Oxidation With Oxygen of Alcohols

Chem. Rev.
2004, 104, 30373058
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Oxidation of Alcohols with Molecular Oxygen on Solid Catalysts

Tamas Mallat* and Alfons Baiker
Institute for Chemical and Bioengineering, Swiss Federal Institute of Technology, ETH Honggerberg, HCI, CH-8093 Zurich, Switzerland
Received October 2, 2003
Contents
1. Introduction
2. Intrinsically Solid Catalysts
2.1. Supported Platinum-Group Metals
2.1.1. Catalysts and Reaction Conditions
2.1.2. Catalyst Deactivation
2.1.3. Reaction Mechanism
2.1.4. Application Range of Pt-Group Metal
Catalysts
2.2. Supported Gold and Silver
2.3. Oxides and Mixed Oxides
2.3.1. Ru-Containing Oxides
2.3.2. Other Oxides
2.4. Molecular Sieves
2.5. Hydrotalcites
2.6. Phosphates
3. Heterogenized Metal Complexes
3.1. Ru-Based Catalysts
3.2. Pd-Based Catalysts
3.3. V- and Mo-Containing Catalysts
(Heteropolyoxometalates)
4. Oxidation of Alcohols on Various Catalysts: A
Comparison
4.1. Primary Alcohols to Aldehydes
4.2. Primary Alcohols to Acids
4.3. Secondary Alcohols
4.4. Diols and Triols
5. Conclusions
6. Abbreviations
7. References
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Tamas Mallat received an M.S. degree in 1972 in chemical engineering

and a Ph.D. in 1976 in technical chemistry, both from the Technical
University of Budapest, Hungary. He was a postdoctoral associate under
G. C. Bond at Brunel University, London, from1978 to 1979. He continued
his academic carrier as a scientist at the Organic Chemical Technology
Research Group of the Hungarian Academy of Sciences. In 1990, he
moved to the Swiss Federal Institute of Technology (ETH), Zurich, where
he is currently a senior scientist. He was awarded a D.Sc. degree in
1994 by the Hungarian Academy of Sciences. His main scientific interest
is heterogeneous catalytic oxidation and enantioselective hydrogenation
in fine chemistry.
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1. Introduction
In t h e pa st yea r s t h er e h a s been a gr owin g dem a n d
for solid ca t a lyst s efficien t in t h e pa r t ia l oxida t ion of
a lcoh ols for t h e pr odu ct ion of fin e a n d specia lt y
ch em ica ls. Th e u se of st oich iom et r ic in or ga n ic r ea gen t s, t h ou gh decr ea sin g, is st ill widespr ea d. Th e
pr esen t st r in gen t ecologica l st a n da r ds in cr ea se t h e
pr essu r e t o develop n ew, en vir on m en t a lly ben ign
m et h ods. In m a n y in st a n ces, h om ogen eou s ca t a lysis
pr ovides power fu l solu t ion s, bu t on a n in du st r ia l
sca le t h e pr oblem s r ela t ed t o cor r osion a n d pla t in g
ou t on t h e r ea ct or wa ll, h a n dlin g, r ecover y, a n d r eu se
of t h e ca t a lyst r epr esen t lim it a t ion s of t h ese pr ocesses.
* To wh om cor r espon den ce sh ou ld be a ddr essed. Tel.: +41(1)-6325515. E -m a il: m a lla t @ch em .et h z.ch .
Alfons Baiker (born 1945) studied chemical engineering and received his
Ph.D. at ETH Zurich in 1974. Afterward, he spent several years at various
universities abroad. In 1980, he completed his habilitation thesis on
ammonia synthesis kinetics at Stanford University, California, where he
was also involved in teaching courses in kinetics and catalysis. After
returning to ETH, he started his own research group, focusing on
heterogeneous catalysis and reaction engineering. In 1989 he became
associate professor and in 1990 full professor at the ETH. His main
research interests are centered around catalyst design, mechanism and
kinetics of catalytic surface processes, asymmetric hydrogenation, selective
oxidation and environmental catalysis, in situ spectroscopy, and the
application of supercritical fluids in catalysis. His goal is to further the
scientific basis required for developing environmentally benign chemical
processes which make optimal use of raw materials and energy.
10.1021/cr0200116 CCC: $48.50 2004 American Chemical Society

Published on Web 04/01/2004
3038 Chemical Reviews, 2004, Vol. 104, No. 6
Applica t ion of solid ca t a lyst s for t h e ga s- or va por ph a se oxida t ion of sim ple, sm a ll-ch a in a lcoh ols t o t h e
cor r espon din g ca r bon yl com pou n ds is well est a blish ed.1-3 An im por t a n t r equ ir em en t is t h e r ea son a ble vola t ilit y a n d t h er m a l st a bilit y of r ea ct a n t a n d
pr odu ct sa st r on g lim it a t ion in t h e syn t h esis of
com plex m olecu les.
Solid ca t a lyst s a ct ive in t h e liqu id ph a se u n der
m ild con dit ion s h a ve a m u ch br oa der a pplica t ion
r a n ge.4,5 A m a jor ch a llen ge in liqu id-ph a se oxida t ion
wit h solid ca t a lyst s is t o pr even t lea ch in g of t h e
a ct ive species.6 Th e r ea ct a n t s a n d pa r t icu la r ly t h e
ca r boxylic a cid-t ype (by)pr odu ct s a r e fr equ en t ly excellen t ch ela t in g a gen t s a n d a cceler a t e dissolu t ion
a n d dea ct iva t ion of t h e ca t a lyst s.
Th e a im of t h is r eview is t o pr ovide a n over view
on t h e va r iou s t ypes of m a t er ia ls t h a t h a ve been
a pplied for t h e h et er ogen eou s ca t a lyt ic oxida t ion of
a lcoh ols in t h e liqu id ph a se a n d ext r a ct som e gen er a l
con clu sion s, wh er e possible. Ou r in t en t wa s n ot t o
be a ll-in clu sive; r a t h er we focu sed on t h e developm en t in t h e pa st 10-15 yea r s. On ly t h ose m et h ods
will be con sider ed wh ich a pply t h e t ech n ica lly a t t r a ct ive a n d en vir on m en t fr ien dly oxida n t , m olecu la r
oxygen . Th e n u m er ou s ca t a lyt ic syst em s u sin g m olecu la r oxygen in com bin a t ion wit h a ddit ives, su ch
a s r edu cin g a gen t s or r a dica l sca ven ger s, a r e n ot
discu ssed h er e du e t o t h e en vir on m en t a l im pa ct of
t h e a ddit ive or t h e copr odu ct for m ed.
Th er e a r e differ en t opin ion s in h et er ogen eou s
ca t a lysis wh et h er com pa r ison of t h e per for m a n ce of
gr ea t ly differ en t ca t a lyt ic m a t er ia ls is fa ir u n der
iden t ica l con dit ion s or u n der t h e best con dit ion s
iden t ified for ea ch ca t a lyst sepa r a t ely. Th e for m er
a ppr oa ch is com m on ly u sed du e t o it s sim plicit y.
Ch oosin g a differ en t set of con dit ion s, h owever , ca n
ea sily r ever se t h e a ct ivit y or select ivit y or der , a s
illu st r a t ed sch em a t ica lly in F igu r e 1. Obviou sly, a
Mallat and Baiker
ca t a lyst s. Th e t h ir d pa r t com pa r es t h e best ca t a lyst s

u sin g som e r epr esen t a t ive a n d fr equ en t ly r epor t ed
t est r ea ct ion s. We h ope t h a t t h is collect ion will be a
va lu a ble r efer en ce sou r ce t o ch em ist s sea r ch in g for
effect ive solid ca t a lyst s a n d gr een oxida t ion m et h ods.
2. Intrinsically Solid Catalysts

2.1. Supported Platinum-Group Metals
Oxida t ion of a lcoh ols a n d polyols over su ppor t ed
n oble m et a l ca t a lyst s h a s been t h or ou gh ly in vest iga t ed in t h e pa st yea r s. Det a ils of t h e ea r ly wor k, in
pa r t icu la r t h e oxida t ion of ca r boh ydr a t es a n d t h eir
der iva t ives (su ga r a lcoh ols, a ldon ic a cids, et c.), will
n ot be discu ssed h er e. Th er e a r e n u m er ou s books a n d
r eviews a va ila ble on t h e t opic, in clu din g t h e gen er a l
r u les of ch em o-, r egio-, a n d st er eoselect ive oxida t ion
of t h ese com plex m olecu les.7-15
2.1.1. Catalysts and Reaction Conditions

P t -gr ou p m et a ls ca n a ct iva t e a lcoh ols a n d m olecu la r oxygen u n der close t o a m bien t con dit ion s a n d
pr odu ce t h e cor r espon din g ca r bon yl com pou n ds or
ca r boxylic a cids in h igh yields. Toda y, va r iou s bi- a n d
m u lt im et a llic ca t a lyst s a r e a pplied t h a t a r e m or e
a ct ive, m or e select ive, a n d less pr on e t o dea ct iva t ion
t h a n m on om et a llic ca t a lyst s.11-20
Th e m ost com m on ly u sed ca t a lyst s con sist of P t or
P d a s a ct ive com pon en t s a n d Bi or P b a s pr om ot er s,
on ca r bon a n d a lu m in a su ppor t s. Ru a n d Rh a r e
u su a lly a pplied wit h ou t pr om ot er s.21-29 Besides Bi
a n d P b, a va r iet y of pr om ot er m et a ls h a ve been
su ggest ed, in clu din g Cd,30,31 Co,30,31 Cu ,32 Se,33 Ce,33,34
Te,35 Sn ,36,37 Au ,36,38 a n d Ru .36,39 Th e n on -n oble m et a l
prom oters a re in a ctive u n der rea ction con dit ions, a nd
t h eir deposit ion on t o t h e a ct ive sit es sh ou ld r esu lt
in lower oxida t ion r a t es. St ill, pr om ot ion of P t or P d
may lead to a considerable rate enhancement (Scheme
1)40-42 a n d t o a r em a r ka ble sh ift in t h e pr odu ct
dist r ibu t ion (Sch em e 2).32,37,43
S c h e m e 1. An Ex a m p le o n th e Ap p lic a tio n o f
P ro m o te d P t-Gro u p Me ta l Ca ta ly s ts ;41
(S e le c tiv itie s a re 100%)
F ig u re 1. Com pa r ison of ca t a lyst s: a t con dit ion s A a n d

B t h e ca t a lyst s I a n d III a r e t h e best , r espect ively, t h ou gh
t h ey a r e in fer ior t o ca t a lyst II wh en t h eir per for m a n ce is
com pa r ed u n der t h e best con dit ion s for ea ch ca t a lyst .
r a n dom ly ch osen set of r ea ct ion con dit ion s ca n n ot

provide a suita ble ba sis for ca t a lyst com pa r ison . H ere
t h e ca t a lyst s a r e com pa r ed on t h e ba sis of t h eir best
r epor t ed per for m a n ce. We a ssu m ed t h a t pu blica t ion s
r epor t a good set of pa r a m et er s a n d t ook t h e best
r esu lt s for com pa r ison t h a t , we h ope, a r e close t o t h e
opt im u m .
The review is divided into three major sections. The
fir st t wo in clu de oxida t ion s over in t r in sica lly h et er ogen eou s (solid) a n d h et er ogen ized m et a l com plex
Th e bim et a llic ca t a lyst s ca n be pr epa r ed by sim u lt a n eou s deposit ion a n d r edu ct ion of t h e m et a l pr ecu r sor s on t o a su it a ble su ppor t .33,44,45 Th e m ost
com m on ly u sed m et h od is, h owever , t h e deposit ion
a n d r edu ct ion of pr om ot er on t o a su ppor t ed P t or P d
ca t a lyst . A va r ia t ion of t h is m et h od is t h e in sit u
m odifica t ion ; i.e., t h e pr om ot er m et a l sa lt is sim ply
a dded t o t h e slu r r y con t a in in g t h e su ppor t ed P t gr ou p m et a l ca t a lyst , a n d t h e m et a l ion is r edu ced
t o m et a l by t h e a lcoh ol r ea ct a n t in t h e ea r ly st a ge of
t h e r ea ct ion .32,46,47 Du r in g pr om ot er deposit ion , m et a l
Catalytic Oxidation of Alcohols with Molecular Oxygen

S c h e m e 2. Th e B e s t Yie ld s o f Hy d ro x y a c e to n e o r
P y ru v ic Ac id Ac h ie v e d by P ro m o tio n o f a 5%
P t/Gra p h ite Ca ta ly s t in th e Ox id a tio n o f
P ro p y le n e Gly c o l (333 K, w a te r, p H 8) 37
Chemical Reviews, 2004, Vol. 104, No. 6 3039

S c h e m e 3. Ox id a tio n o f L -S o rbo s e to
2-Ke to -L -g u lo n ic Ac id o v e r P t Mo d ifie d by S tro n g ly
Ad s o rbin g N - a n d P -Co n ta in in g Co m p o u n d s (323
K, H 2 O, p H 7.3, O 2 , 1 ba r, S e le c tiv ity D e te rm in e d a t
50% Co n v e rs io n )
a da t om s (su bm on ola yer deposit ion ) a n d sm a ll pa r t icles (m u lt ila yer deposit ion ) a r e for m ed on t h e
su r fa ce of t h e P t or P d pa r t icles. In a ddit ion , pa r t icles
con t a in in g on ly t h e pr om ot er m et a l (M 0 or M n +) m a y
develop on the support, as illustrated in Figure 2. The
det er gen t syst em m a y be t h e ch oice for wa t er in solu ble r ea ct a n t s wh en fla m m a ble or ga n ic solven t s
a r e t o be a voided.41,43,71 Non a qu eou s solven t s a n d
r ela t ively h igh t em per a t u r e for t h e r a pid r em ova l of
t h e copr odu ct wa t er a r e r equ ir ed for t h e syn t h esis
of a ldeh ydes; t h ese con dit ion s disfa vor t h e h ydr a t ion
of a ldeh yde t o gem in a l diol a n d t h e su bsequ en t r a pid
deh ydr ogen a t ion t o a cid 72-75 (Sch em e 4).
F ig u re 2. Sch em a t ic r epr esen t a t ion of t h e st r u ct u r e of a
bim et a llic ca t a lyst pr epa r ed by deposit ion /r edu ct ion of t h e
pr om ot er m et a l (gr a y a n d bla ck) on t o a su ppor t ed P t -gr ou p
m et a l (wh it e) ca t a lyst .
promoter influences the performance of the neighborin g P t -gr ou p m et a l sit es on ly; t h u s, t h e pr om ot er con t a in in g pa r t icles on t h e su ppor t a r e on ly spect a t or species. As t h e n on -n oble m et a l pr om ot er a lon e
on t h e su ppor t is u n st a ble in t h e pr esen ce of oxygen a n d dissolves ea sily wit h a su it a ble a n ion or
ch ela t in g a gen t , t h is con t r ibu t ion sh ou ld be m in im ized.48 In con t r a st , m et a l a da t om s on t h e su r fa ce
of P t -gr ou p m et a ls a r e fa r m or e r esist a n t a ga in st
oxida t ion a n d dissolu t ion t h a n t h e cor r espon din g
bu lk m et a ls.49-52
In som e ca ses, good r esu lt s wer e a ch ieved wit h
or ga n ic com pou n ds a s m odifier s. Th ese N- a n d P con t a in in g com pou n ds a r e sim ply a dded t o t h e r ea ct ion m ixt u r e; t h ey a dsor b st r on gly on t h e m et a l
su r fa ce a n d im pr ove t h e r a t e or select ivit y. In t h e
oxida t ion of L -sor bose t o 2-ket o-L -gu lon ic a cid, t h e
select ivit y of P t cou ld be dou bled by a ddit ion of t r a ce
a m ou n t s of a m in es 53,54 or ph osph in es 55,56 (Sch em e 3).
Th e oxida t ion s a r e com m on ly ca r r ied ou t a t 330370 K a n d a m bien t pr essu r e or sligh t ly a bove wit h
a ir or oxygen . Besides t h e u su a l a pplica t ion of a
st ir r ed ba t ch (slu r r y) r ea ct or , t h er e a r e su ccessfu l
exa m ples of con t in u ou s oper a t ion .57-61
An a dva n t a ge of t h e m et h od is t h a t t h e ca t a lyst s
a r e a ct ive a n d select ive in wa t er , t h ou gh or ga n ic
solven t s,62-64 ion ic liqu ids,65 a n d den se (su per cr it ica l) CO 2 h a ve a lso been u sed.61,66-70 A wa t er -
S c h e m e 4. Effe c t o f Wa te r o n th e Re a c tiv ity o f th e

Ald e h y d e In te rm e d ia te o n P t-Gro u p Me ta l
Ca ta ly s ts
Wh en t h e t a r get pr odu ct is a ca r boxylic a cid,

pr ecise con t r ol of t h e a lka lin e pH du r in g r ea ct ion is
cr it ica l t o a ch ieve good select ivit y, en h a n ce t h e r ea ct ion by fa cilit a t in g a ldeh yde h ydr a t ion a n d pr odu ct
desor pt ion fr om t h e a ct ive sit es, a n d a void m et a l
lea ch in g fa vor ed a t h igh pH .60,76-79 Th e in or ga n ic
ba se ca n be r epla ced by a st r on gly a dsor bin g N-ba se
wh en t h e r ea ct a n t or pr odu ct is u n st a ble in ba sic
m ediu m (F igu r e 3). Th is loca lized ba sifica t ion a t t h e
m et a l su r fa ce in cr ea ses t h e r a t e of a lcoh ol deh ydr ogen a t ion wit h ou t sign ifica n t ly in flu en cin g t h e pH of
t h e solu t ion .53
Th e C/S m a ss r a t io va r ies in a br oa d r a n ge; it m a y
be a s low a s 0.01 for a ca t a lyst con t a in in g 1-5 wt %
P t -gr ou p m et a l,41 bu t in ext r em e ca ses t h e m a ss r a t io
ca n exceed 1.80 Sim ila r ly, it is difficu lt t o give a
ch a r a ct er ist ic r a n ge of r ea ct ion r a t e. Th e TOF ca n
a ppr oa ch 10 000 h -1, bu t t h er e a r e exa m ples sh owin g
a lso va lu es below 1 h -1 .81,82 Besides t h e r ole of
r ea ct a n t st r u ct u r e, a pr oba ble r ea son for t h e big
Mallat and Baiker

S c h e m e 5. S im p lifie d Ge n e ra l Ro u te fo r th e
Tra n s fo rm a tio n (D e c o m p o s itio n ) o f a P rim a ry
Alc o h o l o n th e P t-Gro u p Me ta l S u rfa c e 110
S c h e m e 6. S im p lifie d Ro u te fo r th e
Tra n s fo rm a tio n (D e c o m p o s itio n ) o f 2-P ro p a n o l o n
a P d (111) S u rfa c e 129
F ig u re 3. Ra te of oxida tion of L -sorbose to 2-keto-L -gulonic

a cid over 5% P t /Al 2 O 3 m odified by st r on gly a dsor bin g
a m in es a n d a m m on iu m h ydr oxides (323 K, 1 ba r , O 2 ,
wa t er , m odifier /sor bose, 590 ppm ). Modifier s: (1) pyr idin e,
(2) dia za bicyclooct a n e, (3) t r ibu t yla m in e, (4) t r iet h yla m in e,
(5) qu in u clidin e, (6) t et r a bu t yla m m on iu m h ydr oxide, a n d
(7) t et r a m et h yla m m on iu m h ydr oxide.
va r ia t ion is t h e in a ppr opr ia t e ch oice of ca t a lyst

com posit ion . F or exa m ple, a 1 wt % P t /C ca t a lyst wa s
com plet ely in a ct ive in t h e oxida t ion of ph en oxyet h a n ol, bu t a ddit ion of lea d a n d ca dm iu m n it r a t e pr om ot er s t o t h e a qu eou s solu t ion a llowed t h e fa st a n d
a lm ost qu a n t it a t ive t r a n sfor m a t ion t o ph en oxya cet ic
a cid (TOF ) 840 h -1 ).46,83
2.1.2. Catalyst Deactivation

A com m on ly obser ved dea ct iva t ion is t h e over oxida t ion of t h e a ct ive sit es.21,47,73,84-92 It wa s ea r ly
discover ed t h a t t h e r a t e of a lcoh ol oxida t ion is m u ch
h igh er on a r edu ced m et a l su r fa ce t h a n on t h e
oxidized su r fa ce.72,93,94 An im por t a n t con sequ en ce of
t h is differ en ce is t h a t t h e ca t a lyst h a s t o be pr er edu ced befor e a lcoh ol oxida t ion by h ydr ogen or by
t h e r ea ct a n t it self in a n in er t a t m osph er e. 93 F u r t h er m or e, t h e r ea ct or sh ou ld be oper a t ed in t h e oxygen t r a n spor t -lim it ed r egion ; i.e., t h e r a t e of oxygen
su pply sh ou ld be lower t h a n t h e a ct u a l r a t e of a lcoh ol
deh ydr ogen a t ion . In t h e kin et ic r egion , t h e a ct ive
sit es a r e su ccessively oxidized a n d t h eir a ct ivit y
dr ops. In a ba t ch r ea ct or , t h e r a t e of a lcoh ol deh ydr ogen a t ion decr ea ses wit h r ea ct ion t im e du e t o a
decr ea se of a lcoh ol con cen t r a t ion ; t h u s, t h e r a t e of
oxygen su pply h a s t o be a dju st ed by, e.g., decr ea sin g
t h e oxygen con cen t r a t ion or in cr ea sin g t h e t em per a t u r e t owa r d t h e en d of t h e r ea ct ion . Mor e det a ils
on t h e en gin eer in g a spect s of a lcoh ol oxida t ion ca n
be fou n d elsewh er e.19,59,90,95-101
F or m a t ion of st r on gly a dsor bed bypr odu ct s du r in g
a lcoh ol oxida t ion on P t -gr ou p m et a ls h a s been fr equ en t ly r epor t ed. 43,80,85,89,102,103 Typica l side r ea ct ion s
a r e t h e a ldol con den sa t ion a n d oligom er iza t ion of t h e
carbonyl compound product 104-109 a nd the decomposit ion of a lcoh ols m a in ly via t h e ca r bon yl com pou n d
for m ed in sit u , a ffor din g a dsor bed CO a n d ca r bon a ceou s species (C x H y ) (Sch em e 5).97,110-125 E ven deh ydr ogen a t ion of t h e sim plest secon da r y a lcoh ol,
2-pr opa n ol, m a y poison a P t -gr ou p m et a l a lr ea dy a t
r oom t em per a t u r e (Sch em e 6).126-130
In con t r a st t o blockin g of t h e a ct ive sit es by oxygen
or bypr odu ct s, sin t er in g of m et a l pa r t icles a n d m et a l
dissolution (lea ching) results in irreversible deactivat ion .19,42,131,132 Sin t er in g (in cr ea se of a ver a ge m et a l
pa r t icle size) a t close t o a m bien t t em per a t u r e is
a t t r ibu t ed t o a n a t om ic m igr a t ion pr ocess, t h e t r a n spor t of su r fa ce m et a l a t om s ext r a ct ed by ch ela t in g
m olecu les (Ost wa ld r ipen in g). 133 Met a l dissolu t ion a s
M n+ species is facilitated by acidic or strongly alkaline
pH ,134,135 h igh ca t a lyst pot en t ia l (h igh oxygen cover a ge), a n d t h e pr esen ce of com plexin g a gen t s.30,76,136,137
In a m ilder ca se, t h e dissolved species r edeposit on t o
la r ger , t h er m odyn a m ica lly m or e st a ble m et a l pa r t icles, r esu lt in g in pa r t icle size en la r gem en t a n d a
loss of a ct ive su r fa ce a r ea .48,102,138-140 Met a l dissolu t ion ca n be m in im ized by a pplyin g a low oxygen
con cen t r a t ion a t t h e en d of t h e r ea ct ion wh en t h e
a lcoh ol (r edu cin g a gen t ) con cen t r a t ion is low.141
St ill, lea ch in g r em a in s a lim it a t ion in t h e syn t h esis
of (poly)h ydr oxy a cids, a t r a dit ion a l a pplica t ion of P t gr ou p m et a l ca t a lyst s.
2.1.3. Reaction Mechanism

Th e m ech a n ist ic pr oposa ls m a y be divided in t o
t h r ee gr ou ps. Accor din g t o t h e cla ssica l deh ydr ogen a t ion m ech a n ism (m odel A),11,13,21,73,142,143 t h e a dsor bed a lcoh ol deh ydr ogen a t es in t wo elem en t a r y
st eps (Sch em e 7). Th e O-H bon d of a lcoh ol br ea ks
S c h e m e 7. Cla s s ic a l D e h y d ro g e n a tio n
Me c h a n is m o f Alc o h o l Ox id a tio n o v e r P t-Gro u p
Me ta l Ca ta ly s ts (Mo d e l A)
u pon a dsor pt ion on t h e su r fa ce sit es, a ffor din g a n

a dsor bed a lkoxide a n d h ydr ogen .144 In t h e a dsor bed
a lkoxide, t h e -C-H bon d is wea ker t h a n ot h er C-H
bon ds du e t o t h e elect r on -wit h dr a win g effect of
t h e oxygen a t om , lea din g t o t h e pr efer en t ia l br ea kin g of t h e -C-H bon d in t h e r a t e-det er m in in g
st ep.145 Deh ydr ogen a t ion is gen er a lly ca t a lyzed by
ba ses.143,146,147 Adsor bed oxygen (or su r fa ce OH species in a lka lin e m ediu m )148 is n ecessa r y t o oxidize t h e
copr odu ct h ydr ogen a n d t h u s sh ift t h e equ ilibr iu m

t owa r d t h e ca r bon yl com pou n d a n d a cceler a t e t h e
r ea ct ion by liber a t in g fr ee su r fa ce m et a llic sit es. Th e
inferior role of oxygen in this mecha nism is supported
by t h e obser va t ion s t h a t oxygen ca n be r epla ced by
a h ydr ogen a ccept or (e.g., a n olefin )149-153 a n d t h a t
t h e m et a l ca t a lyst is in a r edu ced st a t e du r in g
oxida t ion , a s dem on st r a t ed by elect r och em ica l a n d
E XAF S m ea su r em en t s.91,95,154-158 A fu r t h er su ppor t
for t h is m odel is t h a t a lcoh ol oxida t ion m a y be
a ccom pa n ied by h ydr ogen a t ion a n d h ydr ogen olysist ype side r ea ct ion s, displa yin g a sign ifica n t H -cover a ge of t h e a ct ive sit es (Sch em e 8).125
S c h e m e 8. Re a c tio n N e tw o rk fo r th e
Tra n s fo rm a tio n o f t r a n s-Cin n a m y l Alc o h o l o v e r
5% P d /Al 2 O 3 (Air, 1 ba r, 338 K)
An ot h er cla ss of m ech a n ist ic m odels a ssu m es t h a t

t h e r a t e-det er m in in g st ep in volves dir ect in t er a ct ion
of t h e a dsor bed oxidizin g species wit h t h e a dsor bed
reactant or its partia lly dehydrogena ted intermediate
(m odel B).16,19,57,159 Th is in t er pr et a t ion is su ppor t ed
by n u m er ou s kin et ic st u dies r evea lin g a La n gm u ir H in sh elwood-t ype beh a vior ,87,92,103,160,161 a n d elect r och em ica l 36,41,43,71,92,95,102,162 a n d X-r a y a bsor pt ion
spect r oscopic70 st u dies t h a t in dica t e a pa r t ia l oxygen
cover a ge on t h e m et a l su r fa ce du r in g som e r ea ct ion s.
On t h e ba sis of r ecen t da t a , we fa vor a t h ir d a ppr oa ch (m odel C) a dopt in g t h e cla ssica l deh ydr ogen a t ion m ech a n ism for t h e a lcoh ol f ca r bon yl t r a n sfor m a t ion a n d pr esu m in g t h a t t h e key r ole of oxygen
is t o su ppr ess ca t a lyst dea ct iva t ion du e t o st r on g
a dsor pt ion of bypr odu ct s.125 Accor din g t o t h is m odel,
t h e oxida t ive clea n in g of t h e su r fa ce sit es, or even
pr even t ion of t h e decom posit ion pa t h wa y,128 is t h e
pr im a r y r ole of oxygen a n d n ot t h e oxida t ion of t h e
copr odu ct h ydr ogen . P a r t ia l r egen er a t ion of t h e ca t a lyst s by oxida t ive r em ova l of st r on gly a dsor bed poison in g species ca n lea d t o a dr a m a t ic r a t e a cceler a t ion com pa r ed t o a n a er obic deh ydr ogen a t ion (F igu r e
4),125 a n d t h u s t o t h e (fa lse) con clu sion t h a t oxygen
F ig u re 4. Ca t a lyst dea ct iva t ion du r in g con ver sion of

cin n a m yl a lcoh ol over a 5% P d/Al 2 O 3 ca t a lyst in t olu en e
a t 338 K. The initia l TOF of 450 h -1 in Ar decrea sed r a pidly
t o 10 h -1 du e t o deca r bon yla t ion -t ype side r ea ct ion s (see
Sch em e 8). In t r odu ct ion of a ir en h a n ced t h e TOF t o 2850
h -1 . F or m a t ion of CO a n d it s oxida t ive r em ova l by a ir wer e
con fir m ed by in sit u ATR-IR spect r oscopy.
is dir ect ly in volved in t h e r a t e-det er m in in g st ep of

t h e r ea ct ion . Accor din g t o t h is m odel, som e r ea ct ion s
r u n on ly on a pa r t ia lly oxygen -cover ed m et a l su r fa ce
because chemisorbed oxygen is necessary to eliminate
(oxidize) som e su r fa ce im pu r it ies a n d liber a t e a ct ive
sit es for a lcoh ol deh ydr ogen a t ion .76,163,164
An ot h er field of con t r a dict or y opin ion s is t h e r ole
of m et a l pr om ot er s. Som e fea sible expla n a t ion s for
t h e r a t e a n d select ivit y en h a n cem en t a r e collect ed
below.
(i) Geom et r ic blockin g of a fr a ct ion of a ct ive sit es
m a y be r espon sible for t h e im pr oved ca t a lyst per for m a n ce.36,43,131,134,165 Th is so-ca lled en sem ble effect
is t r a ced ba ck t o t h e bigger a ct ive sit e en sem bles
n ecessa r y for t h e for m a t ion of poison in g in t er m edia t es (by, e.g., C-C bon d clea va ge), com pa r ed t o t h e
sit e r equ ir em en t of t h e a lcoh ol deh ydr ogen a t ion
r ea ct ion . Th is in t er pr et a t ion is in lin e wit h m odel C
of a lcoh ol oxida t ion a n d su ppor t ed by n u m er ou s
elect r oca t a lyt ic st u dies.166-168
(ii) Th e h igh r egioselect ivit y in t h e oxida t ion of
polyfu n ct ion a l a lcoh ols in t h e 2-posit ion h a s been
a t t r ibu t ed t o com plex for m a t ion bet ween t h e r ea ct a n t , a su r fa ce P t or P d a t om , a n d a n eigh bor in g
posit ively ch a r ged Bi or P b pr om ot er (F igu r e
5a ).11,38,60,79,85,135,169 A sim ila r pr oposa l is t h e com plex
F ig u re 5. Models a ssu m in g com plex for m a t ion wit h t h e

su bst r a t e a s t h e r ole of m et a l pr om ot er s in select ive
oxida t ion s.
for m a t ion bet ween a 1,2-diol a n d a Sn IV species on

t h e P t su r fa ce, r esu lt in g in t h e pr efer en t ia l oxida t ion
of t h e secon da r y OH gr ou p (F igu r e 5b).37 Alt h ou gh
t h e specia l r ole of n eigh bor in g P t -gr ou p m et a lpr om ot er su r fa ce sit es in t h e a dsor pt ion a n d deh ydr ogen a t ion of t h e r ea ct a n t is pla u sible, t h e (pa r t ia lly) oxidized st a t e of t h e pr om ot er con t r a st s t o
elect r oca t a lyt ic, LE E D, XP S, a n d E XAF S st u dies.52,158,170
(iii) Th e r a t e a cceler a t ion a n d t h e sh ift in pr odu ct
dist r ibu t ion m a y be a t t r ibu t ed t o bifu n ct ion a l ca t a lysis, a ssu m in g t h a t oxygen or OH r a dica ls a dsor bed
on t h e pr om ot er a t om a r e in volved in t h e a lcoh ol
oxida t ion r ea ct ion .36,111,171 Th is a ssu m pt ion con for m s
wit h m odel B of a lcoh ol oxida t ion . It m a y be gen er a lized a ssu m in g t h a t t h e pr om ot er fa cilit a t es t h e
oxida t ive r em ova l of su r fa ce im pu r it ies, t h u s su ppor t in g m odel C of a lcoh ol oxida t ion . An ot h er pr oba ble expla n a t ion for bifu n ct ion a l ca t a lysis is t h a t t h e
promoter metal a da toms cha nge the a dsorption properties of hydrogen and OH radicals (oxidizing species)
du e t o elect r on ic m odifica t ion of t h e su r fa ce P t or P d
a t om s.52,170
(iv) An or der ed a lloy (in t er m et a llic com pou n d)
for m ed bet ween t h e P t -gr ou p m et a l a n d Bi, P b, or
Te pr om ot er s m a y be t h e r ea l a ct ive sit e,35,80,132,172,173
or t h e bim et a llic sit e m a y in flu en ce t h e select ivit y,174
t h ou gh t h e obser va t ion s a r e con t r a dict or y.
(v) It h a s been sh own t h a t t h e pr om ot in g effect of
Bi is n ot du e t o lea ch in g a s Bi3+ species.173,175-178 Th e
pr esen ce of a la r ge a m ou n t of Bi 3+ com plexes in
solu t ion ca n even in h ibit t h e oxida t ion r ea ct ion ,
pr oba bly du e t o ext en sive r edu ct ion of Bi 3+ t o (in a ct ive) Bi 0 on t o t h e P t su r fa ce by t h e r ea ct a n t a lcoh ol.
2.1.4. Application Range of Pt-Group Metal Catalysts

Th e a pplica t ion r a n ge of su ppor t ed P t -gr ou p m et a ls, wit h a n d wit h ou t pr om ot er s, is ver y br oa d. Up
t o 100% yields h a ve been a ch ieved in t h e oxida t ion
of va r iou s pr im a r y a lcoh ols t o t h e cor r espon din g
ca r boxylic a cids a n d of secon da r y a lcoh ols t o ket on es. Th e pot en t ia l of t h ese ca t a lyst s is r eflect ed by
t h e select ive oxida t ion of on ly on e OH fu n ct ion in
com plex m olecu les su ch a s a ldon ic a cids (Sch em e
9)38,84,85,136,169,179 a n d st er oida l a lcoh ols.62,180
S c h e m e 9. S e le c tiv e Aqu e o u s -P h a s e Ox id a tio n o f
S o d iu m Glu c o n a te a t 6- o r 2-P o s itio n s (H 2 O, O 2 ,
333-338 K) 38,169
Th e select ive oxida t ion of a n a lcoh olic OH gr ou p

h a s been a t t a in ed in t h e pr esen ce of t h e followin g
ot h er fu n ct ion s: a lkoxy a n d a r yloxy gr ou ps,83,181,182
ph en olic h ydr oxyl,183-185 CdC bon d (a llylic a n d isola t ed),63,186 a r om a t ic a ldeh yde,143 a m in o gr ou p,105
qu a t er n a r y a m m on iu m gr ou p,187,188 a cet a m in o fu n ct ion ,8 n it r o gr ou p,29 n it r ile gr ou p,8 a r om a t ic Cl,32,46,189
t r iflu or om et h yl gr ou p,64 N- a n d S-con t a in in g h et er oa r om a t ic r in g,29 a n d cyclopr opyl gr ou p.29 Gen er a lly, ket o-ca r bon yl a n d ca r boxylic gr ou ps a r e r esist a n t t o fu r t h er oxida t ion .
Mallat and Baiker
An im por t a n t lim it a t ion of t h ese ca t a lyst s is t h e

oxida t ion of a liph a t ic a lcoh ols t o a ldeh ydes.16 H ydr a t ion of a liph a t ic a ldeh ydes a n d deh ydr ogen a t ion of
t h e gem in a l diol a r e fa st on t h e P t -gr ou p m et a l
su r fa ce, even in n on a qu eou s solven t s (Sch em e 4).
Ra pid r em ova l of t h e copr odu ct wa t er by a zeot r opic
dist illa t ion im pr oves t h e yield on ly m oder a t ely. 190 In
con t r a st , h ydr a t ion of a r om a t ic a n d R,-u n sa t u r a t ed
a ldeh ydes is m in or ,191,192 a n d t h eir fu r t h er oxida t ion
by oxygen in ser t ion r equ ir es sign ifica n t ly h igh er
ca t a lyst pot en t ia l t h a n t h e deh ydr ogen a t ion st ep.43
Th is is t h e expla n a t ion for t h e good yields in t h e
syn t h esis of a r om a t ic, h et er oa r om a t ic, a n d R,u n sa t u r a t ed a ldeh ydes, even in a qu eou s m edia .
Not on ly t h e oxida t ion of a liph a t ic a lcoh ols t o
a ldeh ydes bu t gen er a lly a lso t h e syn t h esis of a ct iva t ed ca r bon yl com pou n ds is a dem a n din g t a sk du e
t o t h e poor st a bilit y (r a pid deca r bon yla t ion ) of t h e
pr odu ct . Repr esen t a t ive exa m ples for t h ese difficu lt ies a n d som e good solu t ion s a r e t h e oxida t ion of
la ct ic a cid t o pyr u vic a cid (Sch em e 10), 80,172 L -sor bose
S c h e m e 10. Effe c t o f P ro m o te r in th e Ox id a tio n o f
La c tic Ac id to P y ru v ic Ac id (H 2 O, p H 8, 363 K) 80
t o 2-ket o-L -gu lon ic a cid (Sch em e 3),56,76,140,193-196 pa n t oyl la ct on e t o ket opa n t oyl la ct on e,75,197 a n d R,R,Rt r iflu or om et h yl a lcoh ols t o ket on es.64,75
To su m u p, su ppor t ed P t -gr ou p m et a l ca t a lyst s
possess a ver y br oa d a pplica t ion r a n ge. Th e t ech n ica l im por t a n ce of t h e m et h od, in clu din g t h e a dva n t a ge of oxida t ion s in a qu eou s m edia , is r eflect ed
by t h e la r ge n u m ber of pa t en t s. Th e com posit ion of
pr oven ca t a lyst s a n d t h e r a n ge of pr a ct ica lly u sefu l
con dit ion s a r e m u ch ext en ded. A n ega t ive a spect of
t h is va r iet y is t h e dem a n din g opt im iza t ion pr ocess 198,199 sa pr om isin g a r ea for com bin a t or ia l ch em ist r y.27,200
2.2. Supported Gold and Silver

In r ecen t yea r s, t h e u n expect edly h igh a ct ivit y of
Au a s a low-t em per a t u r e CO oxida t ion ca t a lyst 201-204
h a s in it ia t ed in t en sive r esea r ch in t h e u se of Au
n a n opa r t icles for t h e liqu id-ph a se oxida t ion of a lcoh ols. Gen er a lly, t h e a dsor pt ion a n d ca t a lyt ic pr oper t ies of Au st r on gly depen d on t h e pa r t icle size, wh ich
ca n be con t r olled by t h e pr epa r a t ion m et h od a n d t h e
ca t a lyst su ppor t .205-213 A cr u cia l a n d n ot fu lly u n der st ood qu est ion is wh y sm a ll Au n a n opa r t icles
exh ibit beh a vior r a dica lly differ en t t h a n t h a t of bu lk
Au .214-222
Th e a pplica t ion r a n ge of su ppor t ed gold in a lcoh ol
oxida t ion is n ot (yet ) br oa d, a n d u n der m ild con dit ion s (320-350 K a n d 1-3 ba r oxygen ) t h is oxida t ion
r equ ir es a st r on gly a lka lin e a qu eou s m ediu m .223,224
Th e a qu eou s a lka lin e m ediu m m a y r epr esen t a
st r on g lim it a t ion of t h e m et h od, a s va r iou s side
r ea ct ion s ca n dim in ish t h e select ivit y (ket o-en ol
equ ilibr a t ion , Ca n n izza r o r ea ct ion , oxida t ive deca r -
bon yla t ion ).205,224 An ot h er dr a wba ck is t h e for m a t ion

of ca r boxyla t es in st ea d of ca r boxylic a cids, t h ou gh P t gr ou p m et a ls h a ve t h e sa m e lim it a t ion in t h e oxida t ion of pr im a r y a liph a t ic a lcoh ols. In a cidic m edia ,
gold oxidizes a ldeh ydes t o ca r boxylic a cids bu t is
in a ct ive in t h e t r a n sfor m a t ion of a lcoh ols, a n d m et a l
lea ch in g m a y a lso be sign ifica n t .225 An in t er est in g
solu t ion is t h e com bin a t ion of Au wit h a P t -gr ou p
m et a l. A 1% Au -0.1% P d/Al 2 O 3 bim et a llic ca t a lyst
wa s u sed for t h e t r a n sfor m a t ion of 6-h ydr oxyh exa n oic a cid t o a dipic a cid.226 Bot h t h e r ea ct ion r a t e a n d
t h e yield (97%) wer e h igh in wa t er , even in t h e
a bsen ce of a ba se, t h ou gh on ly a t eleva t ed t em per a t u r e (433 K).
Gold is h igh ly a ct ive a n d select ive in t h e t r a n sfor m a t ion of va r iou s diols 205,206,208,218,224,227-230 a n d glycer ol 223,231 t o m on oca r boxyla t es (F igu r e 6). Tr a n sfor -
F ig u re 6. E xa m ples on t h e syn t h esis of m on oca r boxyla t es

fr om a lcoh ols in a qu eou s a lka lin e m ediu m on su ppor t ed
Au n a n opa r t icles.205,223,228
m a t ion of a m in o a lcoh ols t o a m in o a cids is a lso

select ive, bu t good yields h a ve been r epor t ed on ly for
a la n in e.228
Th e u n u su a lly h igh su bst r a t e specificit y of su pported gold is illustra ted by the following compa rison.
Oxida t ion of et h ylen e glycol t o glycolic a cid wa s fa st
(TOF ) 1290 h -1 ), a n d com plet ion of t h e r ea ct ion
r equ ir ed a C/S m a ss r a t io of on ly 0.03. 230 In con t r a st ,
in t h e t r a n sfor m a t ion of 2-h ydr oxyben zyl a lcoh ol t o
sa licyla ldeh yde, t h e TOF wa s on ly a r ou n d 5 h -1 , a t
a n ext r a or din a r y C/S m a ss r a t io of over 7.232,233
Despit e h a vin g som e sim ila r it ies t o su ppor t ed
P t -gr ou p m et a ls, Au is a dist in ct ly differ en t ca t a lyst . In con t r a st t o P t -gr ou p m et a ls, Au ca n n ot
ca t a lyze a lcoh ol deh ydr ogen a t ion in t h e a bsen ce of a
st r on g ba se. F u r t h er oxida t ion of a ldeh ydes t o ca r boxylic a cids is a n oxygen in ser t ion r ea ct ion , a n d
t h is st ep r u n s sm oot h ly on Au , even in or ga n ic
m edia .234 In com pa r a t ive st u dies of a qu eou s-ph a se
a er obic oxida t ion of a lcoh ols wit h su ppor t ed P t , P d,
a n d Au , t h e la t t er wa s t h e m ost select ive a n d t h e
lea st pr on e t o m et a l lea ch in g, t o over -oxida t ion by
oxygen , a n d t o self-poison in g by st r on gly a dsor bed
bypr odu ct s.205,227,231,235 Th e h igh er select ivit y a n d
a bsen ce of ca t a lyst dea ct iva t ion a r e pr oba bly du e t o
weaker adsorption of oxygen, hydrogen, reactant, and
pr odu ct s on Au .119,123,236
A det a iled m ech a n ism of a lcoh ol oxida t ion on Au
n a n opa r t icles h a s n ot been r epor t ed yet . On t h e ba sis
of t h e poor a ct ivit y of Au in t h e a bsen ce of a ba se, it
wa s su ggest ed t h a t t h e r a t e-lim it in g st ep wou ld be
H + a bst r a ct ion fr om a pr im a r y OH gr ou p of glycer ol.223,231 A sim ila r m ech a n ism wa s pr oposed m a n y
yea r s a go for a lcoh ol oxida t ion on P t /C, in volvin g a

secon d st ep, t h e t r a n sfer of a h ydr ide ion t o t h e P t
su r fa ce (Sch em e 11).8,87,237
S c h e m e 11. Alc o h o l Ox id a tio n o n P t (a n d Au )
In v o lv in g D e p ro to n a tio n o f th e Alc o h o lic OH
F u n c tio n by Ad s o rbe d Hy d ro x y l Io n s
We con sider it m or e fea sible t h a t t h e r a t e-det er m in in g st ep is t h e clea va ge of t h e C-H bon d a t t h e

R-carbon atom. A similar mechanism is now generally
accepted for Au electrodes (Scheme 12).238 Despite the
S c h e m e 12. Ra te -D e te rm in in g S te p in th e
Ox id a tio n o f Eth a n e -1,2-d io l o n Au Ele c tro d e in
Aqu e o u s Alk a lin e S o lu tio n
st r u ct u r a l differ en ces bet ween Au n a n opa r t icles a n d

a n ext en ded Au elect r ode su r fa ce, t h er e a r e a lso
sim ila r it ies, su ch a s t h e cr it ica l r ole of a qu eou s
a lka lin e m ediu m a n d t h e a bsen ce of dea ct iva t ion du e
t o decom posit ion pr odu ct s (CO a n d C x H y fr a gm en t s).239,240
An im por t a n t qu est ion is t h e n a t u r e of a ct ive sit es
on Au n a n opa r t icles. E lect r ooxida t ion of et h a n ol on
Au n a n opa r t icles su ppor t ed on gla ssy ca r bon r equ ir ed t h e pa r t ia l cover a ge of Au su r fa ce by oxides.241
An ot h er a n a logy m igh t be t h e m odel pr oposed for CO
oxida t ion .219,242,243 Accor din g t o t h is su ggest ion , t h e
a ct ive sit e con sist s of a n en sem ble of m et a llic Au
a t om s a n d a ca t ion ic Au + species wit h a n eigh bor in g
OH gr ou p (F igu r e 7).
F ig u re 7. Model of t h e a ct ive sit e in t h e oxida t ion of CO

by su ppor t ed Au n a n opa r t icles.219
Silver -ba sed ca t a lyst s a r e well est a blish ed in t h e

ga s-ph a se oxida t ion of a lcoh ols a n d diols 1,3,244-247 bu t
r a r ely u sed in t h e liqu id ph a se. Recen t ly, t h e qu a n t it a t ive t r a n sfor m a t ion of ben zyl a lcoh ol t o ben za ldeh yde in oxygen wa s a ch ieved over a 0.6% Ag/
pu m ice ca t a lyst u n der m ild con dit ion s (348 K, 1
ba r ).248 Th e m a t er ia l sh owed r ea son a bly good a ct ivit y, t h ou gh t h e r ea ct ion over a sim ila r ly pr epa r ed
0.27% P d/pu m ice ca t a lyst wa s a lwa ys fa st er . Th e
synergic effect observed with Pd-Ag/pumice bimetallic ca t a lyst s a n d wit h m ech a n ica l m ixt u r es of t h e
m on om et a llic ca t a lyst s wa s a t t r ibu t ed t o cooper a t ion
bet ween t h e P d 0 a n d Ag 0 a ct ive sit es; con t r ibu t ion of
t h e a lloy ph a se det ect ed by E XAF S wa s exclu ded.
Th e in fer ior per for m a n ce of ca r bon -su ppor t ed Ag,
compared to that of various supported Pt-group metal
Mallat and Baiker
ca t a lyst s, h a s been con clu ded a lso in t h e oxida t ion

of ger a n iol t o cit r a l.28
2.3. Oxides and Mixed Oxides

2.3.1. Ru-Containing Oxides
H ydr a t ed r u t h en iu m dioxide (Ru O 2 xH 2 O) is a
st oich iom et r ic oxida n t t h a t ca n be a pplied a lso a s a
r eu sa ble ca t a lyst .249-254 Th e a m ou n t of wa t er (x) is
u su a lly in t h e r a n ge 1-1.3 equ iv a n d decr ea ses
r a pidly wit h in cr ea sin g t em per a t u r e of h ea t t r ea t m en t .255 Th e m a t er ia l h a s a t wo-dim en sion a l st r u ct u r e of in depen den t ch a in s, in wh ich Ru O 6 oct a h edr a
a r e con n ect ed by pa ir s of O-br idges. H ydr ou s r u t h en iu m dioxide is a m ixed elect r on -pr ot on con du ct or ,
and the coordinatively unsaturated surface atoms can
a ct iva t e m olecu la r oxygen .256,257 Th e oxida t ion a ct ivit y of r u t h en iu m dioxide h a s been a t t r ibu t ed t o t h e
in t er a ct ion of st r on gly bou n d r ea ct a n t a n d wea kly
bou n d oxygen species.258 Th e com plet ely deh ydr a t ed
oxide is in a ct ive in a lcoh ol oxida t ion , a n d va r ia t ion
in t h e degr ee of h ydr a t ion , wh ich ca n be con t r olled
by t h e syn t h esis pr ocedu r e, st r on gly in flu en ces t h e
structure a nd th e ca t a lyt ic a ct ivit y.259,260 The h ydrou s
oxide Ru O 2 xH 2 O ea sily t r a n sfor m s in t o a m ixt u r e
of Ru a n d Ru O 2 u pon t h er m a l t r ea t m en t a t eleva t ed
t em per a t u r e.253
H ydr a t ed r u t h en iu m dioxide a ffor ded over 98%
yield t o cin n a m a ldeh yde in t h e slow oxida t ion of
cin n a m yl a lcoh ol.261 A dr a wba ck of t h e pr ocess is t h a t
2,6-di-tert-bu t yl-p-cr esol a ddit ive wa s n ecessa r y t o
prevent further oxida tion to cinna mic a cid. Rea ctivity
of pr im a r y a n d secon da r y a llylic a lcoh ols, R-ket o
a lcoh ols, R-h ydr oxy-la ct on es, a n d sa t u r a t ed a lcoh ols
decr ea sed in t h is or der . Oxida t ion of pa n t oyl la ct on e
t o ket opa n t oyl la ct on e a t eleva t ed t em per a t u r e wa s
qu a n t it a t ive, a n d t h e per for m a n ce of Ru O 2xH 2O wa s
sim ila r t o t h a t of 5% Ru /C (Sch em e 13).197 Obviou sly,
S c h e m e 13. Ox id a tio n o f P a n to y l La c to n e in
1,2-D ic h lo ro be n ze n e w ith Ru O 2 xH 2 O (a t 453 K)
a n d 5% Ru /C (a t 446 K)
con t in u ou s for m a t ion of t h e copr odu ct wa t er is su fficien t t o m a in t a in t h e h ydr a t ed st a t e a n d t h e oxida t ion a ct ivit y of r u t h en iu m dioxide, even a t a r ou n d
450 K.
A n ovel a ppr oa ch is t h e syn t h esis of r u t h en iu m
oxide n a n oclu st er s in t h e su per ca ges of fa u ja sit e
zeolit e (10% Ru O 2 /F AU).262 On a ver a ge, t h e r u t h enium oxide clusters homogeneously distributed in the
r igid zeolit e fr a m ewor k con t a in ed on ly five Ru a t om s,
a n d t h eir size wa s a bou t 1.3 n m . St r on g in t er a ct ion s
between RuO 2 chains a nd framework Si -O functions
st a bilized t h e oxide n a n opa r t icles du r in g t h e h ydr ot h er m a l syn t h esis (F igu r e 8). Th e r ecycla ble ca t a lyst
wa s a ct ive (TOF ) 0.5-8.5 h -1 ) a n d h igh ly select ive
(>99%) in t h e oxida t ive syn t h esis of ben za ldeh yde,
cycloh exa n on e, 2-cycloh exen -1-on e, cr ot on a ldeh yde,
F ig u re 8. St r u ct u r e of Ru O 2 in t h e su per ca ges of fa u ja sit e

zeolit e.262
1-h ept a n a l, a n d 2-h ept a n on e. In com pa r a t ive exper im en t s, in t h e oxida t ion of ben zyl a lcoh ol, 10% Ru O 2 /
F AU a ffor ded 6-fold h igh er yield t o ben za ldeh yde
t h a n bu lk Ru O 2 xH 2 O. Th is r a t e en h a n cem en t is
pa r t icu la r ly im pr essive wh en con sider in g t h e pr oba ble diffu sion lim it a t ion in side t h e zeolit e pa r t icles.
It wa s dem on st r a t ed t h a t t h e n a r r ow ch a n n els of
fa u ja sit e zeolit e a r ou n d t h e r u t h en iu m oxide clu st er s
st r on gly in flu en ced t h e r ea ct ivit y of bu lky su bst r a t es
(sh a pe select ivit y). In t h e com pet in g oxida t ion of
ben zyl a lcoh ol a n d 9-h ydr oxyflu or en e, on ly ben zyl
a lcoh ol wa s oxidized, t h ou gh bu lk Ru O 2 xH 2 O a ffor ded t h e fa cile oxida t ion of bot h su bst r a t es. Th ese
exper im en t s pr ovide a ddit ion a l eviden ce for t h e loca t ion of r u t h en iu m oxide pa r t icles in side t h e zeolit e
su per ca ges.
Syn t h esis of m ixed oxides by co-pr ecipit a t ion is
a n ot h er a ppr oa ch t o t u n e t h e ca t a lyt ic pr oper t ies of
r u t h en iu m oxide. A r em a r ka ble syn er gism wa s obser ved in t h e oxida t ion of cin n a m yl a lcoh ol by a ddit ion of Co (Co/Ru a t om ic r a t io 1.5; TOF u p t o 38
h -1 ).254 P r im a r y a liph a t ic a lcoh ols wer e less r ea ct ive
(TOF ) 1.3-5 h -1 ), a n d fu r t h er oxida t ion of a ldeh ydes t o ca r boxylic a cids cou ld be su ppr essed on ly
by a ddit ion of a r a dica l sca ven ger . Coba lt oxide a lon e
wa s in a ct ive u n der t h e sa m e con dit ion s, a n d t h e syn er gic effect of Co wa s a t t r ibu t ed t o a ct iva t ion of oxygen in r eoxida t ion of t h e r u t h en iu m h ydr ide species
for m ed a ft er deh ydr ogen a t ion of t h e su bst r a t e.
A sim ila r m u lt icom pon en t ca t a lyst is Ru 0.3 Co2 Ce
oxide.263 Th e bla ck powder syn t h esized by co-pr ecipit a t ion wa s a ct ive (TOF ) u p t o 13 h -1 ) a n d h igh ly
select ive in t h e oxida t ion of a r om a t ic a n d a llylic
a lcoh ols. Over 99% yields wer e obt a in ed in va r iou s
reactions, even in the synthesis of bulky aliphatic and
a r om a t ic a ldeh ydes a n d ket on es (e.g., 2-a da m a n t a n on e, diph en yl ket on e, 1-pyr en eca r boxa ldeh yde;
TOF ) 5-11 h -1 ). An in t er est in g fea t u r e of t h is
t h r ee-m et a l oxide is t h e oxida t ion of pr im a r y a liph a t ic a lcoh ols t o ca r boxylic a cids, a n d R,-pr im a r y
diols t o la ct on es, in good yields (Y ) 64-97%; TOF
) 0.7-2.5 h -1 ). Addit ion of a r a dica l sca ven ger
pr even t ed a ldeh yde oxida t ion , a n d a liph a t ic a ldeh ydes cou ld be pr epa r ed in qu a n t it a t ive yields.
Oxida tion of 1,4-pen ta n ediol (wh ich con ta in s pr im a r y
a n d secon da r y OH fu n ct ion s) a ffor ded m et h yl -bu t yr ola ct on e in 87% yield.
Ot h er effect ive Ru -ba sed m ixed oxides developed
for a lcoh ol oxida t ion in clu de Ru 0.35 Mn F e 1.65 O 4 264 a n d
Ru 0.45Mn F e 1.4Cu 0.15O x.265 Th e ca t a lyst s wer e design ed
u sin g fer r it e spin el (F e 2 Mn O 4 ) a s a m odel, in wh ich
F e is pa r t ia lly su bst it u t ed by Ru a n d Cu . Th e m u l-
t icom pon en t ca t a lyst s wer e pr epa r ed by co-pr ecipit a t ion fr om a qu eou s solu t ion s. Com posit ion a l va r ia t ion s pr oved t h a t Ru is by fa r t h e m ost a ct ive com pon en t . Th e yields wit h Ru 0.35 Mn F e 1.65 O 4 wer e excellen t in t h e oxida t ion of ben zylic, h et er oa r om a t ic,
a llylic, a n d bu lky cycloa liph a t ic a lcoh ols t o a ldeh ydes
a n d ket on es.264 In a ll r ea ct ion s, in clu din g t h e oxida t ion of sim ple a liph a t ic a lcoh ols su ch a s 1-oct a n ol,
t h e select ivit ies wer e a t lea st 99%. Th e ca t a lyst wa s
r eu sa ble wit h ou t sign ifica n t loss in a ct ivit y or select ivit y. Th e TOF s wer e m oder a t e (0.2-4.1 h -1 ), a n d a
C/S mass ratio over 1 wa s used, though the unusually
m ild r ea ct ion con dit ion s (r oom t em per a t u r e, a ir ) a r e
pr oba bly fa r fr om t h e opt im u m .
Su ccessfu l a pplica t ion of con du ct in g lea d-r u t h en iu m a n d bism u t h -r u t h en iu m pyr och lor e oxides in
elect r oca t a lyt ic r ea ct ion s 266,267 in it ia t ed t h eir syn t h et ic a pplica t ion in a lcoh ol oxida t ion .268 Th e ca t a lyst s h a ve a n expa n ded la t t ice pyr och lor e st r u ct u r e
wit h t h e gen er a l com posit ion A2+x Ru 2-x O 6.5-7 , wh er e
A ) Bi or P b a n d 0 < x < 1. Gen er a lly, a n in cr ea sin g
su bst it u t ion (x) en h a n ces t h e ca t a lyt ic a ct ivit y.269
Oxida t ive st a bilit y of Ru -pyr och lor e oxides depen ds
on t h e a m ou n t of oxygen va ca n cies: a la r ge n u m ber
of oxygen defect s decr ea ses t h e st a bilit y.270 Th e bla ck
m a cr opor ou s m a t er ia ls fu n ct ion on ly in st r on gly
a lka lin e a qu eou s m edia .269,271
Ru t h en iu m pyr och lor e oxides wer e a ct ive u n der
m ild con dit ion s in t h e oxida t ive clea va ge of 1,2-cycloh exa n ediol.268,269 Select ivit y t o a dipic a cid (7099%) in cr ea sed a t h igh er C/S r a t ios, wh ich wa s best
a ch ieved in a con t in u ou s-flow t r ickle-bed r ea ct or . A
lim it a t ion of t h e m et h od is t h a t t h e ca t a lyst s a r e
a ct ive in sever a l ot h er oxida t ion r ea ct ion s, in clu din g
t h e oxida t ion of ket on es, pr im a r y a lcoh ols, a n d olefin s. H en ce, it is u n der st a n da ble t h a t Ru-pyr och lor e
oxides wer e n ot select ive in t h e oxida t ive clea va ge of
ca r boh ydr a t es a n d polysa cch a r ides.272,273
Th e pr oba ble m ech a n ism of diol clea va ge over a
P b-Ru pyr och lor e oxide in volves a ch ela t ed diol
in t er m edia t e coor din a t ed t o a P b IV sit e a t t h e ca t a lyst
su r fa ce (Sch em e 14).274 Reoxida t ion of t h e P b II sit e
is m edia t ed by t h e n eigh bor in g Ru dO la t t ice sit e.
S c h e m e 14. Ox id a tiv e Cle a v a g e o f a Vic in a l D io l by
Ru th e n iu m P y ro c h lo re Ox id e
2.3.2. Other Oxides

Most of t h e oxides com m on ly u sed in ga s-ph a se
oxida t ion s a r e ba r ely a ct ive ca t a lyst s wit h m olecu la r
oxygen u n der m ild con dit ion s, a n d r epor t s on t h eir
su ccessfu l a pplica t ion s in t h e liqu id ph a se a r e sca r ce.
An exa m ple is V2 O 5 su ppor t ed on TiO 2 , a well-kn own
ca t a lyst for ga s-ph a se a er obic oxida t ion of va r iou s
su bst r a t es.275-277 Th e m oder a t ely a ct ive m a t er ia l
a ffor ded good yield in t h e oxida t ion of 5-(h ydr oxymethyl)furfural to 2,5-furandicarboxaldehyde (Scheme
15).278 Th e pr efer r ed ca t a lyst con t a in ed m u lt ila yer
V2 O 5 on t h e su ppor t , a st r u ct u r e close t o t h a t of bu lk

S c h e m e 15. Ox id a tio n o f 5-Hy d ro x y m e th y lfu rfu ra l
w ith Air o v e r 15% V 2 O 5 /TiO 2 ,278 5% Ru /C, a n d 5%
P t/Al 2 O 3 22 Ca ta ly s ts
V2 O 5 . F or com pa r ison , su ppor t ed P t -gr ou p m et a l

ca t a lyst s pr odu ced t h e for m yl-ca r boxyl or dica r boxyl
der iva t ives in good yields.22,143
A br oa d r a n ge of oxides a n d m ixed oxides wer e
t est ed in t h e syn t h esis of et h yl pyr u va t e fr om et h yl
la ct a t e.279 Ma n y of t h em wer e su r pr isin gly a ct ive
a lr ea dy a t 403 K a n d con ver t ed et h yl la ct a t e a t a C/S
m a ss r a t io of on ly 0.0002. No bypr odu ct s for m ed on
Sn O 2 a n d Zr O 2 a t low con ver sion s, bu t t h e select ivit y
dr opped r a pidly wit h in cr ea sin g con ver sion , a n d even
t h e best ca t a lyst , Sn O 2 -MoO 3 , ga ve on ly 50% yield.
Mn O 2 is com m on ly u sed a s a n oxidizin g a gen t in a
la r ge excess, bu t u lt r a son ica t ion of t h e a ct iva t ed
oxide (Mn O 2 xH 2 O) pr ovided a ca t a lyt ica lly a ct ive
m a t er ia l. 280 Diph en ylm et h a n ol wa s t r a n sfor m ed t o
ben zoph en on e wit h on ly 0.1 m ola r equ iva len t of
a ct ive m a n ga n ese dioxide a t 363 K in oxygen , bu t
oxida t ion of cin n a m yl a lcoh ol wa s slu ggish , a n d n o
reaction occurred with 2-octanol. It was assumed that
t h e su r fa ce OH gr ou ps wer e t h e a ct ive sit es on t h e
h ydr a t ed ca t a lyst .
H ydr ou s P dO wa s m oder a t ely a ct ive a n d select ive
in t h e oxida t ion of ben zyl a n d cin n a m yl a lcoh ols t o
a ldeh ydes.281 Syn t h esis of bin a r y oxides by a ddit ion
of Co3+, F e 3+, or Mn 3+ a ffor ded fa r m or e efficien t
h ydr a t ed bin a r y oxides (TOF ) 19-25 h -1 ). Non e of
t h e a dded com pon en t s wer e a ct ive a lon e, in t h e
a bsen ce of P dO. A disa dva n t a ge of t h ese co-pr ecipit a t ed m ixed oxides is t h e slow oxida t ion of a ldeh yde
t o ca r boxylic a cid, a side r ea ct ion t h a t cou ld n ot be
elim in a t ed even by t h e a ddit ion of a r a dica l sca ven ger , 2,6-di-tert-bu t yl-p-cr esol. Ot h er im por t a n t side
r ea ct ion s, t h e for m a t ion of ben zen e by deca r bon yla t ion of ben za ldeh yde a n d t h a t of 3-ph en yl-1-pr opa n ol
by t r a n sfer h ydr ogen a t ion of cin n a m yl a lcoh ol, in dica t ed t h a t t h e su bst r a t e a lcoh ol pr esu m a bly r edu ced
P dO t o m et a llic P d in t h e bin a r y oxides a n d t h e
a ct u a l ca t a lyst s wer e oxide-su ppor t ed P d 0 .281
2.4. Molecular Sieves

Va r iou s su bst it u t ed zeolit es, a lso t er m ed r edox
m olecu la r sieves, h a ve been t est ed in a lcoh ol oxida t ion in t h e liqu id ph a se, bu t m ost of t h em r equ ir e a
per oxide a s oxida n t .5,282-288 An except ion is a Cr -
substituted aluminophosphate, CrAlPO-5,289,290 which

ca t a lyzed a lcoh ol oxida t ion wit h oxygen in t h e pr esen ce of a t lea st 0.1 equ iv of TBH P (tert-bu t yl h ydr oper oxide). H owever , a t h or ou gh in vest iga t ion r evea led t h a t t h e r ea l a ct ive species wa s Cr , lea ch ed
in t r a ce a m ou n t s in t h e pr esen ce of oxida n t .6
Recently, a synthetic cryptomela ne-like manganese
oxide oct a h edr a l m olecu la r sieve, K-OMS-2, wa s
pr oposed a s a select ive ca t a lyst t h a t ca n u t ilize
m olecu la r oxygen .291 Th is m a t er ia l, wit h a com posit ion of KMn 8 O 16 n H 2 O, con t a in s on e-dim en sion a l
t u n n els wit h Mn O 6 oct a h edr a l bu ildin g blocks a n d
K + a s t u n n el ca t ion . Rela t ively sim ple syn t h esis
m et h ods a ffor d u p t o 250 m 2 g -1 BE T su r fa ce a r ea ,
t h ou gh t h e por e size is in t h e r a n ge 0.45-0.7
n m 291,292 sa st r on g lim it a t ion in t h e t r a n sfor m a t ion
of bu lky su bst r a t es. Oxida t ion cou ld be a cceler a t ed
by pa r t ia l r epla cem en t of K + by H + ion s t o for m
Br n st ed a cidic H -K-OMS-2. Th e a ct ivit y of H -KOMS-2 wa s, h owever , st ill low in t h e oxida t ion of
various simple aliphatic, cycloaliphatic, aromatic, and
a llylic a lcoh ols (TOF ) 0.035-0.5 h -1 ).292-294 Besides
t h e pr oba ble m a ss t r a n spor t lim it a t ion in t h e n a r r ow
por es, t h e low a ct ivit y m igh t be du e t o ca t a lyst
poison in g by wa t er , t h e on ly copr odu ct of t h e r ea ct ion s. Th e m a jor a dva n t a ge of t h e r ecycla ble ca t a lyst
is t h e excellen t select ivit y: a lwa ys 100% t o t h e
cor r espon din g a ldeh ydes a n d ket on es.
Th e la r ge kin et ic isot ope effect obser ved in t h e
oxida t ion of ben zyl a lcoh ol im plies t h a t r em ova l of
h ydr ogen fr om t h e R-C-a t om is t h e r a t e-con t r ollin g
st ep.293 As con cer n s t h e over a ll pr ocess, t h e r ea ct ion
obeys t h e Ma r s-va n Kr evelen m ech a n ism 295,296 son e
of t h e few exa m ples of t h is m ech a n ism in liqu idph a se oxida t ion r ea ct ion s. Rem ova l of t wo pr ot on s
fr om t h e or ga n ic su bst r a t e is a ccom pa n ied by a t woelect r on r edu ct ion of t h e Mn 4+-t ype Lewis a cidic sit es
(Sch em e 16). Th e Mn 2+ sit es a r e r eoxidized by m oS c h e m e 16. Me c h a n is m o f B e n zy l Alc o h o l
Ox id a tio n o n Ma n g a n e s e Ox id e Oc ta h e d ra l
Mo le c u la r S ie v e , K-OMS -2
lecu la r oxygen , a n d fa cile decom posit ion of t h e in t er m edia t e H 2 O 2 on t h e m olecu la r sieve pr odu ces
wa t er , t h e fin a l copr odu ct .293
2.5. Hydrotalcites
H ydr ot a lcit es (H T), t h a t is, Mg- a n d Al-h ydr oxyca r bon a t es wit h t h e for m u la Mg6Al2(OH )16CO 34H 2O,
a r e r ela t ively n ew m a t er ia ls in ca t a lysis.297-301 Th ese
a n ion ic cla ys con sist of ca t ion ic Br u cit e la yer s wit h
a n ion ic com pou n ds in t h e in t er la yer . Two- a n d t h r eeva len t ca t ion s ca n be in t r odu ced in t o t h e Br u cit e
la yer , a n d t h e a n ion s ca n a lso be va r ied. Th e gen er a l
for m u la of h ydr ot a lcit e-like com pou n ds (a lso t er m ed
la yer ed dou ble h ydr oxides, LDH ) is [M II M III A-H T
) M II 1-xM III x(OH )2]An -x/n m H 2O, wh er e A is a n a n ion .
A r ecycla ble ca t a lyst , Ru -Mg-Al-H T {Ru 0.5 Mg 6 Al 2 (OH )16 CO 3 }, sh owed m oder a t e a ct ivit y (TOF )
0.3-1.9 h -1 ) in t h e oxida t ion of a ct iva t ed a lcoh ols
Mallat and Baiker
wit h m olecu la r oxygen . 302 Th e C/S m a ss r a t io wa s

r a t h er h igh , a r ou n d 1, bu t t h e select ivit y t o ca r bon yl
compounds was usually high, and quantitative transfor m a t ion of som e a r om a t ic a lcoh ols wa s a ch ieved.
Fu rth er oxida tion of a rom a tic a ldeh ydes to ca rboxylic
a cids wa s n ot det ect ed. P r im a r y a lcoh ols wer e t r a n sfor m ed fa st er t h a n secon da r y a lcoh ols. Th e ca t a lyst
h a vin g 7.3 wt % Ru in t h e Br u cit e la yer wa s su per ior
t o m a t er ia ls in wh ich ot h er t r a n sit ion m et a ls (Ni, F e,
Mn , V, or Cr ca t ion s) wer e in t r odu ced a s a ct ive
species. Va r ia t ion of t h e a n ion in t h e in t er la yer of
Ru -Mg-Al-H T sh owed t h a t t h e ca t a lyst wit h ca r bon a t e ion s wa s t h e m ost a ct ive. It h a s been a ssu m ed
t h a t t h e a ct ive sit es a r e h ydr oxyl gr ou ps a ssocia t ed
t o Ru ca t ion s (Sch em e 17).300,302 In t h e fir st st ep, a
S c h e m e 17. Me c h a n is m o f Alc o h o l Ox id a tio n o v e r
Ru -Co -Al-HT 300
ba sic OH gr ou p ca t a lyzes t h e for m a t ion of Ru -a lkoxide, a n d t h e su bsequ en t -elim in a t ion gives t h e ca r bon yl com pou n d. Th e r edox cycle is com plet ed by r eoxida t ion of t h e r edu ced Ru species wit h m olecu la r
oxygen .
F u r t h er su bst it u t ion of Mg ion s wit h Co or Mn ion s
in Ru -Mg-Al-H T led t o a pr om in en t syn er gic effect .303
Th e m ost a ct ive a n d select ive ca t a lyst wa s Ru -CoAl-H T, wh ich oxidized a va r iet y of a r om a t ic a n d
a liph a t ic a lcoh ols t o a ldeh ydes a n d ket on es in good
t o excellen t yields (TOF ) 0.8-14 h -1 ). Ru -Co-Al-H T
wa s a ct ive a lso in t h e oxygen a t ion of a r om a t ic com pou n ds a t ben zylic position s.300 For exa m ple, fluorene
a n d xa n t h en e wer e t r a n sfor m ed a t 343 K t o t h e
cor r espon din g ket on es in 93-98% yield. Th e syn er gic
effect bet ween Ru a n d Co ion s wa s a t t r ibu t ed t o t h e
for m a t ion of h igh er oxida t ion st a t e Ru ion s.300,303
In t er a ct ion bet ween Ru a n d Co wa s eviden ced by
XP S by a sh ift in t h e elect r on ic st a t e of Ru .
A similar catalyst, Ru-Cu-Al-HT, showed low activit y (TOF < 1 h -1 ) wit h m olecu la r oxygen in t h e
a bsen ce of a co-oxida n t , su ch a s P h IO or t et r a bu t yla m m on iu m per ioda t e.304 On t h e ba sis of XP S a n a lysis, a n in t er a ct ion wa s a ssu m ed bet ween t h e t wo
r edox cou ples Cu 0/Cu 2+ a n d Ru 4+/Ru 6+ du r in g a lcoh ol
oxida t ion .
Th ere a re severa l h ydrota lcite-like ma teria ls which
wer e developed for t h e a er obic oxida t ion of a lcoh ols
a n d do n ot con t a in Ru a s t h e a ct ive species. F or
exa m ple, t h e r ecycla ble ca t a lyst Ni-Al-H T 305 a ffor ded
good yields in t h e t r a n sfor m a t ion of a r om a t ic a n d
a llylic a lcoh ols t o t h e cor r espon din g ca r bon yl com pou n ds, bu t t h e r ea ct ion s wer e slow, even a t a C/S
m a ss r a t io a bove 2. Secon da r y ben zylic a lcoh ols wer e
m or e r ea ct ive t h a n pr im a r y a lcoh ols, a n d su bst it u t ed

ben zylic a lcoh ols r ea ct ed fa st er t h a n ben zyl a lcoh ol,
in depen den t of t h e elect r on -wit h dr a win g or elect r on -r elea sin g ch a r a ct er of t h e fu n ct ion . Th e ca t a lyst
wa s poor ly a ct ive in t h e oxida t ion of pr im a r y a n d
secon da r y a liph a t ic a lcoh ols. Th e ca t a lyt ica lly a ct ive
species is pr oba bly Ni in a ssocia t ion wit h a lu m in u m
oxide.305
Nu m er ou s h ydr ot a lcit e-like m a t er ia ls con t a in in g
Co, Cu , Cr , F e, Mn , Ni, a n d Zn wer e t est ed in t h e
solvent-free oxida t ion of ben zyl a lcoh ol. 306 At the high
r ea ct ion t em per a t u r e of 483 K, ben za ldeh yde for m a t ion wa s on ly a bou t 5 t im es fa st er wit h t h e m ost
a ct ive ca t a lyst , Cu -Cr -H T, t h a n t h e u n ca t a lyzed
oxida t ion r ea ct ion .
select ive in t h e a er obic oxida t ion of pr im a r y a m in es

t o n it r iles 325 a n d or ga n osila n es t o sila n ols,326 a n d in
t h e r a cem iza t ion of ch ir a l a lcoh ols.324
A sim ila r ca t a lyst , P d-h ydr oxya pa t it e, wa s pr epa r ed by in t er a ct in g st oich iom et r ic h ydr oxya pa t it e
Ca 10 (P O 4 )6 (OH )2 wit h a solu t ion of P dCl 2 (P h CN)2 .327
Th e ca t a lyst con t a in in g on ly 0.3 wt % P d wa s fa r
m or e a ct ive t h a n t h e Ru a n a logu e (TOF s u p t o 500
h -1 ) a n d a ffor ded good yields t o va r iou s a ldeh ydes
a n d ket on es. Th e u n u sed ca t a lyst con t a in ed m on omeric PdCl2 species grafted by chemisorption onto the
a pa t it e su r fa ce (F igu r e 10). An a lysis of t h e st r u ct u r e
2.6. Phosphates
H ydr oxya pa t it es 307,308 ga in in cr ea sin g in t er est in
ca t a lysis du e t o t h eir u n iqu e pr oper t ies.309-311 H ydroxyapatites can be synthesized by various methods,
including simple co-precipitation,308,312-315 and a great
va r iet y of n ew m a t er ia ls ca n be developed by su r fa ce
m odifica t ion 316-318 or by u sin g t h e ion -exch a n ge a bilit y of a pa t it es.319-321 A Ru -con t a in in g h ydr oxya pa t it e
(Ru H Ap), pr epa r ed by pa r t ia l r epla cem en t of Ca 2+
ion s wit h Ru 3+, ga ve h igh yields in t h e syn t h esis of
a r om a t ic, h et er eoa r om a t ic, R,-u n sa t u r a t ed, a n d a liph a t ic ca r bon yl com pou n ds.322 Th e st a ble a n d r ecycla ble ca t a lyst wa s m oder a t ely a ct ive; t h e C/S m a ss
r a t io wa s a r ou n d 1, despit e t h e h igh Ru con t en t (17
wt %). In t er est in gly, a t 333 K, Ru H Ap oxidized
1-oct a n ol t o oct a n a l in 94% yield wit h ou t fu r t h er
oxida t ion t o ca r boxylic a cid, a n d a t 353 K, oct a n oic
a cid for m ed in 82% yield. P r im a r y a liph a t ic a lcoh ols
wer e pr efer en t ia lly oxidized in t h e pr esen ce of secon da r y a lcoh ols. Th is ch em oselect ivit y r esem bles t h e
pr oper t ies of Ru Cl 2 (P P h 3 )3 323 a n d con t r a st s t h ose of
bu lk Ru ca t a lyst s (Ru O 2 , Ru /Al 2 O 3 ), in dica t in g t h e
pr esen ce of isola t ed Ru ca t ion s a s a ct ive species in
Ru H Ap.322 Th e a ct ive sit es a r e pr oba bly m on om er ic
Ru ca t ion s su r r ou n ded by O a n d Cl, 322 t h ou gh n o Cl
h a s been fou n d r ecen t ly in a sim ila r ca t a lyst . 324 Ru
is st r on gly coor din a t ed t o t h e a pa t it e fr a m ewor k, a n d
t h is in t er a ct ion pr even t s lea ch in g of t h e a ct ive species. Th e st r u ct u r e sh own in F igu r e 9 expla in s wh y
F ig u re 9. Isola t ed Ru 3+ species wit h t h e n ea r est oxygen s

on t h e su r fa ce of h ydr oxya pa t it e, a s iden t ified by XANE S,
XP S, a n d E DX a n a lysis.
t h e a u t h or s cla ssified t h e m a t er ia l a s a su ppor t ed Ru

com plex.322 Accor din g t o t h eir m odel, t h e oxida t ion
is in it ia t ed by a liga n d exch a n ge bet ween t h e a lcoh ol
a n d t h e ch lor in e species a t t h e Ru sit e. Th e ca r bon yl
compound product is formed by -hydride elimination
fr om t h e Ru -a lcoh ola t e. In t er est in gly, t h e a pplica t ion r a n ge of Ru H Ap is qu it e br oa d: it is a ct ive a n d
F ig u re 10. St r u ct u r e of a s-syn t h esized P d-exch a n ged

h ydr oxya pa t it e (left ) a n d it s r est r u ct u r in g t o a su ppor t ed
m et a l ca t a lyst (r igh t ) u n der a lcoh ol oxida t ion con dit ion s.
of t h e r ecover ed sa m ple r evea led, h owever , t h a t

du r in g r ea ct ion P d 2+ wa s r edu ced t o P d 0 by t h e
r ea ct a n t a lcoh ol a n d t h e a ct u a l ca t a lyt ic species wer e
a pa t it e-su ppor t ed P d n a n opa r t icles wit h a n a ver a ge
dia m et er of 4 n m . Accor din gly, t h is ca t a lyst belon gs
t o t h e cla ss of su ppor t ed P t -gr ou p m et a ls discu ssed
in sect ion 2.1.
P d 2+ wa s r esist a n t a ga in st r edu ct ion wh en a n on st oich iom et r ic, Ca -deficien t h ydr oxya pa t it e, Ca 9 (H P O 4 )(P O 4 )5 (OH ), wa s a pplied for ion -exch a n ge
u sin g t h e sa m e m et h od a s descr ibed a bove. In t er est in gly, t h is ca t a lyst wa s a ct ive in H eck a n d Su zu ki
r ea ct ion s bu t n ot in a lcoh ol oxida t ion wit h m olecu la r
oxygen .327
Recen t ly, Cu 2 (OH )P O 4 a n d Cu 4 O(P O 4 )2 h a ve been
pr oposed for t h e a qu eou s-ph a se a er obic oxida t ion of
ben zyl a lcoh ol a n d cycloh exa n ol.328 Th e rea ct ion r a t es
wer e low, a n d t h e h igh est yield of t h e cor r espon din g
ca r bon yl com pou n ds wa s on ly 12%.
3. Heterogenized Metal Complexes

F or im m obiliza t ion of solu ble ca t a lyst s a ct ive
wit h m olecu la r oxygen , va r iou s con ven t ion a l t ech n iqu es 329-333 h a ve been a pplied, in clu din g in cor por a t ion of m et a l ion s in t o la t t ices, a dsor pt ion on a
h igh su r fa ce a r ea su ppor t , ion exch a n ge, cova len t
bon din g via t et h er s, a n d en t r a pm en t in t o a por ou s
su ppor t . As con cer n s t h e st a bilit y of t h ese h ybr id
ca t a lyst s, sim ple a dsor pt ion on a su ppor t ca n r a r ely
pr even t lea ch in g of t h e a ct ive species, a n d t h e oxida t ive st a bilit y of polym er ic su ppor t s is fr equ en t ly
in su fficien t .
In som e ca ses, n ew m a t er ia ls a r e design ed a n d
descr ibed a s su ppor t ed m et a l com plexes, bu t t h e
pu blish ed da t a r evea l t h a t , du r in g pr epa r a t ion , t h e
m et a l ion s wer e r edu ced t o m et a l (M 0 ). F or exa m ple,
a polyt it a za n e-pla t in u m com plex on m a gn esiu m
oxide su ppor t wa s su ggest ed a s a su ppor t ed com plex
ca t a lyst for a lcoh ol oxida t ion .334-337 Th e bla ck color
of t h e fin a l m a t er ia l a n d pa r t icu la r ly t h e XP S da t a
in dica t e, h owever , t h a t t h e ca t a lyst likely con t a in ed

sm a ll P t pa r t icles disper sed in t h e or ga n ic-in or ga n ic
m a t r ix. Accor din gly, t h ese m a t er ia ls belon g t o su ppor t ed P t -gr ou p m et a ls (sect ion 2.1) a n d will n ot be
discu ssed h er e.
3.1. Ru-Based Catalysts

A sim ple m et h od, a dsor pt ion on a ct iva t ed ca r bon ,
wa s a pplied for t h e h et er ogen iza t ion of Ru (P P h 3 )3 Cl 2 .338 Th e su ppor t en h a n ced t h e r ea ct ivit y of t h e
com plex in t h e oxida t ive clea va ge of vicin a l diols t o
a ldeh ydes, a n d fa ir t o good yields a t m oder a t e r a t es
(TOF ) 1.5-3 h -1 ) wer e a ch ieved in h ydr oph obic
solven t s. Th e h igh est select ivit y t o a ldeh ydes wa s
m ea su r ed in t h e oxida t ion of t er m in a l diols, t h ou gh
t h e t r a n sfor m a t ion of in t er n a l vicin a l diols t o a ldeh ydes a n d cyclic diols t o R,-dia ldeh ydes wa s
a lso efficien t . A disa dva n t a ge of t h e m et h od is t h e
h igh C/S m a ss r a t io (u p t o 4), a n d it is n ot kn own
wh et h er t h e ca t a lyst is t r u ly h et er ogen eou s a n d
r ecycla ble. F or m a t ion of a dia lkoxyr u t h en iu m com plex lea din g t o a six-m em ber ed t r a n sit ion st a t e wa s
pr oposed for t h e r ea ct ion m ech a n ism , a s illu st r a t ed
in Sch em e 18.
S c h e m e 18. Cle a v a g e o f 1,2-D io ls by Ru (P P h 3 ) 3 Cl 2 /C
v ia a S ix -Me m be re d -Rin g Tra n s itio n S ta te 338
A gen er a l deficien cy of t h e a dsor pt ion t ech n iqu e is

t h a t t h e m et a l in it s h igh est oxida t ion st a t e h a s
t h e lowest a ffin it y t o t h e su ppor t , r esu lt in g in con sider a ble lea ch in g of t h e a ct ive species du r in g oxida t ion .332 Th is lim it a t ion is illu st r a t ed by t h e oxida t ion of a lcoh ols wit h a n ot h er ca r bon -su ppor t ed Ru
com plex, [Ru Cl 2 (p-cym en e)]2 .339 Th e ca t a lyt ic pr oper t ies of t h e im m obilized com plex r em a in ed sim ila r t o t h ose of t h e h om ogen eou s com plex.340,341 Ben zylic a n d a llylic a lcoh ols wer e oxidized in t h e pr esen ce of 5 m ol % ba se, Cs 2CO 3. Rea son a ble r a t es (TOF
) 1.6-14 h -1 ) a n d good yields of t h e ca r bon yl
derivatives were achieved, but the C/S mass ratio was
well a bove 1, a n d m or e t h a n 30% of t h e com plex
lea ch ed ou t of t h e su ppor t du r in g a 9-fold ca t a lyst
r ecyclin g t est .
P olyoxom et a la t es 342-346 a r e pr oven ca t a lyst s of
oxida t ion a n d deh ydr ogen a t ion r ea ct ion s. Th ey a r e
su fficien t ly st a ble, possess h igh oxida t ion pot en t ia l,
a n d a r e r eoxidized by m olecu la r oxygen . An effect ive
h et er ogen eou s oxida t ion ca t a lyst , Ru -su bst it u t ed
silicot u n gst a t e, [(n -C 4 H 9 )4 N]4 H [SiW 11 Ru (H 2 O)O 39 ]
2H 2 O, wa s syn t h esized by t h e r ea ct ion of Ru Cl 3 wit h
t h e polyoxom et a la t e in a n or ga n ic solven t .347 Th e
ca t a lyst wa s in solu ble in va r iou s wea kly pola r or ga n ic solven t s a n d cou ld be r ecycled wit h ou t a n y
sign ifica n t loss in a ct ivit y. A st r on g syn er gic effect
wa s obser ved bet ween t h e Ru 3+ a ct ive sit e a n d t h e
Mallat and Baiker
polyoxom et a la t e [SiW 11 O 39 ]8-, a llowin g fa st r ea ct ion

(TOF ) 15-23 h -1 ) even a t low C/S r a t ios of on ly a
few weigh t per cen t . Va r iou s a liph a t ic, cycloa liph a t ic,
a n d a r om a t ic ket on es wer e pr epa r ed in 67-99%
yield. Oxida t ion of pr im a r y a liph a t ic a n d a r om a t ic
a lcoh ols wa s slower a n d ga ve a m ixt u r e of a ldeh yde
a n d ca r boxylic a cid. Oxida t ion of a llylic a lcoh ols
ba r ely pr oceeded. In con t r a st , t h e ca t a lyst wa s a ct ive in t h e oxida t ion of som e a lka n es, su ch a s a da m a n t a n e.
At t a ch in g liga n ds t o a n in solu ble polym er su ppor t
is a popu la r st r a t egy t o h et er ogen ize solu ble com plexes, bu t it h a s n ever wor ked ver y well. A r ecen t
exa m ple is t h e im m obiliza t ion of a Ru (III)-Sch iff
ba se com plex on t h e su r fa ce of a ch lor om et h yla t ed
st yr en e-divin ylben zen e cr oss-lin ked copolym er via
sequ en t ia l a t t a ch m en t of et h ylen edia m in e, sa licyla ldeh yde, a n d Ru Cl 3 (F igu r e 11).348,349 No bypr odu ct
F ig u re 11. P olym er -a n ch or ed Ru (III)-Sch iff ba se com plex.349
wa s det ect ed in t h e oxida t ion of ben zyl a lcoh ol t o

ben za ldeh yde, bu t a bou t 35% of Ru wa s lost du r in g
t h e lea ch in g t est wit h in less t h a n 6 h .
P er r u t h en a t e a n ch or ed t o a n Am ber list a n ion exch a n ge r esin via qu a t er n a r y a m m on iu m gr ou ps
wa s or igin a lly developed a s a clea n oxida n t .350 La t er
it wa s sh own t h a t it ca n a lso be u sed a s a ca t a lyst
wit h oxygen for t h e t r a n sfor m a t ion of pr im a r y a lcoh ols t o pu r e a ldeh ydes (Sch em e 19).351 Non a ct iva t ed
S c h e m e 19. Ox id a tio n o f Alc o h o ls by a
P e rru th e n a te S u p p o rte d o n a P o ly m e r (Am be rlis t
An io n -Ex c h a n g e Re s in ) 351
a n d secon da r y a lcoh ols r ea ct ed m or e slowly. F u r t h er

oxida t ion of a ldeh ydes t o ca r boxylic a cids wa s n ot
det ect ed, even in t h e oxida t ion of a liph a t ic a lcoh ols.
Oxida t ion of t er t ia r y a m in o a lcoh ols a n d epoxya lcoh ols t o a ldeh ydes ga ve 90-95% yields. In t h e
fa st est r ea ct ion , in t h e oxida t ion of ben zyl a lcoh ol, a
TOF of 20 h -1 wa s a ch ieved, t h ou gh a t a C/S m a ss
r a t io of over 9sa va lu e ch a r a ct er ist ic of st oich iom et r ic oxida n t s r a t h er t h a n ca t a lyst s. A fu r t h er lim it a tion to practical application is the difficulty of catalyst
r ecyclin g, likely du e t o oxida t ive degr a da t ion of t h e
polym er ic su ppor t .352
In a soph ist ica t ed a ppr oa ch , per r u t h en a t e wa s
im m obilized a s a t et h er ed com plex on a m or e st a ble
in or ga n ic m a t er ia l, m esopor ou s silica lit e MCM-41
(F igu r e 12).352 Th e ca t a lyst wa s r ecycla ble wit h ou t
a n y det ect a ble m et a l lea ch in g or declin e in t h e
ca t a lyt ic per for m a n ce. Va r iou s a r om a t ic a n d a llylic
a lcoh ols wer e oxidized qu a n t it a t ively t o a ldeh ydes a t
F ig u re 12. P er r u t h en a t e im m obilized on a m esopor ou s

silica lit e MCM-41.
353 K, a t a C/S m a ss r a t io of on ly 0.1. Th e pr esen ce

of CdC bon ds a n d Cl, MeO, Bn O, NO 2 , CF 3 , or F
fu n ct ion s in t h e a r om a t ic r in g did n ot dist u r b t h e
r ea ct ion s. Secon da r y a liph a t ic a lcoh ols a n d a lken ols,
su ch a s cycloh exa n ol a n d cycloh exen ol, did n ot r ea ct .
Th ou gh t h e a pplica t ion r a n ge is n ot br oa d, t h is is t h e
m ost a ct ive h et er ogen ized h om ogen eou s ca t a lyst for
t h e oxida t ion of a lcoh ols wit h m olecu la r oxygen ,
a ffording TOF values up to 170 h -1. Even distribution
of t h e a ct ive species on t h e su ppor t su r fa ce a n d t h e
a bsen ce of m a ss t r a n spor t lim it a t ion in t h e m esopor ou s st r u ct u r e of MCM-41 286 seem t o be cr it ica l t o
t h e good per for m a n ce.
A ver sa t ile r ou t e t o pr epa r e solid ca t a lyst s is
entrapment of a soluble transition-metal complex into
organically modified sol-gel silica (ORMOSIL).353,354
Th e key st r u ct u r a l pr oper t ies of doped sol-gel m a t er ia ls, e.g., h ydr oph ilic-h ydr oph obic ch a r a ct er a n d
por e size dist r ibu t ion , ca n be t a ilor ed a ccor din g t o
t h e r equ ir em en t of t h e r ea ct ion . A gen er a l lim it a t ion
of t h e m et h od is t h a t wide por es ca n n ot pr even t
lea ch in g of t h e a ct ive species, wh ile t oo n a r r ow por es
h a m per t h e diffu sion of bu lky su bst r a t es t o t h e a ct ive sit es. Recen t ly, t et r a -n -pr opyla m m on iu m per r u t h en a t e (TP AP ) wa s em bedded in t o m et h yl-m odified h ydr oph obic silica , u sin g m et h ylt r im et h oxysila n e a s a sol-gel pr ecu r sor .355 Th e lea ch -pr oof ca t a lyst possessed h igh su r fa ce a r ea a n d a n a r r ow
por e size dist r ibu t ion of a r ou n d 1.2 n m . Tr a n sfor m a t ion of a lcoh ols t o ca r bon yl com pou n ds wa s fa st
on ly in t h e ca se of ben zyl a lcoh ol (TOF s in t h e r a n ge
1-13 h -1 ).
3.2. Pd-Based Catalysts

There is a n increa sing interest in the synth esis a n d
ca t a lyt ic a pplica t ion of (h et er ogen ized) liga n d-st a bilized gia n t clu st er s t h a t m a y be con sider ed a s m odels
of su ppor t ed m et a l ca t a lyst s, or a s a lin k bet ween
h om ogen eou s a n d h et er ogen eou s ca t a lysis. 356-361 Th e
gia n t P d clu st er s dissolve in com m on solven t s a n d
a ct a s h om ogen eou s ca t a lyst s,362 t h ou gh t h ey ca n be
immobilized on a support to produce a heterogeneous,
ea sily r ecycla ble ca t a lyst .
In t h e fir st a pplica t ion t o h et er ogen eou sly ca t a lyzed oxida t ion of a lcoh ols wit h m olecu la r oxygen , a
five-sh ell P d clu st er , P d 561 ph en 60 (OAc)180 (ph en )
1,10-ph en a n t r olin e), wa s im m obilized on TiO 2 wh ile
pr eser vin g t h e or igin a l st r u ct u r e a n d size (ca . 3
n m ) of t h e pr ecu r sor .363,364 Th e clu st er con t a in ed
P d 0 a t om s in t h e in n er pa r t a n d ca t ion ic species (P d +
a n d P d 2+) on t h e su r fa ce, st a bilized by ph en liga n ds
a n d OAc a n ion s. Th e ca t a lyst wa s r eu sa ble, wit h
som e loss in yield a n d select ivit y. Va r iou s pr im a r y
a llylic a lcoh ols wer e oxidized in AcOH t o R,-u n sa t u r a t ed a ldeh ydes in u p t o 99% yield, a t good r a t es
(TOF ) 0.3-15 h -1 ). Th e r ea ct ion s wer e slower in
ben zen e, bu t est er ifica t ion of ger a n iol cou ld be elim in a t ed.
Th e r ea ct ion m ech a n ism is a ssu m ed t o be deh ydr ogen a t ion of t h e a llylic a lcoh ol coor din a t ed t o a
ca t ion ic P d species, followed by oxida t ion of t h e
su r fa ce h ydr ide wit h oxygen t o for m wa t er . Th e
su ppor t ed clu st er sh owed low a ct ivit y for t h e oxida t ion of secon da r y a llylic a n d ben zylic a lcoh ols, wh ich
wa s a t t r ibu t ed t o st er ic cr owdedn ess a r ou n d t h e P d
ca t ion s. Isom er iza t ion a n d h ydr ogen a t ion of t h e
substrate on reduced surface sites were also observed.
A h ydr ogen t r ea t m en t in a cet on it r ile r em oved t h e
ph en liga n ds fr om t h e su r fa ce of P d 561 ph en 60 (OAc)180 /
TiO 2 a n d decr ea sed t h e r ea ct ivit y of t h e ca t a lyst
by a fa ct or of 5.364 Clea r ly, t h e ph en liga n ds pla y
a n im por t a n t yet u n kn own r ole in t h e oxida t ion
pr ocess.
Tr ea t m en t of P d 4 ph en 2 (CO)2 (OAc)4 wit h Cu (NO 3 )2
in t h e pr esen ce of oxygen ga ve a m on odisper sed
eigh t -sh ell n a n oclu st er wit h t h e a ppr oxim a t e com posit ion of P d 2060 (NO 3 )360 (OAc)360 O 80 a n d a n a ver a ge size of 3.8 n m .365 Th e m a t er ia l, im m obilized on
TiO 2 , a ffor ded h igh yields in t h e oxida t ion of pr im a r y a r om a t ic a llylic a lcoh ols (TOF u p t o 20 h -1 )
a n d ben zylic a lcoh ols (TOF ) 3 h -1 ) t o t h e cor r espon din g a ldeh ydes. E lect r on -wit h dr a win g gr ou ps
r et a r ded t h e r ea ct ion , a n d oxida t ion of sa t u r a t ed
a lcoh ols (1- a n d 2-oct a n ol) ba r ely occu r r ed. A com pa r ison of P d 2060 (NO 3 )360 (OAc)360 O 80 a n d P d 561 ph en 60 (OAc)180 n a n oclu st er s r evea led sign ifica n t differ en ces
in t h eir r ea ct ivit y t owa r d a llylic a n d ben zylic a lcoh ols.365
A pa lla diu m -pyr idin e com plex, {P d(OAc)2 (py)2 },
wa s im m obilized on t h e ext er n a l su r fa ce of h ydr ot a lcit e by a sim ple a dsor pt ion st ep.366-369 Th e h ydr otalcite-supported Pd(II) catalyst was active in a broad
r a n ge of a lcoh ol oxida t ion r ea ct ion s (TOF u p t o 10
h -1 ) a n d ga ve good yields t o a ldeh ydes a n d ket on es.
Th e ca t a lyst wa s, h owever , r a t h er u n st a ble, a n d P d 2+
wa s ea sily r edu ced t o P d 0 pa r t icles wh en t h e a lcoh ol
con cen t r a t ion (r edu cin g a gen t ) or t h e r ea ct ion t em per a t u r e exceeded a cer t a in lim it .369 Besides, t h e
oxida t ion wa s slu ggish a n d in com plet e wit h ou t a ddit ion of a t lea st 4 equ iv of pyr idin e t o P d(II).
Appa r en t ly, t h is h et er ogen iza t ion m et h od wa s n ot
fu lly su ccessfu l.
3.3. V- and Mo-Containing Catalysts

(Heteropolyoxometalates)
The importance of polyoxometalates and heteropolya cids in ca t a lyt ic oxida t ion r ea ct ion s 342-346 h a s been
br iefly discu ssed in a pr eviou s sect ion in con n ect ion
wit h Ru -ba sed ca t a lyst s. Th e pr esen ce of Ru is n ot a
r equ ir em en t for oxida t ion a ct ivit y. A h et er ogen ized,
st a ble, a n d r eu sa ble ca t a lyst wa s pr epa r ed by im pr egn a t ion of a m ixed-a dden da h et er opolya n ion sa lt
on t o a ct iva t ed ca r bon (10 wt % Na 5 P Mo2 V2 O 40 /C).346
Mallat and Baiker
Ta ble 1. Ox id a tio n o f Alip h a tic Alc o h o ls to Ald e h y d e s
su bst r a t e
ca t a lyst
T, K
solven t
TOF , h -1
Y, %
S, %
r ef
1-oct a n ol
1-oct a n ol
1-oct a n ol
1-oct a n ol
1-oct a n ol
1-dodeca n ol
1-dodeca n ol
5%P t -1%Bi/Al 2 O 3
Ru 0.35 Mn F e 1.5 Cu 0.15 O x
Ru 3+-h ydr oxya pa t it e
P r 4 N +Ru O 4 -/or m osil(SiO 2 )
Ru O 4 -/polym er
Pt
Ru Co1.5 O x
333
295
333
348
358
333
383
P h CH 3
P h CH 3
P h CH 3
P h CH 3
P h CH 3
C 7 H 16
P h CH 3
142
0.2
0.4
1
1.1
13
1.3
76
51
94
70
91
77
50
85
100
99
100
100
93
189
264
322
355
351
146
254
Ta ble 2. Ox id a tio n o f B e n zy l Alc o h o l to B e n za ld e h y d e
ca t a lyst
T, K
solven t
TOF , h -1
Y, %
S, %
r ef
0.5% P d/Al 2 O 3
0.3% P d/h ydr oxya pa t it e
1.4% Ru /Al 2 O 3
Ru O 2 xH 2 O
10% Ru O 2 /F AU zeolit e
Ru 0.35 Mn F e 1.5 Cu 0.15 O x
Ru 0.3 Co2 CeO x
H -K-OMS-2
Ru -Mg-Al-h ydr ot a lcit e
Ru -Co-Al-h ydr ot a lcit e
[Ru Cl 2 (p-cym en e)]2 /C
Ru O 4 -/polym er
NR 3 +Ru O 4 -/MCM-41
P d 2060 (NO 3 )360 (OAc)360 O 80 /TiO 2
Na 5 P Mo10 V2 O 40 /C
353
363
356
353
353
295
333
383
333
333
353
383
348
353
348
333
373
scCO 2
P h CF 3
P h CF 3
P h CH 3
P h CH 3
P h CH 3
P h CF 3
P h CH 3
P h CH 3
P h CH 3
P h CH 3
P h CH 3
P h CH 3
P h CH 3
P h CH 3
AcOH
P h CH 3
1585
500
40
1.4
8.5
3.4
10
0.5
1.1
9.3
2
4.7
20
170
13
3
4.5
87
99
>98
16
>99
95
>99
97
95
96
>99
92
>95
100
100
92
97
95
>99
100
>99
100
>99
100
97
96
>99
100
100
100
97
100
371
327
29
262
262
264
263
292
302
303
322
339
351
352
355
365
346
Som e a r om a t ic pr im a r y a n d secon da r y a lcoh ols wer e

select ively oxidized t o ca r bon yl com pou n ds in 9398% yield in t olu en e wit h ou t fu r t h er oxida t ion t o
a cids (Sch em e 20). It wa s a ssu m ed t h a t r eoxida t ion
S c h e m e 20. Ge n e ra lize d S c h e m e fo r Alc o h o l
Ox id a tio n w ith Ca rbo n -S u p p o rte d
N a 5 P Mo 10 V 2 O 40 346
1 du e t o t h e low m ola r con cen t r a t ion of t h e a ct ive

species in t h e ca t a lyst . Th e ca t a lyst s wer e a ct ive a lso
in t h e deh ydr ogen a t ion of ben zylic a m in es t o a ldeh ydes a n d ket on es in t wo st eps via t h e Sch iff ba se
in t er m edia t e.
Th e sa m e st r a t egy, gr a ft in g a n a m m on iu m m olybdova n a doph osph a t e on t o ca r bon , pr ovided a n effect ive a n d t r u ly h et er ogen eou s ca t a lyst , (NH 4 )5 H 6 P V8 Mo4 O 40 /C.370 Th e ca t a lyst ga ve 46-92% yields in t h e
oxida t ion of a llylic a n d ben zylic a lcoh ols t o ca r bon yl
com pou n ds u n der con dit ion s sim ila r t o t h ose descr ibed a bove.346 In t er est in gly, in a con t r ol r ea ct ion
t h e u n su ppor t ed h et er opolyoxom et a la t e wa s in a ct ive (Sch em e 21). Lim it a t ion s t o t h e a pplica t ion of
S c h e m e 21. Effe c t o f Ca rbo n S u p p o rt o n th e
Ox id a tio n Ac tiv ity o f (N H 4 ) 5 H 6 P V 8 Mo 4 O 40 370
of t h e ca t a lyst a n d n ot t h e deh ydr ogen a t ion st ep wa s

r a t e-lim it in g. Ar om a t ic a lcoh ols wit h elect r on -don a t in g or -wit h dr a win g su bst it u en t s r ea ct ed a t sim ila r
r a t es (TOF ) 4.5 h -1 ), except h ydr oxyben zyl a lcoh ols (n o yield). Oxida t ion of a liph a t ic secon da r y
a lcoh ols wa s slow a n d in com plet e, a n d pr im a r y
a lcoh ols wer e in er t . On ly 1 m ol % of t h e im m obilized ca t a lyst r ela t ive t o t h e su bst r a t e wa s u sed. Th is
r a t io, h owever , cor r espon ds t o a C/S m a ss r a t io over
t h is ca t a lyst a s a select ive a lcoh ol oxida t ion ca t a lyst a r e t h e n ecessa r y h igh C/S m a ss r a t io (u p t o 3)
a n d t h e good a ct ivit y of t h e m a t er ia l in t h e oxida t ion of a m in es, a lkyl-su bst it u t ed ph en ols, a n d a lka n es.370
be considered only as semiquantitative, since in many

ca ses t h e r ea ct ion con dit ion s a pplied a r e obviou sly
fa r fr om t h e opt im u m .
Ta ble 3. Ox id a tio n o f 2-Hy d ro x y be n zy l Alc o h o l to

S a lic y la ld e h y d e
4.1. Primary Alcohols to Aldehydes

ca t a lyst
T, K
TOF ,
h -1
Y, %
r ef
2% P t -3.6% Bi/C
1% P t /C + P b(OAc)2
318
303
8500
9440
97
90
372
81
Ta ble 4. Ox id a tio n o f 2-(Hy d ro x y m e th y l)p y rid in e
ca t a lyst
T, K
TOF ,
h -1
Y, %
S, %
r ef
Ru 0.35 Mn F e 1.5 Cu 0.15 O x

295
333
333
353
0.4
0.3
1.3
0.6
84
50
91
>99
99
76
92
>99
264
302
303
322
Ta ble 5. Ox id a tio n o f 2-(Hy d ro x y m e th y l)th io p h e n e
ca t a lyst
1.4% Ru /Al 2 O 3
Ru 0.3 Co2 CeO x
Ru 0.35 Mn F e 1.5 Cu 0.15 O x
H -K-OMS-2
T , K solven t
356
363
333
295
383
333
353
TOF ,
h -1 Y , % S , % r ef
P h CF 3 27
>98 >99 29
P h CF 3
6.9
99
- 327
P h CF 3 13
>99 >99 263
P h CH 3 3.1
97
99 264
P h CH 3 0.5 100 100 292
P h CH 3 14
91
91 303
P h CH 3 3
94
94 322
4. Oxidation of Alcohols on Various Catalysts: A

Comparison
It is som et im es difficu lt t o ju dge t h e ca t a lyt ic per for m a n ce of a n ew m a t er ia l. On e wa y is t o com pa r e
t h e va r iou s ca t a lyt ic m a t er ia ls t o t h e st a t e-of-t h e-a r t
ca t a lyst s in som e fr equ en t ly u sed t est r ea ct ion s. Th e
com pa r ison ba sed on t h e da t a in Ta bles 1-16 sh ou ld
Select ive oxida t ion of a liph a t ic a lcoh ols t o a ldeh ydes wit h m olecu la r oxygen is pr esu m a bly t h e m ost
dem a n din g t r a n sfor m a t ion . Th e m a jor it y of kn own
ca ta lysts a re poorly a ctive or possesses low select ivit y
in t h ese r ea ct ion s, a n d det a iled r esu lt s a r e r a r ely
r epor t ed. In t h e oxida t ion of 1-oct a n ol a n d 1-dodeca n ol (Ta ble 1), P t a n d pa r t icu la r ly a P t /Al 2 O 3
pr om ot ed by Bi a r e by fa r t h e m ost a ct ive m a t er ia ls,
t h ou gh t h ey a r e n ot ver y select ive. E ven t h e m oder a t e yield of 76-77% t o a n a liph a t ic a ldeh yde is n ot
t ypica l for P t -gr ou p m et a ls, sin ce t h ese ca t a lyst s a r e
h igh ly a ct ive in t h e deh ydr ogen a t ion of t h e h ydr a t ed
a ldeh yde a n d u su a lly pr odu ce t h e ca r boxylic a cid in
h igh yield (Sch em e 4).68 Wh en h igh select ivit y t o
a ldeh yde is cr it ica l, va r iou s Ru -con t a in in g ca t a lyst s
offer a bet t er ch oice.
P r im a r y a r om a t ic (ben zylic) a lcoh ols ca n be r ea dily
transformed to aldehydes that are relatively resistant
t o fu r t h er oxida t ion , a t lea st u n der m ild con dit ion s.
F or exa m ple, oxida t ion of ben zyl a lcoh ol, t h e m ost
com m on ly r epor t ed t est r ea ct ion , is ch a r a ct er ized by
excellen t select ivit ies a n d yields on a lm ost a ll ca t a lyst s (Ta ble 2). Ou t st a n din g ca t a lyst s a r e P d/Al 2 O 3 ,
P d/h ydr oxya pa t it e, a n d per r u t h en a t e su ppor t ed on
m esopor ou s silica t e MCM-41. P er r u t h en a t e is pa r t icu la r ly a t t r a ct ive wh en fu r t h er oxida t ion t o ben zoic
a cid h a s t o be a voided, t h ou gh syn t h esis of t h e
ca t a lyst via t et h er in g is dem a n din g.
Tr a n sfor m a t ion of 2-h ydr oxyben zyl a lcoh ol t o sa licyla ldeh yde is of pr a ct ica l im por t a n ce, a n d t h is
r ea ct ion is t h e fa st est a m on g a ll a lcoh ol oxida t ion
r ea ct ion s over solid ca t a lyst s (Ta ble 3). Th e ca t a lyst s
a n d r ea ct ion con dit ion s a r e discu ssed m a in ly in t h e
pa t en t lit er a t u r e. Th e best TOF s a r e close t o 10 000
h -1 over P t /C pr om ot ed by Bi or P b; t h e pr om ot ion is
ca r r ied ou t by sim ple a ddit ion of t h e pr om ot er m et a l
sa lt t o t h e r ea ct ion m ixt u r e. Su ppor t ed gold n a n o-
Ta ble 6. Ox id a tio n o f Cin n a m y l Alc o h o l to Cin n a m a ld e h y d e
ca t a lyst
T, K
solven t
TOF , h -1
Y, %
S, %
r ef
5% P t -0.8% Bi/Al 2 O 3
1.4% Ru /Al 2 O 3
Rh
Ru O 2 xH 2 O
Ru Co1.5 O x
Ru 0.35 Mn F e 1.5 Cu 0.15 O x
Ru 0.3 Co2 CeO x
H -K-OMS-2
[Ru Cl 2 (p-cym en e)]2 /C
Ru O 4 -/polym er
P d 561 ph en 60 (OAc)180 /TiO 2
P d 2060 (NO 3 )360 (OAc)360 O 80 /TiO 2
313
363
356
343
383
383
295
333
383
333
333
353
383
348
348
333
333
H 2 O + det er gen t
P h CF 3
P h CF 3
2-P r OH
P h CH 3
P h CH 3
P h CH 3
P h CF 3
P h CH 3
P h CH 3
P h CH 3
P h CH 3
P h CH 3
P h CH 3
P h CH 3
AcOH
AcOH
144
72
27
10
5
38
3.9
10
0.5
1.1
14
5.9
2
10
1.8
15
19
94
87
98
80
79
90
95
>99
95
95
94
99
80
>95
90
99
91
>98
98
96
79
94
100
>99
100
97
94
99
100
100
99
98
43
327
29
23
254
254
264
263
292
302
303
322
339
351
355
363
365
Mallat and Baiker
Ta ble 7. Ox id a tio n o f Ge ra n io l to Citra l
ca t a lyst
T,
K
5% P t -1% Bi/Al 2 O 3
1.4% Ru /Al 2 O 3
Rh
H -K-OMS-2
P d 561 ph en 60 (OAc)180 /TiO 2
333
356
343
383
333
333
353
333
solven t
TOF ,
h -1
Y,
%
S,
%
r ef
P h CH 3 13
>99 >99 189
P h CF 3
6
86 97 29
2-P r OH 10
71 85 23
P h CH 3
0.5
95 100 292
P h CH 3
0.5 100 100 302
P h CH 3
0.8
71 80 303
P h CH 3
2
85 94 322
PhH
0.4
70 100 363
pa r t icles a lso per for m well, t h ou gh t h e a ver a ge TOF

cou ld n ot be ca lcu la t ed.233
Mor e dem a n din g t est r ea ct ion s a r e t h e pa r t ia l
oxida t ion of t h e h et er oa r om a t ic a lcoh ols 2-(h ydr oxym et h yl)pyr idin e (Ta ble 4) a n d 2-(h ydr oxym et h yl)t h ioph en e (Ta ble 5). Th e yields a r e h igh , bu t t h e
a ct ivit y of t h e ca t a lyst s is u su a lly low. Most ca t a lyst s
con t a in ion ic or m et a llic Ru a s t h e a ct ive species. Th e
good per for m a n ce of Ru /Al2O 3 a n d P d/h ydr oxya pa t it e
in t h e syn t h esis of 2-for m ylt h ioph en e is su r pr isin g
in t h e ligh t of t h e well-kn own poison in g effect of
su lfu r com pou n ds on P t -gr ou p m et a ls.373-375 A com pa r ison of t h e da t a in Ta bles 2-5 sh ows t h a t r ela t ively sm a ll st r u ct u r a l ch a n ges ca n lea d t o dr a m a t ica lly differ en t ca t a lyst per for m a n ce. H en ce, a ssessm en t of t h e ca t a lyst s on t h e ba sis of t h ese sim ple t est
r ea ct ion s m a y be m islea din g.
Syn t h esis of R,-u n sa t u r a t ed a ldeh ydes fr om t h e
cor r espon din g a lcoh ols is a fa cile r ea ct ion wit h m ost
solid ca t a lyst s, sim ila r t o t h e oxida t ion of pr im a r y
ben zylic a lcoh ols. Ma n y ca t a lyst s give h igh yields a t
a r ea son a ble r a t e in t h e oxida t ion of, for exa m ple,
cin n a m yl a lcoh ol (Ta ble 6) a n d ger a n iol (Ta ble 7). In
bot h r ea ct ion s, t h e m ost a ct ive ca t a lyst s a r e su ppor t ed P t -gr ou p m et a ls. Am on g t h e n on m et a llic ca t a lyst s, Ru -Co m ixed oxide is a good ch oice, t h ou gh
som e ot h er Ru -ba sed ca t a lyst s give h igh er select ivit y
t o t h e R,-u n sa t u r a t ed a ldeh yde. Oxida t ion of ger a n iol t o tran s-cit r a l (a n d of n er ol t o cis-cit r a l) is
u su a lly h igh ly st er eoselect ive (E / Z or Z / E > 95/5,
respectively),23,263,264 though the values are not always
m en t ion ed.
4.2. Primary Alcohols to Acids

Th er e a r e ver y few t est r ea ct ion s com m on ly u sed
t o com pa r e differ en t t ypes of ca t a lyst s in t h e a lcoh ol
f ca r boxylic a cid t r a n sfor m a t ion . Addit ion a lly, fu r t h er oxida t ion of a ldeh ydes t o a cids is fr equ en t ly
con sider ed a s a n u n desir ed side r ea ct ion , a n d t h e
ca t a lyst s a n d con dit ion s a r e opt im ized in or der t o
a void t h is t r a n sfor m a t ion . Ta ble 8 com pa r es som e
ca t a lyst s in t h e oxida t ion of 1-oct a n ol a n d 2-ph en oxyet h a n ol. Th e Ru -ba sed m ixed oxide is n ot ver y
a ct ive bu t a ffor ds t h e fr ee ca r boxylic a cid in h igh
yield wit h ou t bypr odu ct for m a t ion in t h e n on a qu eou s m ediu m . P t -gr ou p m et a ls a r e a ct ive a n d select ive, t h ou gh on ly in a qu eou s a lka lin e m edia ; in t h e
a bsen ce of ba se, oxida t ion of t h e a ldeh yde in t er m edia t e is slow a n d t h e a ct ive sit es a r e pa r t ia lly blocked
by t h e st r on gly a dsor bin g ca r boxylic a cid.
P r om ot ed P t -gr ou p m et a ls a r e t h e m ost com m on ly
u sed ca t a lyst s for t h e oxida t ive syn t h esis of ca r boxylic a cids (a s sa lt s), in clu din g t h e oxida t ion of a br oa d
r a n ge of fu n ct ion a lized a lcoh ols 32,46,63,83,376 a n d polyh ydr oxy com pou n ds.11-15 A r ecen t in du st r ia lly im por t a n t exa m ple is t h e oxida t ion of a ch olin e sa lt or
h ydr oxide over 5 wt % P d/C t o give 90% yield t o
bet a in e:187,188,377
[Me 3 N +CH 2 CH 2 OH ]OH - + O 2 f
Me 3 N +CH 2 COO - + 2H 2 O (1)
Th e select ivit y of su ppor t ed Au is a lso excellen t in

t h e oxida t ion of a m in o a lcoh ols t o a m in o a cids.228
4.3. Secondary Alcohols

Oxida tion of secon da ry a lcoh ols to keton es is highly
select ive, a n d qu a n t it a t ive t r a n sfor m a t ion wit h ou t
a n y bypr odu ct for m a t ion u n der m ild con dit ion s is n ot
u n u su a l. Repr esen t a t ive t est r ea ct ion s for a liph a t ic
a n d cycloa liph a t ic a lcoh ols a r e t h e oxida t ion s of
2-oct a n ol (Ta ble 9), cycloh exa n ol (Ta ble 10), cyclopen t a n ol (Ta ble 11), a n d 2-a da m a n t a n ol (Ta ble 12).
Ru /Al 2 O 3 seem s t o be t h e m ost a ct ive ca t a lyst (Ta ble
9, TOF ) 300 h -1 ), t h ou gh t h e ou t st a n din g a ct ivit y
m igh t be du e t o t h e eleva t ed r ea ct ion t em per a t u r e
a n d solven t -fr ee con dit ion s. Ot h er Ru -con t a in in g
ca t a lyst s (e.g., Ru -silicot u n gst a t e) a n d su ppor t ed P t
a n d P d a lso per for m well.
Th e oxida t ion of secon da r y a r om a t ic a lcoh ols is
illu st r a t ed by t h e t r a n sfor m a t ion s of 1-ph en ylet h a n ol
(Ta ble 13) a n d diph en ylm et h a n ol (Ta ble 14). Th e
a ct ivit y of su ppor t ed P t -gr ou p m et a ls is r em a r ka bly
h igh er t h a n t h ose of ot h er ca t a lyst s; t h e yields a r e
excellen t wit h a ll ca t a lyst s.29,41,327
Ta ble 8. Ox id a tio n o f Alip h a tic Alc o h o ls to Ca rbo x y lic Ac id s
su bst r a t e
ca t a lyst
T, K
solven t a
TOF , h -1
Y, %
S, %
r ef
1-oct a n ol
1-oct a n ol
1-oct a n ol
2-ph en oxyet h a n ol
2-ph en oxyet h a n ol
5% P t -1% Bi/Al 2 O 3
P d/r esin
Ru 0.3 Co2 CeO x
1% P t /C + Cd(OAc)2 + P b(OAc)2
10% P d/C + Bi(NO 3 )3
333
373
333
343
343
H 2O
H 2O
P h CF 3
H 2O
H 2O
29
0.1
2.5
840
82
93
90
97
98
100
97
97
100
189
82
263
46
46
Wa t er is u sed t oget h er wit h som e ba se, a n d t h e pr odu ct is t h e ca r boxylic a cid sa lt .
4.4. Diols and Triols
Ta ble 9. Ox id a tio n o f 2-Oc ta n o l
ca t a lyst
T,
K
TOF , Y,
h -1 %
solven t
1.4% Ru /Al 2 O 3
1.4% Ru /Al 2 O 3
5% P t -1% Bi/Al 2 O 3
423 n on e
300
356 P h CF 3
18
328 H 2 O +
78
det er gen t
0.3% P d/h ydr oxya pa t it e 363 P h CF 3
6.3
Ru 0.35 Mn F e 1.5 Cu 0.15 O x
295 P h CH 3
1
333 P h CF 3
6.5
Ru 0.3 Co2 CeO x
333 P h CH 3
4.6
353 P h CH 3
1
Ru -silicot u n gst a t e
383 i Bu OAc
13
S,
%
95
91 >99
78 100
r ef
29
29
a
91
- 327
84 100 264
98 100 263
97 97 303
96 100 322
79 88 347
a Cs. Keresszegi, T. Mallat, and A. Baiker, unpublished data

(C/S, 10 wt %; 1 ba r O 2 ; 3 h ; det er gen t , sodiu m dodecylben zen e
su lfon a t e).
Ta ble 10. Ox id a tio n o f Cy c lo h e x a n o l
ca t a lyst
T,
K
10% P t /MgO
10% Ru O 2 /F AU zeolit e
Ru 0.35 Mn F e 1.5 Cu 0.15 O x
Ru 0.3 Co2 CeO x
373
353
295
333
373
solven t
TOF , Y ,
h -1 %
H 2 O (pH 9) 7
P h CH 3
1.4
P h CH 3
0.3
P h CF 3
1
i
Bu OAc
23
S,
%
r ef
70 100 378
43 >99 262
71 100 264
81 98 263
54 81 347
Ta ble 11. Ox id a tio n o f Cy c lo p e n ta n o l
ca t a lyst
T,
K
10% P t /MgO
1.4% Ru /Al 2 O 3
H -K-OMS-2
373
356
363
383
solven t
TOF ,
h -1
Y,
%
S,
%
r ef
100 100 378

H 2 O (pH 9) 9.1
P h CF 3
4.5 >91 >99 29
5.8
84
- 327
P h CF 3
0.07
67 100 292
P h CH 3
Ta ble 12. Ox id a tio n o f 2-Ad a m a n ta n o l
ca t a lyst
Ru 0.3 Co2 CeO x
Ru 0.35 Mn F e 1.5 Cu 0.15 O x
T,
K
solven t
TOF ,
h -1
333 P h CF 3
295 P h CH 3
353 P h CH 3
373 i Bu OAc
5
0.5
1.5
20
Y,
%
S,
%
r ef
>99 >99 263

94 100 264
95
95 322
98
99 347
P a r t ia l oxida t ion of va r iou s diols a n d glycer ol t o

h ydr oxya cids a n d la ct on es, ket oa cids, a n d h ydr oxyket on es is a field of in du st r ia l in t er est . Th e r ea ct ion
m ediu m is wa t er , a n d t h e pr ecise con t r ol of pH or
t h e a m ou n t of ba se is cr it ica l t o a ch ieve h igh select ivit ies. Th e per for m a n ce of t h ese ca t a lyst s is com pa r ed below in t h e oxida t ion of et h ylen e glycol a n d
glycer ol t o m on oca r boxyla t es.
E t h ylen e glycol ca n be t r a n sfor m ed qu a n t it a t ively
t o glycolic a cid by P t /C wh en on ly 1 equ iv of ba se is
a dded a n d t h e a ct u a l oxygen con cen t r a t ion a t t h e
m et a l su r fa ce is kept low by wor kin g a t r eflu x
t em per a t u r e in a ir (Ta ble 15).146 Su ppor t ed Au seem s
t o be a bet t er ch oice: it com bin es a n excellen t r a t e
wit h h igh select ivit y.205,208,227-230 Th e su per ior select ivit y of gold h a s been sh own a lso in t h e oxida t ion of
pr opa n e-1,2-diol t o la ct a t e.228
Su ppor t ed Au n a n opa r t icles a r e t h e ca t a lyst of
choice also for the oxidation of glycerol to glyceric acid
(Ta ble 16).223,231 Th e a ct ivit y of P t /C is sim ila r , bu t
t h e select ivit y is lower .
5. Conclusions
In t h is r eview, we h a ve explor ed t h e h et er ogen eou s
ca ta lytic methods a va ila ble for the selective oxida t ion
of a lcoh olic OH gr ou ps t o ca r bon yl or ca r boxyl fu n ction a l grou ps, u sin g m olecu la r oxygen a s the only oxida n t. A grea t n u m ber of n ew ca ta lysts h a ve been suggested in recent years for the clean oxidation of alcoh ols wit h m olecu la r oxygen . Ma n y of t h em a r e ba sed
on Ru a n d, t o a sm a ller ext en t , on P d species in
va r iou s for m s.
Th er e a r e sever a l ca t a lyst s t h a t pr ovide h igh yields
in ea ch cla ss of t h e r ela t ively sim ple t est r ea ct ion s
discu ssed h er e. Th e select ion of a n a ppr opr ia t e ca t a lyst m a y be ba sed on ot h er fa ct or s, su ch a s t h e ea sy
syn t h esis of t h e ca t a lyst a n d it s st a bilit y, su fficien t ly
low C/S m a ss r a t io, a n d h igh r ea ct ion r a t e (TOF ). A
closer in spect ion of t h e pu blish ed da t a r evea ls t h a t
som e ca t a lyst s possess su r pr isin gly low a ct ivit y, a n d
for m ost r ea ct ion t ypes t h ey do n ot offer a r ea l a lt er n ative to the conventional supported Pt-group metalss
m a t er ia ls wh ose a ct ivit y wa s discover ed in t h e 19t h
cen t u r y. Th e la r ge n u m ber of pa t en t s r eflect s a
con sider a ble in du st r ia l in t er est in t h e a pplica t ion of
su ppor t ed (a n d pr om ot ed) P t -gr ou p m et a l ca t a lyst s,
Ta ble 13. Ox id a tio n o f 1-P h e n y le th a n o l to Ac e to p h e n o n e
ca t a lyst
T, K
solven t
TOF , h -1
Y, %
S, %
r ef
1.4% Ru /Al 2 O 3
1.4% Ru /Al 2 O 3
5% P t -0.8% Bi/Al 2 O 3
Ru 0.35 Mn F e 1.5 Cu 0.15 O x
H -K-OMS-2
Na 5 P Mo10 V2 O 40 /C
356
423
333
363
295
383
333
333
353
348
373
P h CF 3
n on e
H 2 O + det er gen t
P h CF 3
P h CH 3
P h CH 3
P h CH 3
P h CH 3
P h CH 3
P h CH 3
P h CH 3
40
340
340
490
3.5
0.5
0.5
6.2
3
3
4.5
>98
98
97
98
98
99
100
100
98
90
94
>99
>99
100
100
100
100
98
100
100
29
29
41
327
264
292
302
303
322
355
346
Mallat and Baiker
Ta ble 14. Ox id a tio n o f D ip h e n y lm e th a n o l to

B e n zo p h e n o n e
T,
K
ca t a lyst
TOF ,
h -1
solven t
5% P t -0.8% Bi/Al 2 O 3
348 H 2 O +
700
det er gen t
P d/r esin
373 H 2 O
0.9
Ru 0.35 Mn F e 1.5 Cu 0.15 O x 295 P h CH 3
4
Ru 0.3 Co2 CeO x
333 P h CF 3
11
H -K-OMS-2
383 P h CH 3
0.5
Ru -Mg-Al-h ydr ot a lcit e 333 P h CH 3
1.2
Ru -Co-Al-h ydr ot a lcit e 333 P h CH 3
9.3
Ru 3+-h ydr oxya pa t it e 353 P h CH 3
3
383 t-Bu OAc
15
C/S
H Ap
HT
M n +-X
Y,
%
S,
%
r ef
99 100
41
100
>99
100
100
96
>99
99
82
264
263
292
302
303
322
347
85
86
>99
100
100
96
>99
91
Ta ble 15. Ox id a tio n o f Eth y le n e Gly c o l to Gly c o la te
ca t a lyst
T, K
p O 2, ba r
TOF ,
h -1
Y, %
S, %
r ef
9% P t /C
5% P t /C
5% P d/C
1% Au /C
373
323
323
343
0.2
2
2
2
7
475
500
1000
100
67
73
93
100
71
77
98
146
205
205
205
Ta ble 16. Ox id a tio n o f Gly c e ro l to Mo n o c a rbo x y la te

a t 333 K
ca t a lyst
TOF , h -1
Y, %
S, %
r ef
1% Au /gr a ph it e
1% Au /C
5% P t /C
65
100
105
84
56
47
92
100
74
223
223
223
dom in a n t ly in a qu eou s m edia . Th er e a r e en cou r a gin g

exa m ples on t h e in du st r ia l a ccept a n ce of t h is gr een
t ech n ology, t h ou gh sever a l ot h er pr oject s h a ve been
a bor t ed du e t o u n sa t isfa ct or y r esu lt s. Obviou sly,
replacement of stoichiometric and homogeneous catalyt ic oxida t ion m et h ods by h et er ogen eou s ca t a lyt ic
oxida t ion s wit h m olecu la r oxygen h a s a lr ea dy begu n
in t h e in du st r y, t h ou gh a cceler a t ion of t h is pr ocess
n ecessit a t es m or e efficien t solid ca t a lyst s.
Con sider in g t h e t opic fr om t h e poin t of view of
su bst r a t e st r u ct u r e, t h e fa st a n d select ive oxida t ion
of a liph a t ic a n d cycloa liph a t ic a lcoh ols is cer t a in ly
a n u n solved pr oblem . Th e difficu lt ies a r e m u lt iplied
when more complex structures, such a s polyfu n ction a lized a n d t h er m ola bile a lcoh ols, h a ve t o be oxidized.
Th is a r ea m a y be t h e m ost pr om isin g a n d r ewa r din g
field for fu t u r e developm en t .
6. Abbreviations
A% M/Y
A% M 1 -B %
M 2 /X
A% MO x /Y
Ax B y C z ...O n
m et a l (M) su ppor t ed on Y, m et a l con t en t (A)

in wt %
bim et a llic ca t a lyst su ppor t ed on a solid (X);
m et a l con t en t (A, B ) in wt %
su ppor t ed oxide; oxide con t en t (A) in wt %
m ixed oxide con t a in in g elem en t s A, B, C
OMS
S
TOF
X
Y
ca t a lyst /su bst r a t e m a ss r a t io

h ydr oxya pa t it e
h ydr ot a lcit e
solid m a t er ia l (X) con t a in in g M n + ion s in t h e
m a t r ix
oct a h edr a l m olecu la r sieve
select ivit y, in m ol %
t u r n over fr equ en cy; m ola r r a t io of con ver t ed
su bst r a t e t o t h e a ct ive com pon en t of t h e
ca t a lyst , per u n it t im e (h -1 ); it r efer s t o
t h e a ver a ge r a t e a t h igh con ver sion
con ver sion , in m ol %
yield, in m ol %
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Oxidation With Oxygen of Alcohols

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Chem. Rev.

2004, 104, 30373058

Oxidation of Alcohols with Molecular Oxygen on Solid Catalysts

Tamas Mallat received an M.S. degree in 1972 in chemical engineering

10.1021/cr0200116 CCC: $48.50 2004 American Chemical Society

3038 Chemical Reviews, 2004, Vol. 104, No. 6

Mallat and Baiker

ca t a lyst s. Th e t h ir d pa r t com pa r es t h e best ca t a lyst s

2. Intrinsically Solid Catalysts

2.1.1. Catalysts and Reaction Conditions

F ig u re 1. Com pa r ison of ca t a lyst s: a t con dit ion s A a n d

r a n dom ly ch osen set of r ea ct ion con dit ion s ca n n ot

Catalytic Oxidation of Alcohols with Molecular Oxygen

Chemical Reviews, 2004, Vol. 104, No. 6 3039

S c h e m e 4. Effe c t o f Wa te r o n th e Re a c tiv ity o f th e

Wh en t h e t a r get pr odu ct is a ca r boxylic a cid,

3040 Chemical Reviews, 2004, Vol. 104, No. 6

Mallat and Baiker

F ig u re 3. Ra te of oxida tion of L -sorbose to 2-keto-L -gulonic

va r ia t ion is t h e in a ppr opr ia t e ch oice of ca t a lyst

2.1.2. Catalyst Deactivation

2.1.3. Reaction Mechanism

u pon a dsor pt ion on t h e su r fa ce sit es, a ffor din g a n

Catalytic Oxidation of Alcohols with Molecular Oxygen

Chemical Reviews, 2004, Vol. 104, No. 6 3041

copr odu ct h ydr ogen a n d t h u s sh ift t h e equ ilibr iu m

An ot h er cla ss of m ech a n ist ic m odels a ssu m es t h a t

F ig u re 4. Ca t a lyst dea ct iva t ion du r in g con ver sion of

is dir ect ly in volved in t h e r a t e-det er m in in g st ep of

F ig u re 5. Models a ssu m in g com plex for m a t ion wit h t h e

for m a t ion bet ween a 1,2-diol a n d a Sn IV species on

3042 Chemical Reviews, 2004, Vol. 104, No. 6

2.1.4. Application Range of Pt-Group Metal Catalysts

Th e select ive oxida t ion of a n a lcoh olic OH gr ou p

Mallat and Baiker

An im por t a n t lim it a t ion of t h ese ca t a lyst s is t h e

2.2. Supported Gold and Silver

Catalytic Oxidation of Alcohols with Molecular Oxygen

bon yla t ion ).205,224 An ot h er dr a wba ck is t h e for m a t ion

F ig u re 6. E xa m ples on t h e syn t h esis of m on oca r boxyla t es

m a t ion of a m in o a lcoh ols t o a m in o a cids is a lso

Chemical Reviews, 2004, Vol. 104, No. 6 3043

yea r s a go for a lcoh ol oxida t ion on P t /C, in volvin g a

We con sider it m or e fea sible t h a t t h e r a t e-det er m in in g st ep is t h e clea va ge of t h e C-H bon d a t t h e

st r u ct u r a l differ en ces bet ween Au n a n opa r t icles a n d

F ig u re 7. Model of t h e a ct ive sit e in t h e oxida t ion of CO

Silver -ba sed ca t a lyst s a r e well est a blish ed in t h e

3044 Chemical Reviews, 2004, Vol. 104, No. 6

Mallat and Baiker

ca t a lyst s, h a s been con clu ded a lso in t h e oxida t ion

2.3. Oxides and Mixed Oxides

F ig u re 8. St r u ct u r e of Ru O 2 in t h e su per ca ges of fa u ja sit e

Catalytic Oxidation of Alcohols with Molecular Oxygen

2.3.2. Other Oxides

Chemical Reviews, 2004, Vol. 104, No. 6 3045

V2 O 5 . F or com pa r ison , su ppor t ed P t -gr ou p m et a l

2.4. Molecular Sieves

3046 Chemical Reviews, 2004, Vol. 104, No. 6

substituted aluminophosphate, CrAlPO-5,289,290 which

Mallat and Baiker

wit h m olecu la r oxygen . 302 Th e C/S m a ss r a t io wa s

Catalytic Oxidation of Alcohols with Molecular Oxygen

m or e r ea ct ive t h a n pr im a r y a lcoh ols, a n d su bst it u t ed