DOI: 10.1002/cctc.
201200008
Significant Formation of Adipic Acid by Direct Oxidation of
Cyclohexane Using Supported Nano-Gold Catalysts
Ahmad Alshammari,*[a] Angela Koeckritz,[b] Venkata Narayana Kalevaru,[b]
Abdulaziz Bagabas,[a] and Andreas Martin[b]
Adipic acid (AA) is one of the highest volume chemicals in
world use with a wide range of commercial applications. This
paper demonstrates the possibility of producing significant
proportions of AA by the selective oxidation of cyclohexane
(CH) in one step using various supported gold-nanoparticle
(AuNP) catalysts. The catalysts were characterized by ICP, BET,
XRD, X-ray photoelectron microscopy, and TEM. The catalytic
activity tests were carried out in the liquid phase using auto-
claves in the temperature range of 100170 8C at 10 bar. A CH
Introduction
The selective oxidation chain of cyclohexane (CH) to adipic
acid (AA) is an important reaction for the industrial manufac-
turing of polyamides (e.g., nylon 6,6), polyurethanes, polyes-
ters, plasticizers, intermediates for pharmaceuticals, and insecti-
cides.[13] AA is also used in the medicine and food indus-
tries.[4, 5] In 2008, the global consumption of AA was around
2.5 million metric tons, mostly as a precursor for the produc-
tion on nylon 6,6. The worldwide growth rate for AA is about
3 % per year, which is expected to reach 811 % by 2015.[6]
These statistics clearly indicate a great demand for this com-
modity chemical (AA) in the global market. Thus, developing
novel, clean, and green pathways for AA production is an im-
portant research target (Scheme 1). AA rarely occurs in
nature.[7] Historically, AA was synthesized from various fats by
oxidation. Today, AA is obtained in a two-step oxidation pro-
cess starting from CH. The first step is the oxidation of CH to
cyclohexanone and cyclohexanol with  5 % conversion of CH
at a temperature of around 150 8C and a pressure of 1020 bar
in air with a cobalt or manganese catalyst.[8, 9] The second step
is the oxidation of the cyclohexanone/cyclohexanol mixture
(the so-called KA oil) to AA by nitric acid.[10]
Scheme 1. One-step oxidation of CH to AA by O2.
Research focuses mainly on the production of the KA mix-
ture in the first step, because there are different ways to yield
this intermediate, unlike the second step (conversion to AA),
which is normally done by reaction with nitric acid. This pro-
1330  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
conversion of over 25 %, with 26% selectivity of AA and 70%
selectivity of KA oil (cyclohexanone + cyclohexanol), was ach-
ieved over a nano-gold/TiO2 (anatase) catalyst. The superior
performance of this catalyst is attributed to the smaller size of
AuNPs, which has an average particle size of 2 nm. Good corre-
lation between activity and Au particle size could be achieved.
Overall, the particle size of the AuNPs showed a strong influ-
ence on catalytic performance.
cess is not environmentally friendly because a large amount of
nitrogen oxides (N2O and NOx) is formed.
Besides the commercial process, there are other alternative
routes for producing AA. For example, AA can be obtained by
direct oxidation of CH using hydrogen peroxide, by carbonyla-
tion of butadiene, by dimerization of methyl acrylate, or by fer-
mentation of glucose. Some process options for AA production
in the absence of HNO3 usage have been proposed by various
research groups in different patents.[11, 12] These approaches
gave poor selectivities (S = 3050 %) toward the desired prod-
ucts. An additional problem with most of these processes is
the use of soluble homogeneous catalysts, which leach out
during the course of the reaction and pose difficulty in separa-
tion after the reaction. The usage of solid catalysts in the
direct oxidation of CH to AA is also known. For example, F. T.
Starzyk et al., have applied iron phthalocyanine encapsulated
in Y-zeolite as a catalyst for the direct oxidation of CH to
AA.[13] However, this process suffers from much longer induc-
tion periods, that is, the catalyst requires about 300 h to reach
CH conversion of approximately 35 % and needs 600 h to get
[a] Dr. A. Alshammari, Dr. A. Bagabas
National Nanotechnology Research Center
King Abdulaziz City for Science and Technology
P. O. Box 6086, Riyadh 11442 (Saudi Arabia)
Fax: (+ 966) 1-481-4574
E-mail: aalshammari@kacst.edu.sa
[b] Dr. A. Koeckritz, Dr. V. N. Kalevaru, Dr. A. Martin
Department of Heterogeneous Catalytic Processes
Leibniz Institute for Catalysis at the University of Rostock
Albert-Einstein-Str. 29a, 18059 Rostock (Germany)
Fax: (+ 49) 381-1281-51246
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/cctc.201200008.
ChemCatChem 2012, 4, 1330 1336
Formation of Adipic Acid by Direct Oxidation

higher amounts of AA in the product stream, which makes the
process commercially unattractive.
To date, a variety of gold-based catalysts have been exam-
ined, for example, Au/graphite,[14] Au/MCM-41,[15] Au/SBA-15,[16]
and Au/SiO2,[17] . Most of these catalysts showed zero or very
poor activity, and no AA was formed in the first step of the re-
action.[18] The aim of this work is, consequently, to explore and
develop a green route for the direct oxidation of CH to AA
with novel, supported nano-gold catalysts. Herein, we report
for the first time the possibility of producing AA from CH in
one-step.
Results and Discussion
XRD investigation
The XRD patterns of the fresh Au catalysts are displayed in
Figure 1. XRD patterns reveal that no reflections (crystalline
phases) corresponding to metallic Au could be detected in the
TiO2 and Al2O3 supported gold nanoparticles (AuNPs), which
might be a result of their high dispersion. TEM also indicated
the formation of small Au particles in these two samples (Fig-
ure 2 a and b). However, the gold catalysts supported on MgO,
CaO, and ZrO2 exhibited crystalline-gold metallic phases and
intense reflections corresponding to their supports. In addition,
the MgO- and CaO-supported samples showed two diffraction
lines at 2 q = 38.28 (d = 2.35 ) and at 2 q = 43.48 (d = 2.03 ),
which correspond to the metallic Au phase.

Catalyst properties
The physicochemical characterization data of various catalysts
are presented in Table 1. Inductively coupled plasma optical
emission spectroscopy (ICP-OES) analysis confirmed that the
loading of Au on various supports is in agreement with the
nominal content of Au (1 wt %). The BET surface areas of the
catalysts were found to depend on the type of support used
and varied from 27 to 261 m2g 1. The average particle size of
Au was estimated by TEM to vary from 2 to 8 nm, whereas the
crystallite size obtained by XRD was approximately 5 to 6 nm
(Table 1).

Table 1. Au contents, BET surface areas, and particle/crystallite size of Au

in different supported Au catalysts.

Catalyst ICP SBET[a] TEM[b] XRD[c] Figure 1. XRD patterns of fresh 1 % Au catalysts with different supports:
[wt %] [m2 g 1] [nm] [nm] a) MgO, b) CaO, c) ZrO2, d) TiO2, e) Al2O3.
Au/CaO 0.7 34 5.9 4.7
Au/MgO 0.8 27 7.7 5.7
Au/ZrO2 0.9 39 3.9 4.9
Au/TiO2 0.9 43 2.2 amorphous XPS investigation
Au/Al2O3 0.8 261 3.1 amorphous
The X-ray photoelectron spectroscopy (XPS) results, which
[a] BET surface area. [b] Particle size of Au. [c] Crystallite size of Au. demonstrate binding energy (BE) and atomic ratios, obtained
from supported gold catalysts are given in Table S1. The BE
values of Au 4f7/2 and 4f5/2 spectral lines varied narrowly from
83.3 to 83.7 eV, and 87.4 to 87.6 eV, respectively. These BE
Thermal analysis
values indicate that the gold in the catalysts exists in metallic
Thermogravimetric analysis (TGA) plots of uncalcined Au cata- form, which is in accordance with the literature.[19]
lysts supported on different metal oxides (e.g., MgO, CaO,
ZrO2, TiO2, Al2O3) are presented in Figure S1. It is clear that the
TEM investigation
stability of Au catalysts is depended on the nature of the sup-
ports used. All the studied catalysts showed two stages of The TEM image of AuNPs supported on TiO2 (anatase) is illus-
weight loss; the initial weight loss observed for all catalysts trated in Figure 2 a). The AuNPs supported on several other
was a result of the loss of weakly bound water/moisture metal oxide supports (MgO, CaO, ZrO2, and Al2O3) are also pre-
(<150 8C), the second was a result of loss of structurally bound sented in Figure 2 b). The TEM images of all catalysts showed
water (150300 8C). Au/TiO2 and ZrO2 catalysts showed the a good gold dispersion with different Au particle size distribu-
lowest weight loss (6 and 11 %, respectively) up to 900 8C. In tion. The TiO2 and Al2O3 supports resulted in a narrow particle
addition, the alumina-supported catalyst loses weight continu- size distribution of 14 nm. It is evident from particle size dis-
ously with rising temperature, whereas all others, except CaO, tribution (shown as insert in Figure 2 a) and b) that TiO2 exhib-
showed only a marginal weight loss from 350 to 900 8C. its the smallest AuNPs and that the majority of AuNPs are in
the range of 12 nm. Thus, relatively high dispersion can be
expected from this support. However, in case of non-reducible

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 A. Alshammari et al.

Catalytic evaluation

Prior to performing the catalytic

tests, some blank tests were
conducted initially under similar
conditions to those of real tests
to determine whether the oxida-
tion of CH can occur in the ab-
sence of catalyst and/or tert-
butyl hydroperoxide (TBHP), in
particular, according to a radical
mechanism. Such blank tests (in
the absence of catalyst but in
presence of TBHP and also in ab-
sence of both TBHP and catalyst)
showed almost negligible CH
conversion of only approximate-
ly 2 % after 4 h of reaction, and
no AA was found in the product
stream. This result clearly implies
that 1) no significant reaction
takes place under the conditions
applied and 2) the nature of the
catalyst plays a key role on the
performance. The influence of
the different supports on the
catalytic performance of AuNP
catalysts was evaluated first and
the results are presented in
Figure 3. It is quite clear that the
nature of the support has a sig-
nificant influence on the conver-
sion of CH and the selectivity of
the products. TiO2-supported
Figure 2. a) TEM and HR-TEM images of AuNPs supported on TiO2. The inset shows a histogram of Au particle size AuNPs exhibited superior perfor-
distribution. b) TEM images of AuNPs supported on MgO, CaO, Al2O3, and ZrO2. The inset shows a histogram of mance in terms of conversion of
Au particle size distribution. CH and the formation of AA
a result of the presence of the
smallest AuNPs and their high
supports (MgO and CaO) (Figure 2 b), the formation of consid- dispersion on this particular support. Therefore, these results
erably bigger Au particles is seen and their size varies in the provided further evidence on the necessity of smaller-size Au
range from 1 to 8 nm. particles, which play a crucial role in improving the perfor-
High resolution (HR)-TEM image of AuNPs supported on TiO2 mance of AuNP catalysts. The conversion of CH and selectivity
revealed that the Au particles were almost spherical and highly to AA, obtained over the TiO2-supported catalyst were 16.4
diffused into the matrix of the supports, and that some of and 21.6 %, respectively. Cyclohexanone and cyclohexanol
them were located on the surface of the support. HR-TEM were the major products of the reaction and the sum of their
images (Figure 2 a) enabled the observation of the crystal selectivity is found to vary from 45 to 70 %. The selectivity of
planes of AuNPs. The lattice plane fringes of the AuNPs were these two products, however, depends upon the reaction con-
used to calculate the d-spacing values, and were compared ditions and the nature of the catalyst support. The MgO- and
with those of bulk Au. The d-spacing value was estimated to CaO-supported solids displayed the poorest performance.
be 0.23 nm, which corresponds well to the Au [111] crystal Moreover, the highest amount of undesired side products such
plane. This result confirmed that the precursor of HAuCl4 was as CO and CO2 (sum selectivity of up to 35 %) were observed
reduced to Au0. for these two supports. Based on this result, it can be said that
MgO and CaO are not suitable supports for this reaction. In
terms of AA selectivity, the decreasing order of the perfor-
mance is: TiO2 > Al2O3 > ZrO2 > MgO > CaO. Different research
groups have attempted to use gold-based catalysts for the

1332 www.chemcatchem.org  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemCatChem 2012, 4, 1330 1336
Formation of Adipic Acid by Direct Oxidation

tional effect on the conversion

of CH, which is progressively in-
creased from 2.4 to 28 % with
rising temperature from 100 to
170 8C. The selectivity to AA is
also increased from approxi-
mately 6 to 26 % with increasing
temperature up to 150 8C at
which point it remains more or
less constant with further in-
crease in reaction temperature
to 170 8C. Cyclohexanol was the
major product at low reaction
temperatures (Scyclohexanol = 66.5 %
at 100 8C) implying that cyclo-
hexanol was the primary product
of the reaction. However, upon
raising the temperature, the rate
of oxidation increased, which in
Figure 3. Effect of support on the oxidation of CH over AuNPs/SU catalysts (SU = MgO, CaO, ZrO2, TiO2, Al2O3). turn accelerates the conversion
X = conversion, S = selectivity. of cyclohexanol into cyclohexa-
none and then to AA. Therefore,
the selectivity to AA increased
direct oxidation of CH to AA previously, but these efforts were with increasing temperature up to 150 8C. However, further rise
unsuccessful and they could not achieve more than 1 % yield in temperature to 170 8C resulted in a detrimental effect on
of AA.[1417] the formation of desired products and promoted formation of
We have shown here, for the first time, the possibility of syn- unwanted products, mainly the total oxidation products. From
thesizing AA from CH in one step with acceptably good yields. these results, a reaction temperature of 150 8C appears to be
It is evident from these results that TiO2 is the best support the optimum for better selectivity of desired products at rea-
among those tested, hence, it has been selected for further in- sonably good conversion, hence, this temperature has been
vestigation, particularly, for optimization of the reaction condi- chosen for further investigation. Additionally, the effects of
tions to enhance the yield of AA. other reaction parameters, such as 1) catalyst amount, 2) reac-
tion time, 3) stirring speed, 4) reaction pressure etc., on the
performance were checked and those results were reported
Optimization of the reaction conditions elsewhere.[20a,b]

Reaction temperature
The effect of the reaction temperature on the catalytic perfor-
mance has been chosen as an example in this paper and is de-
picted in Figure 4. It is clear that the temperature has a promo-
Amount of catalyst
Figure 5 demonstrates the influence of the catalyst amount on
the performance of the CH oxidation. It is evident that the con-

Figure 4. Effect of the reaction temperature on the oxidation of CH over Au/ Figure 5. Effect of catalyst amount on the oxidation of CH over Au/TiO2
TiO2 catalyst. catalyst.

ChemCatChem 2012, 4, 1330 1336  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemcatchem.org 1333

version of CH and the selectivity to AA are found to be in-
creased from 7 to 26 % and 11 to 26 %, respectively, with in-
crease in catalyst from 200 to 400 mg. The yield of AA ob-
tained in this case is approximately 8 %, which is a remarkable
outcome. Subsequently, the selectivity to AA remained relative-
ly constant with increase in catalyst amount. Notably, the se-
lectivity to AA increased at the expense of selectivity to cyclo-
hexanone. This result indicates that the formation of AA seems
to occur from the overoxidation of cyclohexanone. The selec-
tivity to cyclohexanol varies from 46 to 58 % with an increase
in catalyst from 200 to 400 mg. Further, at high catalyst
amounts (500 mg), the selectivity to cyclohexanol decreases,
whereas, the selectivity to cyclohexanone increases. This indi-
cates that the cyclohexanone is forming from cyclohexanol by
simple oxidation. Nevertheless, it is clear that a high catalyst
amount of 500 mg led to adverse effects on the performance
through decreased selectivity toward desired products and in-
creased formation of by-products. From this study, a catalyst
amount of 400 mg seems to be optimum.
Reusability and stability of the catalyst
To check the reusability and stability of the catalyst, recycling
tests and catalyst washing experiments were carried out using
the catalyst we determined to be best (i.e. 1 % Au/TiO2); the re-
sults are depicted in Figure 6. After the first run, the catalyst
was separated by filtration, washed, dried at 120 8C, and then
subjected to the second run under the same reaction condi-
tions. The catalyst was used for four such cycles. It is observed
that a slight decrease in the conversion of CH and the selectivi-
ty of products is observed after four runs. Interestingly, the se-
lectivity towards cyclohexanol decreased from the first run to
the second and then remained more or less constant. On the
whole, it can be said the catalyst performance decreased after
four runs, which might be a result of either leaching or deacti-
vation or because of marginal loss of catalyst mass during the
process of recovery of the catalyst. A slight decrease in the
amount of recovered catalyst sample from run to run was ob-
served. However, the former seems to be appropriate if XPS re-
Figure 6. Recycling results of Au/TiO2 catalyst for the oxidation reaction of
CH.
1334 www.chemcatchem.org  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
A. Alshammari et al.
sults are considered. XPS analysis of fresh and spent (after
4 cycles) catalysts gave some indications on the loss of Au
from the catalyst, probably a result of leaching. In addition,
TEM results (not shown here) of spent catalysts revealed ag-
glomeration and a wide particle size distribution.
Correlation of catalytic activity and particle size with the
performance of supported Au catalysts
We have investigated the reason behind the superior perfor-
mance of TiO2-supported Au catalyst compared to other solids.
The correlation between the Au particle size (from TEM) and
surface gold-to-support atomic ratio (Au/SU) derived from XPS
and catalytic performance is shown in Figure 7. The activity re-
Figure 7. Correlation between CH conversion, selectivity to AA and KA oil,
and catalyst properties of supported AuNPs.
sults are in good agreement with the particle size of Au,
hence, the conversion of CH and selectivity to AA changed in
a similar fashion to that of Au size. As expected, the smallest
AuNPs exhibited the best performance. The conversion of CH
decreased from 26 % on TiO2-supported AuNPs to 9 % on CaO-
supported AuNPs, whereas the Au size increased from approxi-
mately 2 nm (TiO2) to 68 nm (CaO). Furthermore, the XPS re-
sults revealed strong evidence that the performance increases
with enrichment of Au in the near-surface region. It can be
clearly seen in Figure 7 that the TiO2 supported AuNPs dis-
played the highest surface Au/SU atomic ratios compared to
others, hence the enhanced performance. The high dispersion
of Au and high active Au metal area is further evidence for the
beneficial effect of TiO2. The better performance of TiO2 is
a result of small Au size, high Au enrichment in the near-sur-
face region, high dispersion, and higher active metal area. Nev-
ertheless, the contribution of other parameters, such as surface
acidity and reducibility, cannot be ruled out. Further studies
are necessary to explore these aspects in more detail.
Conclusions
Gold nanoparticles supported on TiO2 (anatase) furnished
a green chemistry route for the one-step oxidation of cyclo-
ChemCatChem 2012, 4, 1330 1336
Formation of Adipic Acid by Direct Oxidation
hexane to adipic acid. Particle size of Au has a strong influence
on the catalytic performance. Under optimum conditions
(400 mg of Au/TiO2 catalyst, acetonitrile as solvent (5 mL), tert-
butyl hydroperoxide as initiator, 10 bar of O2, 150 8C), it was
possible to produce adipic acid with approximately 8 % yield
from the best case. Good correlation between Au size, disper-
sion, Au/support ratio and catalytic activity were obtained for
the first time.
Finally, we hope that this route opens a new way for the oxi-
dation not only of CH, but also various other hydrocarbons to
produce a variety of useful chemicals. Moreover, further im-
provements in the catalysts and catalytic performance would
make this methodology extremely attractive for a number of
oxidation reactions.
Experimental Section
Materials
Tetrachloroauric acid (99 %, Fluka), trisodium citrate dihydrate
(99.5 %, Fluka), and tannic acid (98 %, Aldrich) were commercially
available and were used as received. Metal oxide materials were
also commercially available. Deionized water (18.2 MW cm) was ob-
tained from a Milli-Q water purification system (Millipore).
Catalysts preparation
The catalysts were prepared in two steps using different oxidic
supports such as CaO, MgO, ZrO2, TiO2, and Al2O3. The first step
was the preparation of the colloidal gold nanoparticles (AuNPs) by
the reduction of HAuCl4 in aqueous solution using 1 % tannic acid
and 1 % sodium citrate. The second step was the impregnation of
the colloidal AuNPs with a suitable oxidic support to obtain slurry,
which was stirred for 2 h at RT the excess solvent was then re-
moved by rotary evaporation. The obtained solid was oven dried
at 120 8C for 16 h and then calcined at 350 8C for 5 h in air. The
loading of gold was fixed at 1 wt %. More details on the catalyst
preparation are described in the literature.[19]
Characterization
The Au content was determined by inductively coupled plasma op-
tical emission spectroscopy (model: optima 3000XL), by using a mi-
crowave pressure digestion (MDS 200, CEM) with hydrofluoric acid
and water regions.
Thermogravimetric thermal analyses were performed with a Shi-
madzu TGA-50. Catalysts of about 10 mg were heated from 20 to
900 8C at a rate of 5 8C min 1 and a flow rate of 25 mL min 1 in an
air atmosphere.
BET surface areas and pore size distribution of the catalysts were
obtained on a Micrometrics Gemini III-2375 (USA) instrument by N2
physisorption at 77 K. Prior to the measurements, the known
amount of the catalyst was evacuated for 2 h at 150 8C to remove
physically adsorbed water.
X-ray diffraction patterns were recorded for phase analysis and
crystallite size measurement on a Philips Xpert pro diffractometer,
operated at 40 mA and 40 kV by using CuKa radiation and a nickel
filter, in the 2 q range from 2 to 808 in steps of 0.028, with a sam-
ChemCatChem 2012, 4, 1330 1336  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
pling time of one second per step. The crystallite size was estimat-
ed using Scherrers equation.
The binding energies and atomic ratios from supported gold cata-
lysts were obtained by X-ray photoelectron spectroscopy (Model:
ESCALAB 220iXL). Measurements were carried out at constant
energy of 150 eV (survey), 25 eV (for quantification) and without
charge compensation. Monochromatic AlKa radiation (1486.6 eV)
was employed as the X-ray source. The binding energy scale was
calibrated with pure and clean Cu, Ag, and Au samples.
The morphology was investigated using a high-resolution transmis-
sion electron microscope (model: JEM-2100F JEOL). Samples were
mounted on carbon-coated copper grids. The average particle di-
ameter and size distribution were calculated using Java image tool
software (ImageJ) by considering the data of 100200 particles.
Catalytic evaluation
Catalytic tests were carried out by using 100 mL Parr autoclaves
(equipped with a glass tube inside), charged with catalyst (0.3 g),
CH (5 mL), acetonitrile as solvent (25 mL), and tert-butyl hydroper-
oxide (0.1 g) under 10 bar of O2. The identification of the reaction
products from the oxidation of cyclohexane was confirmed by
using a gas chromatograph (Agilent 6890 N) fitted with an HP-5
column and a flame ionization detector. A suitable derivatization
procedure was adopted for better analysis of acid products, for ex-
ample, adipic acid. To obtain the acids (e.g., adipic acid) in the
ester form, a product sample (500 mL) was esterified with trimethyl-
sulfonium hydroxide (400 mL) in the presence of an internal stan-
dard (3-pentanone, 100 mL). After derivatization of the acid into
ester, 0.2 mL of this sample was injected off-line and analyzed by
gas chromatography.
Acknowledgements
The authors gratefully thank King Abdulaziz City for Science and
Technology (KACST) for financing this work. The authors would
also like to thank M. Ababtain (KACST) for TEM analysis and
Schneider and Radnik (LIKAT) for solid analyses.
Keywords: green chemistry gold nanoparticles oxidation
titanium
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Received: January 6, 2012
Published online on July 23, 2012

1336 www.chemcatchem.org  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemCatChem 2012, 4, 1330 1336