt to
prevent deactivation of the Pt during glycerol oxidation at
333 K and 300 kPa O
2
in the absence of base. Although the
catalyst demonstrated a small increase in rate (<15%), it
delayed deactivation significantly.
Diacid production is dicult to achieve over monometallic
Pt/C catalysts, with the highest selectivity to tartronic acid
being reported by Carrettin et al. at 23%.
63
The production of
diacid can be improved by using a promoter, such as Bi. For
example, a PtBi/C catalyst was able to achieve an 80% selectiv-
ity to tartronic acid from glyceric acid (not glycerol) oxidation
at a pH = 1011 at 323 K under 0.75 cm
3
min
1
of flowing
air.
95
At a lower pH (34), a high selectivity to hydroxypyruvic
acid was reported confirming the major role that pH plays in
glycerol oxidation over Pt catalysts. Kimura utilized a 5% Pt
1% Bi/C catalyst to lessen the influence deactivation during
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glycerol oxidation in acidic solutions.
96
He was able to achieve
almost 80% selectivity to dihydroxyacetone (DHA) at 323 K and
a pH between 2 and 3.
Bradner et al. and Hu et al. both observed that a monome-
tallic Pt catalyst had an initial TOF of about 0.25 s
1
and a low
selectivity to dihydroxyacetone, whereas the addition of Bi
increased the TOF of the catalyst significantly and increased
the selectivity to dihydroxyacetone (see Table 15). Loss of DHA
selectivity after consecutive reactions led Bradner et al. to
speculate that Bi leached from the catalyst during the reaction.
Garcia et al. showed a significant increase in selectivity to dihy-
droxyacetone with a PtBi/C catalyst at 333 K in flowing air in
which they claimed Bi sterically-hindered strong adsorption of
acid products and increased selectivity to dihydroxyacetone by
sterically hindering Pt nanoparticles thus preventing further
oxidation.
97
3.7 Glucose and other sugars
The catalytic oxidation of glucose and other sugars or sugar
alcohols has been thoroughly investigated over the past several
decades because of their low cost and simple production from
biomass. Both monosaccharides and disaccharides can be oxi-
dized to sugar acids, which are useful chemicals for the food
and cosmetics industries. Sugars are also interesting because
of their unique long-chain polyol structure and the equili-
brium between their cyclic tautomers in aqueous solution.
Sugars are primarily in the closed ring form in neutral water,
but both basic and acidic conditions catalyze ring opening.
Similar to glycerol, the rate of sugar oxidation depends primar-
ily on the pH and catalytic metal, whereas the product distri-
bution depends mostly on the solution pH and temperature.
As discussed earlier, Pt and Pd catalysts suer deactivation in
both acidic and basic environments whereas Au is more resist-
ant to deactivation, presumably because of its noble nature. In
this section, the oxidation of several dierent sugars over sup-
ported metal catalysts will be discussed, with a focus on
glucose oxidation.
3.7.1 Gold catalysts. Biella et al. reported that a 0.89%
Au/C catalyst oxidized glucose in aqueous solution in flowing
O
2
at 20 cm
3
min
1
, with or without added base, with 100%
selectivity to gluconic acid.
98
The initial TOF of glucose oxi-
dation at the controlled pH of 9.5 was 3.6 s
1
at 323 K, but was
substantially lower (0.6 s
1
) without added base even though
the temperature was 50 K higher (373 K). Thus, it appears that
Au can catalyze the oxidation of glucose without base at
modest temperatures, in contrast to the case of glycerol
oxidation. A high selectivity to gluconic acid is achieved by
avoiding excessive pH and temperature, which typically accel-
erates glucose isomerization to fructose as depicted in Fig. 9.
Glucose isomerization to fructose is not catalyzed by the metal
but by the solution medium. Thus, the conversion of glucose
to fructose is not accounted for in the determination of oxi-
dation rates reported here. Onal et al. studied the formation of
byproducts in the selective oxidation of glucose and found that
significant glucose isomerization to fructose started at 343 K
when the pH was 7, but glucose isomerization was rapid at
323 K at a pH of 9.5.
99
Other byproducts such as sorbitol,
mannose, glycolaldehyde, and maltose were not observed until
the reaction temperature reached 343 K at a pH of 9.5, and
even then they were found in small quantities.
Table 16 reports the TOF from selected examples of glucose
oxidation over supported Au catalysts. In basic conditions, the
initial TOF of glucose oxidation was in the range of about 1 to
10 s
1
. The high rate of glucose oxidation at relatively mild
basic conditions is simply because the ring-open form of the
sugar is an aldehyde instead of an alcohol. As discussed
Fig. 9 Major glucose oxidation products reported in the literature. Fructose is
an isomerization product of glucose at high pH and temperature. Only -D-glu-
copyranose is shown to simplify the scheme. Other possible cyclic isomers
include -D-glucopyranose, -D-glucofuranose, and -D-glucofuranose.
Table 15 Turnover frequencies and reaction conditions for glycerol oxidation over Pt/C and PtBi/C catalysts
2
(kPa) pH TOF
a
(s
1
) Dihydroxyacetone selectivity (%) Reference
5% Pt/C 3.6 398 Flow 4 0.24 0 84
5% Pt5% Bi/C 4.5 398 Flow 4 0.65 51 84
5% Pt/C 5 343 Flow 7 0.27 12.9 86
3% Pt0.6% Bi/C 5 343 Flow 7 0.41 44.3 86
a
TOF calculated or re-calculated on based on available surface metal.
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earlier with HMF, the oxidation of the aldehyde side chain is
much more rapid than the alcohol side chain. The highest
TOFs are reported by Ishida et al. and are 45 s
1
for Au/ZrO
2
and 42 s
1
over 0.86% Au/Al
2
O
3
at 323 K.
100
The same authors
report a TOF over a 1% Au/C catalyst of 10 s
1
, which suggests
a potential support eect for glucose oxidation over Au. In
addition, Ishida et al. showed that the synthesis procedure for
preparing Au catalysts can greatly aect the final activity. Solid
grinding of the support with a volatile organo gold complex
works best for Al
2
O
3
- and ZrO
2
-supported Au, but deposition
precipitation works well for TiO
2
- and CeO
2
-supported Au. In
similar work, Benko et al. tested glucose oxidation over SiO
2
-,
TiO
2
-, CeO
2
-, and C-supported Au catalysts,
101
but the highest
TOF of 4.1 s
1
was found on a Au/C catalyst.
High TOFs for glucose oxidation were also reported by
Comotti et al. in several publications. For example, a 1% Au/C
catalyst with 3.8 nm and 2.4 nm particles had TOFs of 15.2
and 16.2 s
1
, respectively.
103,104
It should be noted that
glucose concentration in solution may aect the oxidation
rate. Prusse et al. determined the initial rate of oxidation
increased with glucose concentration up to 20 wt% and then
decreased at higher concentrations of glucose. A volcano-type
relationship with a peak at 20 wt% glucose concentration was
found and had a maximum TOF of 1.7 s
1
at 313 K and
900 kPa O
2
.
109
Comotti et al. also tested the catalytic activity of unsup-
ported Au nanoparticles in solution for glucose oxidation.
102
The soluble Au nanoparticles had a TOF of 18 s
1
, which is
consistent with many of the other reports for supported Au
catalysts (see Table 16). The authors also noticed that Au par-
ticle size of the homogeneous nanoparticles increased during
glucose oxidation from 3.6 nm to 10 nm, which could aect
the measured rates. Interestingly, Comotti et al.
103
reported a
lower TOF for Au/C in the absence of added base than Biella.
98
The pH dropped throughout the run from 6.0 to 2.6. Evidently,
Au was not active at low pH.
110,111
Baatz et al. studied the long term stability of Au catalysts for
glucose oxidation.
107
In particular, a 0.3% Au/Al
2
O
3
catalyst
with a Au particle size ranging from 1.2 to 3 nm was recycled
20 times at 313 K and maintained a fairly consistent TOF of
6.2 s
1
. Mirescu et al. also demonstrated high selectivity and
activity of 0.45% Au/TiO
2
at 313 K, with no deactivation after
17 recycle experiments with a TOF of 2.7 s
1
.
108
Mirescu et al. explored the initial oxidation activity of a
0.45% Au/TiO
2
catalyst for a variety of sugar substrates as sum-
marized in Table 17 and Fig. 10.
112
Although the selectivity to
the sugar acid was very high in all cases, the substrate aected
the TOF of the reaction. It should be mentioned that the TOF
of glucose oxidation reported in Table 17 is about two orders
of magnitude lower than many of those reported in Table 16.
However, the result reported in Table 17 corresponds to an
experiment utilizing a very low concentration of glucose, which
may account for the much lower TOF. The oxidation of the dis-
accharide maltose, which is formed from the condensation of
two molecules of glucose, had a TOF of 0.27 s
1
, which is
almost identical to the TOF of glucose (0.28 s
1
) at identical
conditions. It appears that the ring opening of the disacchar-
ide (maltose) to an open chain on one side is identical to
the ring opening of the monosaccharide (glucose). When the
maltose concentration was increased from 0.01 M to 0.1 M the
TOF increased to 1.3 s
1
. The oxidation of lactose, which is
formed by the condensation of two dierent sugars (galactose
Table 17 Turnover frequencies and product selectivities for sugar oxidations
a
Substrate TOF (s
1
) Selectivity to product acid (%)
Glucose (hexose) 0.28 >99.5
Galactose (hexose) 0.17 >99.5
Arabinose (pentose) 0.12 >99.5
Xylose (pentose) 0.10 >99.5
Maltose (disaccharide) 0.27 >99.5
Maltose (disaccharide)
b
1.3 >99.5
Lactose (disaccharide) 0.09 >99.5
a
Reaction conditions: 0.01 M substrate, 450 substrate : Au (mol : mol),
313 K, 500 cm
3
min
1
O
2
, pH = 9. Catalyst: 0.45 wt% Au/TiO
2
(particle
size: 1.5 nm). Ref. 112.
b
0.1 M Maltose, 4500 maltose : Au (mol : mol).
Table 16 Turnover frequencies and reaction conditions for glucose oxidation over selected Au catalysts
2
(kPa) pH
c
TOF (s
1
) Reference
0.86% Au/Al
2
O
3
2.6 323
b
9 42 100
Au Nanoparticles 3.6 303
b
9.5 18
a
102
1% Au/C 3.4 323
b
9.5 16.2
a
103
1% Au/C 3.8 323
b
9.5 15.2
a
104
1% Au/C 5.4 323
b
9 10 100
0.3% Au/Al
2
O
3
1.5 313
b
9 6.2
a
105
1.06% Au/NPC 2.6 323
b
9.5 6.0 106
0.1% Au/Al
2
O
3
2.25 313
b
9 4.5
a
107
0.8% Au/C (WGC) 10.5 318
b
9.5 4.1
a
101
0.89% Au/C 4.42 323
b
9.5 3.6
a
98
0.45% Au/TiO
2
1.5 333
b
11 2.7
a
108
0.3% Au/Al
2
O
3
6 313 900 9 1.7
a
109
0.45% Au/TiO
2
1.5 313
b
11 1.1
a
108
0.89% Au/C 4.42 373 300 Not controlled 0.6
a
98
1% Au/C 3.4 343 300 Not controlled 0.05
a
103
a
b
No pressure reported.
c
The pH was controlled by addition of NaOH solution.
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and glucose), had a lower TOF (0.09 s
1
) than either of its
monosaccharides. Galactose had a lower TOF (0.17 s
1
) than
its stereoisomer glucose.
The rates reported by Mirescu et al. (Table 17) are similar to
other reports on galactose and arabinose oxidation over sup-
ported Au catalysts. Kusema et al. performed galactose oxi-
dation with a 2% Au/Al
2
O
3
catalyst with 2.6 nm particle size
and found a TOF of 0.18 s
1
at a pH = 10 and 333 K.
113
An
acidic medium had a significantly lower TOF of 0.012 s
1
, and
shifted the product distribution toward galactonolactone
(45%). The oxidation of arabinose with supported Au catalysts
has been investigated by Kusema et al. as well.
114
A 1%
Au/Al
2
O
3
catalyst at a pH = 8 and 333 K had a TOF of 0.320 s
1
for conversion of 0.1 M arabinose to arabinonic acid (99%).
Simakova et al., however, reported a TOF of 0.29 s
1
for arabi-
nose oxidation with 2% Au/Al
2
O
3
at 333 K ( presumably the
same catalyst).
115
The authors proposed that the reaction is
structure sensitive since when rate was plotted versus particle
size, 2.3 nm size Au particles showed the greatest rate of reac-
tion. Smolentseva et al. also reported the rate of arabinose oxi-
dation of 0.101 s
1
over a 4% Au/CeO
2
catalyst with Au
particles about 2.3 nm in size at 333 K and a pH = 8.
116
It
should be noted that the TOF for arabinose oxidation over Au
is significantly lower than that for glucose oxidation under
similar conditions. Smolentseva et al. also reported that
bimetallic PdAu/CeO
2
catalyst had a TOF of 0.275 s
1
, higher
than both the rate of monometallic Pd, 0.029 s
1
, and Au,
0.090 s
1
under similar conditions. The bimetallic alloy was
suggested to have a higher activity than the monometallic cata-
lysts because of a bifunctional mechanism in which Pd disso-
ciated dioxygen while Au oxidized arabinose.
3.7.2 Platinum and palladium catalysts. A major barrier in
glucose oxidation with supported Pt and Pd catalysts is their
rapid deactivation over a wide range of reaction conditions.
Extensive research has therefore investigated the promotion
and alloying of Pt and Pd catalysts to improve their resistance
to deactivation. Reaction rate profiles for carbohydrate oxi-
dation over Pt and Pd, catalysts are relatively rare, which is
surprising given the problem of deactivation. Single point
evaluations of conversion and selectivity may be misleading
because of rapid deactivation of the catalyst. In addition,
because of metal over-oxidation and strong adsorption of
byproducts on Pt and Pd, many studies are deliberately run
under conditions that are limited by O
2
transport to the cata-
lyst to avoid the formation of metal oxides. One study that
reported sucient information to calculate a TOF was per-
formed by Delidovish et al. who measured a TOF for glucose
oxidation of 0.05 s
1
for a 5% Pt/C catalyst at 333 K and pH of
9 and the TOF was independent of the Pt particle size between
1.1 and 4.5 nm.
117
At the same conditions, a 2% Pd/C catalyst
Fig. 10 Sugars used as substrates in Table 17 and their ring opening products that are in equilibrium in aqueous solution. Only the beta and dextro ring and linear
forms were shown to simplify the scheme. Maltose and lactose are disaccharides in which one ring opens.
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with 6.3 nm Pd particles had a TOF of 1.3 s
1
, but a similar
catalyst with 3 nm Pd particles had a significantly lower TOF of
approximately 0.5 s
1
. Deactivation was thought to be caused
by the over-oxidation of Pd as revealed by X-ray photoelectron
spectroscopy. Nevertheless, the selectivity of the glucose oxi-
dation reaction was above 95% to gluconic acid in all cases.
Since the selectivity of glucose oxidation is nearly 100% to
the acid at low temperatures and moderately basic conditions,
bimetallic particles of Pt or Pd have been investigated as a
possible way to reduce the rapid deactivation. Abbadi et al.
showed that the pH had a significant eect on rate of reaction
and rate of deactivation.
118
At acidic conditions (i.e. no control
of pH) a 5% Pt/C quickly deactivated during oxidation of
0.05 M glucose at 333 K. While attempts to reactivate the cata-
lyst by dihydrogen flow for 30 min were not successful,
addition of KOH did reactivate the Pt catalyst. Addition of Bi as
a promoter helped delay deactivation of the catalyst. Besson
et al. also showed the same eect of reduced deactivation
during glucose oxidation after promoting Pd with Bi. More
specifically, a 4.7% Pd/C catalyst demonstrated 82.6% conver-
sion of glucose after 24 h whereas a 4.7% Pd0.47% Bi/C cata-
lyst reached 99.6% conversion after only 2.5 h. The Bi-
promoted catalyst was also recycled successfully, although
leaching was not investigated.
119
The addition of Bi to a bi-
metallic PtPd catalyst was also shown by Biella et al. to
increase the TOF of glucose oxidation based on total surface
metal versus just Pd, where the Bi promoted PtPd tri-metallic
catalyst was reported to have a TOF of about 0.2 s
1
and
demonstrated limited deactivation.
98
Witonska et al. has shown that Te can be used instead of Bi
as a promoter for Pd-catalyzed oxidation of glucose and that a
significant increase in TOF was realized.
120
A 5% Pd/SiO
2
cata-
lyst had a TOF of 0.79 s
1
, while a 5% Pd5% Te/SiO
2
catalyst
had a TOF of 48.1 s
1
at 333 K. The 5% Pd2% Te/Al
2
O
3
,
however, only had a TOF of 1.64 s
1
. The authors believed that
both Pd and Te had an increased dispersion on Al
2
O
3
, which
may have reduced the eectiveness of Te as a promoter of the
Pd. Whereas Bi has been shown to leach into solution,
especially at high weight loadings, the leaching of Te was
about five times less. Karsi et al. extended the use of
oxophilic promoters by studying the eect of Bi, Tl, Sn, and
Co promoters on Pd catalysts. The Bi-promoted catalysts
exhibited the highest TOF of 34.2 s
1
, followed by Tl, Sn, and
then Co. The authors suggest that Bi does not just act as a
steric promoter of Pd particles by preventing the adsorption
of acid byproducts, but also prevents over-oxidation of Pd
metal to PdO. Bismuth, however, leached at about the same
rate as Tl and Co. The Sn promoter did not leach
extensively into solution, but it did not prevent deactivation
of the Pd either.
121,122
A high TOF of glucose oxidation over
promoted Pd catalysts, which is of the same magnitude as
that on Au, might suggest that the mechanism for the alde-
hyde to acid oxidation of glucose is similar over both Au and
Pd. The deactivation profile of the two catalysts, however,
appears to be very dierent, most likely because Au is so
noble.
4. Factors aecting the evaluation of
reaction rates
4.1 Deactivation of the catalyst
The deactivation of metal catalysts is a serious issue that must
be addressed prior to commercialization of oxidation pro-
cesses. Not only are transition metals expensive, but purifi-
cation of bio-renewable feedstocks from biomass remnants
can also be expensive. Deactivation of catalysts is often
reported in papers without attributing it to a specific cause.
Sintering, leaching, and over-oxidation of the metal as well as
strong adsorption of products or byproducts on the metal
surface are among the possibilities. While the addition of a
promoter, such as Bi on Pt and Pd prevents some deactivation,
specific modes of deactivation need to be identified so that the
catalyst stability can be improved.
Although Au is a noble metal that is resistant to over-
oxidation and leaching, recent work has shown that inhibition
of Au (and Pt) by trace ketone byproducts formed during oxi-
dation can inhibit oxidation reactions.
88
At high pH, the pres-
ence of compounds with secondary alcohol groups, such as
sugar acids or other polyols, can produce ketones and enones
that strongly adsorb to the active catalytic sites. Indeed, the
addition of simple ketones at the beginning of a reaction can
decrease oxidation rate by over 90%. Acetone and its aldol con-
densation product, mesityl oxide, both significantly poisoned
Au and Pt surfaces used in glycerol oxidation. These results
suggest that Au-catalyzed alcohol oxidation reactions may have
diculty dealing with carbohydrate impurities present in
biomass feedstocks since basic conditions are needed for high
activity.
As discussed earlier, Pt and Pd catalysts are thought to be
deactivated by the adsorption of gluconic acid and other
byproducts from glucose oxidation.
123125
Moreover, the deacti-
vation of Pt during glucose oxidation was enhanced at neutral
and acidic pH. For example, Abbadi et al. showed a rapid deac-
tivation of 5% Pt/C at any pH below 7 whereas little deactiva-
tion was observed above a pH of 7.
118
Attempts to reactivate
the catalyst by reduction with H
2
after poisoning did not
restore catalytic activity, indicating that over-oxidation of the
metal catalyst was not the sole mechanism of deactivation.
Deactivation was attributed to the strong adsorption of CO
formed by decarbonylation or the strong adsorption of free
gluconic acid. Recently, the decarbonylation of benzaldehyde,
a product of benzyl alcohol oxidation, produced adsorbed CO
on the surface of Pd/Al
2
O
3
as observed by ATR-IR spectroscopy.
The authors reported that decarbonylation occurs preferen-
tially on Pd(111) sites.
126
Although many authors claim that over-oxidation of Pt and
Pd metal catalysts is the cause of deactivation, very few provide
experimental evidence. A brief discussion of the oxidation
state of Pt and Pd during alcohol oxidation was provided by
Mallet and Baiker.
127
The active site for dissociative adsorption
of the alcohol and -hydride elimination is considered to be
the reduced metal, Pt(0) and Pd(0).
117
Deactivation by
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over-oxidation of the metal has been deduced when the cata-
lyst is regenerated by reduction with dihydrogen or by treat-
ment with alcohol in an inert atmosphere. Gogova et al.
showed that deactivation by over-oxidation was reversible for
supported Pd in a CSTR by replacing dioxygen with dinitrogen
for a short amount of time at reaction temperature.
128
The
metal oxide surface was thought to be re-reduced in situ by the
alcohol groups of glucose. Markusse et al. studied the for-
mation of surface PtO by measuring the PtO distance using
EXAFS during cyclohexanol oxidation.
129
The use of cyclohexa-
nol as a substrate was thought to prevent decarbonylation
of the product aldehyde and therefore minimize formation
of CO or C
x
H
y
species that could strongly adsorb on the
surface. Markusse et al. also found that treating the catalyst
with dihydrogen or with cyclohexanol in dinitrogen re-
activated the catalyst and reduced the PtO contribution
measured in EXAFS. The same result was found using
the quick EXAFS technique for Pd/Al
2
O
3
during cinnamyl
alcohol oxidation in organic solvent at 333 K.
130
Keresszegi
et al. used EXAFS to reveal that both Pd and Bi were oxidized
on a Bi-promoted Pd/Al
2
O
3
catalyst used for 1-phenylethanol
oxidation at 333 K.
131
As expected, when both metals
were oxidized, their rate of leaching into solution was accele-
rated.
132
It appears that over-oxidation of Pt and Pd catalysts
can contribute to deactivation under certain oxidizing
conditions.
4.2 Utilizing basic supports to produce organic acids
The previous sections have discussed extensively the positive
role of added base on the rate of metal-catalyzed alcohol oxi-
dation reaction. The addition of homogeneous base, however,
presents negative environmental and economic impacts since
the high pH of the medium is corrosive and the product salts
need to be neutralized to release free acid. Thus, there has
been a recent push to find alternatives to the use of homo-
geneous bases.
A logical area of exploration is the use of solid bases as sup-
ports for metal catalysts. However, the acid products of the oxi-
dation will likely adsorb strongly on the solid bases, or worse,
react with the support, thereby leaching it into solution.
If solid bases are to be used for catalyst supports, the inter-
action between them and the organic acid products would
need to be quite weak, which likely precludes their use in
aqueous media where acids are formed.
There are a number of reports in the literature investigating
the use of hydrotalcite materials as catalyst supports in alcohol
oxidation reactions.
21,42,43,133,134
Typically, these investigations
were conducted in non-polar solvents (i.e. toluene or xylene),
which presents no problem when aldehydes were the final
product. Leaching of hydrotalcite supports in aqueous sol-
utions can be significant.
135
Even if the supported transition
metal does not leach, it is possible that the hydrotalcite
support is dissolved by the product acid. Therefore, analysis of
leaching of the basic support is imperative when aqueous solu-
tions are involved.
25
4.3 Mass transfer limitations
The initial TOF of glycerol oxidation has been shown to be
about 1 to 6 s
1
at approximately 333 K, however there are a
number of reports with much lower initial rates. One possible
reason for a low observed rate of reaction is the slow rate of
transfer of O
2
from the gas phase to the liquid, or diusivity of
O
2
in the liquid and catalyst pores. If the O
2
in the aqueous
solvent is consumed faster than the rate of diusion of O
2
from the gas phase to the liquid phase, then the reactor
system is considered to be mass transfer limited. The solubility
of dioxygen in water is quite low compared to other non-polar
solvents; at 333 K and 1000 kPa, Henrys law predicts an O
2
solubility of approximately 0.007 M. Thus, the amount of cata-
lyst loaded into the reactor must be kept relatively low so that
there is an adequate flux of O
2
from gas phase to the liquid
phase.
4.4 Structure sensitivity and TOF calculation
Mori et al. gave careful thought to the analysis of the oxidation
rate of phenylethanol over Pd catalysts with various Pd particle
sizes.
11
First, the initial rates were determined at 10% conver-
sion of alcohol at 363 K without base. Based on the size of Pd
nanoparticles, assuming an FCC cuboctahedral shape, the
number of face atoms and the number of edge and corner
atoms were estimated and used to normalize the rate of oxi-
dation. The turnover frequencies were therefore normalized in
three dierent ways: by the number of surface atoms, by the
number of face atoms (those with a high coordination
number), and by the number of edge and corner atoms (those
with a low coordination number). If all of the surface atoms of
Pd were active species, then the TOF based on total surface
atoms would be independent of the Pd particle size. However,
the results showed a clear dependence of TOF on the metal
particle size. Since only the TOF values normalized by the
number of low coordination sites were independent of the
cluster size, Mori et al. concluded that phenylethanol alcohol
oxidation is structure-sensitive and the low coordination Pd
atoms are the active species.
In contrast, glycerol oxidation does not appear to depend
on the particle size of supported Au catalysts in basic aqueous
solution. The structure insensitive oxidation of glycerol over
supported Au catalysts has a TOF of about 5 s
1
at about
333 K. The structure insensitivity of supported Au for alcohol
oxidation in basic aqueous solution is consistent with the
work of Abad et al.
136
and Shang et al.,
137
which suggests that
the rate of alcohol oxidation is directly proportional to the
amount of exposed Au. The support also did not appear to
play an important role in glycerol oxidation over supported Au
catalysts. While the majority of the catalysts contained Au
particles smaller than 5 nm, Ketchie et al. showed that even
very large particles of Au (20 to 40 nm) on a carbon support
had oxidation rates of about 2 s
1
at 333 K with a 2 to 1 ratio
of substrate to base. However, glycerol oxidation over a 0.5%
Au/C catalyst with 7.3 nm surface average diameter particles
had a TOF of 17 s
1
, which is the highest rate reported in the
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literature by three times and does not fit the idea of structure
insensitivity for the reaction.
24
Gold is a dicult metal to accu-
rately quantify the number of active sites available, which is
needed to calculate a TOF. The relative inability of Au particles
to adsorb dihydrogen, dioxygen, and carbon monoxide at
room temperature rules out the use of chemisorption as a
method to count sites. The lack of a good evaluation of the
amount of available surface metal by the chemisorption of a
gas makes the TEM a valuable resource to estimate the
amount of surface metal. The images obtained from the TEM
and the nanoparticle size measurements are typically a small
sample size of the overall catalyst and do not always accurately
reflect the actual average diameter of the supported metal. In
addition, larger particles (10 to 30 nm) from the agglomeration
or sintering of Au during catalyst synthesis can increase the
average particle size, even if a significant portion of the par-
ticles are small. While a histogram of Au particle size was not
included for the 0.5% Au/C catalyst, the micrograph clearly
shows a bimodal distribution with many particles 23 nm in
size and some particles 1030 nm in size. A bimodal distri-
bution of particles can artificially inflate the TOF because the
smaller particles have a greater amount of surface atoms in
comparison to the larger particles. If it were assumed that the
average particle size was 2.5 nm (estimated as 40% dispersion),
the previous TOF of 17 s
1
would be about 6 s
1
which is close
to the TOF for glycerol oxidation found in the literature. Thus,
the oxidation of glycerol is most likely structure insensitive
and a TOF significantly greater than 10 s
1
can be explained by
inaccurate quantification of available surface metal.
5. Conclusions
The oxidation of alcohols and aldehydes is an important reac-
tion in chemicals production and is especially relevant in the
production of chemicals from biomass sources. While oxi-
dations have long been performed using highly toxic oxidants,
the environmental and economic benefits of supported metal
catalysts are significant. The oxidation of alcohols over sup-
ported transition metals is rapid at mild temperatures
(295333 K) and facilitated by the addition of base.
Mechanistically, the oxidation of alcohols proceeds through
a first oxidation step to aldehydes and through a second oxi-
dation step to carboxylic acids. The first oxidation, alcohol to
aldehyde, is dicult, whereas the second oxidation of alde-
hyde to acid is rapid in water. The second oxidation step is so
fast that the transport limits must be carefully considered and
avoided if a kinetic rate is to be determined. Kinetic results
should be obtained at low levels of substrate conversion since
deactivation of the metal surface can be rapid. This deactiva-
tion can be due to over-oxidation of the metals (Pt and Pd) but
also can be the result of product or byproduct adsorption,
especially by ketones, acids, and carbon monoxide. Adjusting
reaction conditions, alloying materials to create bimetallic cat-
alysts, and/or utilizing oxophilic promoters can be used to
increase the stability and thus longevity of heterogeneous
catalysts.
Tuning the product selectivity to acid or aldehyde may be
most easily achieved by selection of the solvent, since water
solvent favors the formation of acid. As with any sequential
reaction, comparison of catalyst activity with respect to
product selectivity should be made at equal levels of conver-
sion of the substrate. The rapid rate of alcohol oxidation, as
well as the potential to tune product selectivity, makes tran-
sition metal catalysts attractive materials for use in the emer-
ging biomass-derived chemicals market.
Acknowledgements
Support from the National Science Foundation (Grant Nos.
OISE 0730277 and EEC-0813570) is gratefully acknowledged.
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