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Selective Oxidation of Glucose Over Carbon-supported Pd and Pt Catalysts

Article  in  Catalysis Letters · November 2010

DOI: 10.1007/s10562-010-0430-0

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Catal Lett
DOI 10.1007/s10562-010-0430-0
2010 SSAT PLENARY PRESENTATION
Selective Oxidation of Glucose Over Carbon-supported
Pd and Pt Catalysts
Irina V. Delidovich • Oxana P. Taran • Lyudmila G. Matvienko
Alexander N. Simonov • Irina L. Simakova •
Alesya N. Bobrovskaya • Valentin N. Parmon
Received: 11 June 2010 / Accepted: 6 August 2010
Ó Springer Science+Business Media, LLC 2010
Abstract Selective oxidation of glucose into gluconic
acid by molecular oxygen over carbon-supported Pt and Pd
catalysts was studied. Under examination were kinetic
regularities of the process in respect of the electronic state
of the noble metal surface, dispersion of the active com-
ponent particles as well as substrate:Pt(Pd) ratio. Catalytic
activity of the Pt/C catalysts being normalized to the dis-
persion of the platinum particles appeared independent of
the particles mean diameter in the 1–5 nm range. A neg-
ative particle size effect for the Pd/C catalysts, caused by
feasibility of oxidation of the surface of noble metal par-
ticles with the size less than 3 nm, was observed. Pt/C
catalysts exhibited lower specific activity and provided
poor selectivity of the glucose oxidation in comparison
with Pd/C. Deactivation of Pd/C catalysts arising from the
formation of surface Pd(II) oxides was retarded when the
reaction was carried out under an oxygen-diffusion control.
Keywords Glucose  Gluconic acid 
Selective oxidation  Pt  Pd  Particle size effect
1 Introduction
Being renewable and widespread feedstock, natural carbo-
hydrates are attractive substrates for industrial production
I. V. Delidovich (&)  O. P. Taran  L. G. Matvienko 
A. N. Simonov  I. L. Simakova  A. N. Bobrovskaya 
V. N. Parmon
Boreskov Institute of Catalysis SB RAS, Akad. Lavrentiev
Prosp., 5, Novosibirsk 630090, Russia
e-mail: DIV@catalysis.ru
O. P. Taran  L. G. Matvienko  A. N. Simonov  V. N. Parmon
Novosibirsk State University, Pirogova St., 2, Novosibirsk
630090, Russia
•
of commodity chemicals. In particular, selective oxidation
of sugars yields commercially relevant polyoxiacids. For
example, gluconic acid is the product of selective oxidation
of glucose in the C1 position and widely used in pharma-
ceutical, food, chemical and textile industries. At present,
gluconic acid is industrially produced via enzymatic
technique with the annual output of 6 9 104 tons [1].
Alternative chemical [2], electrochemical [3] and catalytic
[4] methods of selective oxidation of carbohydrates are well
known as well. Among the listed methods, the oxidation of
sugars with molecular oxygen in aqueous media in the
presence of heterogeneous supported catalysts is considered
as the most economically promising and environmentally
friendly technique [5].
Platinum group metals, in particular Pt and Pd, are
known to exhibit highest catalytic activities towards
selective oxidation of carbohydrates [6]. Promising results
on high activity of monometallic Au catalysts for the car-
bohydrate oxidation have been reported recently, too [7].
However, the present study is focused on the monometallic
platinum and palladium carbon-supported catalysts, since
some of the fundamental issues on their catalytic properties
for selective oxidation of glucose still need clarification.
Besides, gold-based catalysts seem less economically
sound due to a higher price for Au in comparison with Pt
and Pd, as well as due to the complexity of the preparation
procedures of Au/C catalysts with disperse gold nanopar-
ticles [8]. The carbonaceous materials are attractive as
supports for catalysts for liquid-phase oxidation due to
their high specific surface area and developed pore-struc-
ture, high durability and stability in aqueous solutions in a
wide range of pH.
The review of the most important publications devoted
to catalytic properties of platinum and palladium for the
selective oxidation of glucose is provided by extensive
123
 I. V. Delidovich et al.

treatises by Mallat and Baiker [6] as well as Besson and various dispersions and exclude contamination of the
Gallezot [9]. Note that the reported data on the activity of noble metal surface with any organic or inorganic
Pt and Pd catalysts and their selectivity to gluconic acid impurities.
formation differ noticeably. For example, Abbadi and van 3. To elucidate the interrelation of the catalytic activity
Bekkum [10] as well as Besson et al. [11] observed the and the electronic state of the active component of the
89–95% selectivity to gluconate during the glucose oxi- catalysts, the latter is studied using XPS before and
dation over carbon-supported Pt and Pd catalysts. The after the reaction.
selectivity of 60–70 and 80–90% at low and high sub-
strate conversions, respectively, was registered by Dirkx
and van der Baan [12] in the presence of Pt/C catalyst.
2 Experimental
Comparative studies of catalytic behaviour of platinum
and palladium catalysts for the oxidation of aldoses per-
2.1 Catalysts Preparation and Characterization
formed by Kiyoura et al. [13] and Nakayama et al. [14]
suggest that the catalytic activity of palladium is much
Mesoporous graphite-like carbon material of the SibunitÒ
higher than that of platinum. On the contrary, Comotti
family was used as a support. The preparation procedures
et al. [15] claimed that the turnover frequency (TOF) for
and properties of Sibunit carbons are described elsewhere
the gluconic acid production via selective oxidation of
[17]. Textural characteristics of the Sibunit carbon support
glucose over Pt/C catalyst exceeds that over Pd/C by a
were obtained from the data on nitrogen adsorption mea-
factor of 30 or even higher. The disagreements in the data
sured at 77 K with an automatic volumetric device ASAP
reported by different authors demonstrate that the cata-
2400 (Micrometritics). The BET specific surface area,
lytic properties of supported Pt and Pd catalysts are
SBET, was 350 m2 g-1, mean pore diameter 7 nm, while the
determined not only by the nature of the active compo-
calculated total micropore volume was 0.000 cm3 g-1. The
nent but also a set of parameters (metal precursors, active
40–90 lm support fraction was used for the catalyst
component dispersion, electron state of metal, texture and
synthesis.
chemical properties of the support, etc.) may affect con-
Three 5 wt% Pt/C catalysts with various dispersion of
siderably the catalytic performance of supported noble
platinum were synthesized by impregnation as described
metal catalysts.
elsewhere [18]. Dispersion of platinum particles was
The aim of the present study is careful elucidation of the
controlled by varying temperature regimes during reduc-
influence of dispersion and oxidation state of carbon-sup-
tion of Pt (Pt/C-1 and Pt/C-2), while NH4Cl was intro-
ported platinum and palladium nanoparticles on their cat-
duced to the impregnating solution during the noble metal
alytic activity towards selective oxidation of glucose. The
precursor adsorption on the carbon support for the prep-
particle size effect for the Pt/C catalysts for this reaction
aration of the Pt/C-3 sample with larger platinum parti-
has not been studied earlier. The necessity of the catalyst
cles. A palladium catalyst 2 wt% Pd/C (Pd/C-1) was
pre-reduction before oxidation of glucose is well known
prepared using the deposition–precipitation method
and reported in literature [12, 16]. However, we were
described before [19]. Palladium catalysts with diverse
interested in a deeper insight into the electronic state of
dispersion were prepared by calcination of Pd/C-1 in
fresh and deactivated catalysts depending on the nature and
hydrogen flow at 150 °C (Pd/C-2), 200 °C (Pd/C-3) and
dispersion of the active component.
300 °C (Pd/C-4) following the procedure adapted from
Thus, in order to perform a reasonable comparative
[20]. All of the synthesized catalysts were thoroughly
study of the catalytic activity of carbon-supported platinum
washed with water until no chloride-ions were detected in
and palladium nanoparticles in respect of the chemical
the washing solution.
nature, dispersion and oxidation state of noble metal the
The metal surface area available for the adsorption of
following steps were undertaken:
organic substrate was measured by the CO pulse chemical
1. SibunitÒ carbon obtained by pyrolysis of hydrocarbons adsorption [21]. The catalysts were heated in hydrogen
followed by the activation [17] is used as the support. atmosphere to 100 °C at the rate of 10 °C/min, held at
The chosen carbonaceous material has a mesoporous 100 °C for half an hour and cooled to room temperature.
structure with a negligible micropore volume which Then the pulse chemical adsorption was carried out using a
minimizes the mass transport limitations. mixture of 10% CO with H2. The dispersion of metal
2. Pt/C samples are synthesized using the same impreg- particles in the catalysts was estimated under assumption of
nation technique, and all Pd/C samples are prepared CO:M = 1:1 stoichiometry. The average particle size was
via the same deposition–precipitation method. The calculated using the following equation and reported data
applied techniques allow preparation of catalysts with on physical properties of Pt and Pd [22]:

123
Selective Oxidation of Glucose
   
VM AM
ds ¼ 6 =DM ¼ 6 =DM
aM q  N0  aM
where AM is atomic weight, q is the density of metal, N0 is
the Avogadro constant, aM is the average effective area of a
metal atom on the surface and DM is metal dispersion.
Transmission electron microscopy (TEM) studies were
carried out using a JEOL JEM-2010 electron microscope
operated at 200 kV. Histograms of the particle size distri-
butions and mean diameters of platinum particles were
obtained by statistical (200–500 particles) processing of
electron microphotographs. X-ray photoelectron spectra
(XPS) were measured with a SPECS apparatus using
monochromatic AlKa without a compensation of the sur-
face charge. The samples were mounted on a standard
holder with conducting double-sided masking tape Scotch
3 MÓ.
2.2 Catalytic Tests
The glucose oxidation was carried out in agitated
(900 rpm) aqueous suspensions using a three-necked glass
reactor equipped with a peristaltic pump for alkali (3 M
NaOH) supply and combined electrode for the pH regis-
tration. All experiments were carried out at 60 °C, atmo-
spheric pressure and pH = 8.8–9.2, the latter being
constantly controlled in the course of the reaction.
Prior to the addition of glucose into the aqueous sus-
pension (20 mL) of the catalyst, the active component of
the latter was reduced by dihydrogen, which was bubbled
through the deaerated suspension during 30 min under
vigorous agitation. Deaeration of the suspension and
removal of the dissolved dihydrogen was performed by
feeding Ar into the reactor for 20 min before and after the
catalyst reduction. After that 2.5 g of glucose were dis-
solved in the reaction mixture (the initial glucose concen-
tration ca. 0.6 M), pH was adjusted to 9 via addition of the
required amount of 3 M NaOH and dioxygen was supplied
through the suspension with the 10 mL/min rate. The
reaction was carried out for 7 h; samples for analysis were
periodically drawn from the reaction mixture. Selected
experiments were carried out without a preliminary
reduction of the active component of the catalyst by
dihydrogen. The molar noble metal to the glucose substrate
ratio in the reaction mixture was 1:750 for all the Pt/C
catalysts and 1:750, 1:1500, 1:2000 and 1:6000 for the
Pd/C catalysts.
2.3 Analytic Methods
The analyzed aliquots of the reaction mixture were thor-
oughly filtered and the concentrations of glucose and
fructose as well as that of gluconic acid were measured by
HPLC using a Shimadzu Prominence LC-20 system
equipped with a SPD-M20A diode-array detector (detec-
tion wavelength k = 190 nm) and Luna 5l NH2 100A
column (Phenomenex, 250 mm 9 3.0 mm) thermostated
at 40 °C. The eluent (35 vol% 0.02 M H3PO4 (pH 2) ?
65 vol% acetonitrile) was supplied at the 1 mL min-1 flow
rate.
The selectivity to gluconic acid was calculated as the
ratio of the amount of formed gluconic acid to the amount
of consumed glucose; the yield of gluconic acid was cal-
culated as the ratio of the amount of formed gluconic acid
to the initial amount of glucose. The calculations were
performed with regard to a change in the reaction mixture
volume during the experiments which is due to the addition
of the alkali solution.
The total organic carbon content in the filtered reaction
mixture aliquots was measured by a Shimadzu Total
Organic Carbon Analyzer, TOC-VCSH.
All solutions were prepared using Milli-Q (Millipore,
USA) water.
3 Results and Discussion
3.1 Physicochemical Properties of Catalysts
TEM characterization of the platinum catalysts and Pd/C-1
sample revealed that the noble metal particles are mainly
spherical. The estimated average linear (dl)/surface average
(ds) diameters of the Pt and Pd particles are shown in
Tables 1 and 2, respectively. The particle size distribution
is narrow and uniform for Pt/C-1 (Fig. 1) and Pt/C-2, while
the Pt/C-3 catalyst prepared with addition of NH4Cl con-
tains particles with diameter ranging from 2 to 9 nm
(Table 1). An incubation of Pd/C-1 in a H2 flow at tem-
peratures below 200 °C for 1 h does not result in a sig-
nificant increase of palladium particles in diameter as
evidenced by the TEM characterization of Pd/C-2 and
Pd/C-3 catalysts. Elevation of the reduction temperature up
to 300 °C (Pd/C-4) causes the agglomeration of Pd nano-
particles and broadening of the particle size distribution
(Fig. 2). The size of the majority of metal particles in the
Pd/C-4 catalyst ranges from 2 to 15 nm (cf. 2–4 for the
parent Pd/C-1 sample). Several isolated noble metal
agglomerates with the size up to 30 nm were detected in
the Pd/C-4 catalyst as well.
The data on the active component dispersion determined
by the pulse CO chemisorption is presented in Tables 1 and
2 for the synthesized Pt/C and Pd/C catalysts. The differ-
ences of the ds values determined independently by CO
chemisorption and TEM grow with an increase in the par-
ticle size and are most pronounced for Pt/C-3 and Pd/C-4
catalysts (see line 3 of Table 1 and line 4 of Table 2).
123
 I. V. Delidovich et al.

Table 1 Properties of 5% Pt/C catalysts

N Catalyst Average diameter of Pt particlesa Glucose conversion after Selectivity after 7 h of reaction Initial TOFc TOCd (%)
3b
(nm) (%) (%) rate 9 10
hdli hdsi hdCOi 1h 7h Gluconic acid Fructose

1 Pt/C-1 1.1 ± 0.5 1.2 1.5 32 85 77 3 2.4 0.05 93

2 Pt/C-2 1.9 ± 0.7 2.1 3.3 12 51 62 20 1.1 0.05 95
3 Pt/C-3 4.5 ± 2.9 5.8 10.0 1 5 33 67 0.3 0.05 96
Glucose oxidation conditions: t = 60 °C, pH = 9, molar ratio glucose:Pt = 750:1, V = 20 mL, [Glucose]0 = 0.6 M, dioxygen supply
rate = 10 mL/min
a P P P
hdli = di/N, hdsi = d3i / d2i , where di is the diameter of a Pt particle, N is the total number of particles; hdCOi = average diameter of
particles, determined by the CO pulse chemical adsorption
b
Initial rate of the gluconic acid formation [molGluconic acid 9 h-1]
c
TOF was calculated as the quotient of initial reaction rate to the metal dispersion: [TOF] = [molGluconic acid 9 s-1 9 mol-1
Pt ]
d
Content of total organic carbon in the reaction mixture after the experiment in % from the calculated value

Table 2 Properties of 2% Pd/C catalysts

N Catalyst Molar ratio Average diameter of Pd Glucose conversion Selectivity after 7 h of Initial TOFc TOCd (%)
glucose:Pd paricles (nm) after (%) reaction (%) rate 9 103b
hdli hdsi hdCOi 1h 3.5 h 7h Gluconic acid Fructose

1 Pd/C-1 750 3.0 ± 1.0 3.1 4.4 61 88 95 95 1 7.8 0.5 100

2 Pd/C-2 750 3.2 ± 1.5 3.8 5.1 64 92 92 97 1 7.9 0.6 98
3 Pd/C-3 750 3.3 ± 1.3 4.1 5.5 64 89 94 96 1 8 0.6 99
4 Pd/C-4 750 6.3 ± 3.2 7.0 11.4 65 90 95 96 1 7.9 1.3 97
5 Pd/C-1 1000 3.0 ± 1.0 3.1 4.4 63 88 95 94 3 5.2 0.4 96
6 Pd/C-1 1500 3.0 ± 1.0 3.1 4.4 31 61 71 86 12 2.4 0.3 98
7 Pd/C-1 2000 3.0 ± 1.0 3.1 4.4 15 39 50 76 18 1.5 0.3 98
8 Pd/C-1 6000 3.0 ± 1.0 3.1 4.4 6 11 25 60 40 0.3 0.2 100
9 Pd/C-3 1500 3.3 ± 1.3 4.1 5.5 28 57 72 83 15 2.4 0.4 97
10 Pd/C-4 1500 6.3 ± 3.2 7.0 11.4 37 71 87 92 7 3.4 1.1 99
Reaction conditions: t = 60 °C, pH = 9, V = 20 mL, [Glucose]0 = 0.6 M, dioxygen supply = 10 mL/min
a P P P
hdli = di/N, hdsi = d3i / d2i , where di is the diameter of a Pt particle, N is the total number of particles; hdCOi = average diameter of
particles, determined by the CO pulse chemical adsorption
b
Initial rate of the gluconic acid formation [molGluconic acid 9 h-1]
c
TOF was calculated as the quotient of initial reaction rate to the metal dispersion: [TOF] = [molGluconic acid 9 s-1 9 mol-1
Pd ]
d
Content of total organic carbon in the reaction mixture after the experiment in % from the calculated value

Commonly, the discrepancy of the TEM and CO-chemi-
sorption data can be explained either by poisoning and
blockage of the noble metal surface or by the presence of
large metal particles along with highly dispersed ones. The
majority of the former can be missed by TEM analysis due
to their very low concentration on the surface of the sup-
port. Methods employed in this work for preparation
of catalysts with different dispersion have no principal
differences. Hence the discrepancy of the TEM and
CO-chemisorption data would appear for all of the cata-
lysts synthesized if the surface of the noble metal was
poisoned and blocked for CO adsorption. As one can see
this is not the case (Tables 1, 2), and, consequently, the
observed phenomenon is most likely caused by the pres-
ence of crude agglomerates of platinum and palladium
formed during the calcination procedure.
XPS examination of Pt/C-2 and Pd/C-1 catalysts stored
in contact with air for two months (Fig. 3) revealed that
platinum on the surface of nanoparticles has two electronic
states with binding energies 71.6 and 73.3 eV for Pt4f7/2
and palladium has three electronic states with binding
energies 335.3, 336.1 and 337.1 eV for Pd3d5/2. Inspection
of the survey XP spectra of the catalysts revealed the
presence of the corresponding noble metal and oxygen only
in the contents of the active component to argue for the
absence of the contaminating admixtures such as chlorine.

123
Selective Oxidation of Glucose

(337.1 eV) [23]. XPS measurements of Pd/C with different

Pd particle size demonstrated that interactions of dispersed
Pd metal particles with carbon surface result in the palla-
dium core level shifts to increase Pd3d5/2 binding energy
[24, 25]. In this connection the intense peak at 336.1 eV
could be related to Pd0 in a highly dispersed state giving
the following atomic ratio of Pd0:Pd0 (dispersed):Pd2? =
1.8:1:2.3.

3.2 Catalytic Oxidation of Glucose

3.2.1 Reaction Mixture Composition

HPLC analysis of the reaction mixture evidences the accu-

Fig. 1 TEM micrograph and the particle size distribution diagram for
5% Pt/C-1
Based on the acquired XPS data, it was concluded that
platinum in Pt/C-2 catalyst stored in air for two months has
two electronic states Pt0 and Pt2? with the atomic ratios of
Pt0:Pt2? = 1.4:1. The acquired XPS data for Pd/C-1 cata-
lyst exposed to air for two months suggest that the active
component of the catalyst contains palladium metal parti-
cles with binding energy 335.3 eV as well as its oxide
mulation of at least two products in the course of oxidation of
glucose over Pt/C and Pd/C catalysts—the target gluconic
acid and by-product fructose. It was found that Pd/C catalysts
provide a substantially higher selectivity to gluconic acid
than Pt/C. It is evident that fructose is formed via base-cat-
alyzed isomerisation of parent glucose in the presence of
NaOH and promoted by the temperature elevation [26]. The
selectivity to fructose reaches a constant value in 30 min
after feeding glucose to the reactor and adjusting pH to 9, and
does not change during the run. The amount of fructose
formed increases with decreasing activity of the catalysts
under study (see Tables 1, 2). Hence, gluconic acid and

Fig. 2 TEM micrographs and

the particle size distribution
diagrams for 2% Pd/C catalysts:
a Pd/C-1 and b Pd/C-4

Fig. 3 Typical XP Pt 4f core (a) (b)

level spectra of Pt/C-2 (a) and
Intencity (arb. units)

Intencity (arb. units)

Pd 3d core level spectra of

Pd/C-1 (b). The catalysts were
stored in air for 2 month

68 70 72 74 76 78 80 332 336 340 344 348

Binding Energy (eV) Binding Energy (eV)

123

fructose are formed via independent parallel routes, and no
fructose oxidation takes place under the reaction conditions.
The latter observation is corroborated by the results obtained
by Esslis Yei et al. [27] who observed that fructose, like
glucose, is adsorbed on the surface of Pt particles but not
further dehydrogenated or oxidized under the process con-
ditions of selective glucose oxidation.
In terms of mass balance, gluconic acid and fructose are
the only products of the glucose oxidation over Pt/C-3
(Table 1, line 3) and all palladium catalysts studied
(Table 2). Joint selectivity to gluconic acid and fructose
after 7 h of the glucose oxidation in the presence of highly-
dispersed platinum catalysts Pt/C-1 and Pt/C-2 equals ca.
80% (Table 1, lines 1 and 2), to indicate a deeper oxidation
of the main reaction products. A detailed study of the
products of catalytic oxidation of glucose performed by
Dirkx and van der Baan [12] revealed that glucuronic and
guluronic acids are the uppermost by-products of the
reaction. Further oxidation of gluconic acid over platinum
results in the predominant formation of glucaric acid [28].
The TOC analysis of the reaction mixture before and after
the glucose oxidation over Pt/C-1 and Pt/C-2 catalysts
showed no changes in the organics content thus indicating
no deep oxidation to yield volatile or gaseous products
under the process conditions (Table 1).
3.2.2 Catalytic Performance of the Pt/C and Pd/C
Catalysts
It is well known that the surface of highly dispersed par-
ticles of platinum and palladium is partially oxidized by air
oxygen to result in a decrease in the surface concentration
of metal active sites M0 [12, 16]. The oxidized surface of
noble metals is believed to be unable to adsorb carbohy-
drate substrate and thus seems catalytically inactive in the
reaction under consideration [6].
The activity of the pre-reduced (by dihydrogen) and not-
reduced Pt/C-2 catalysts towards the glucose selective
oxidation turned out to be identical, while the pre-reduction
of the Pd/C-3 sample resulted in twofold increase in its
activity. Possibly, the Pt2? surface sites are capable of
oxidizing glucose to produce catalytically active Pt0, while
palladium surface oxides are not completely reduced by
monosaccharide due to the lower red-ox potential of Pd in
comparison with Pt [29].
The comparison of the performance of the synthesized
Pt/C catalysts indicates that an increase in the mean
diameter of platinum particles results in a decrease in their
initial activity and selectivity towards the glucose oxida-
tion, while the TOF remain the same (see Table 1).
The TOF of all Pt/C catalysts were calculated according
to the formula:
123
I. V. Delidovich et al.
 
TOF ¼ W molGluconic acid  h1 =nðmolPt Þ  D;
where W is the rate of the gluconic acid formation during
first 90 min, n is the overall platinum amount in the reac-
tion mixture, and D is the platinum dispersion.
As one can see the calculated TOF values were nor-
malized to the exposed surface area of Pt determined by the
pulse CO-chemisorption method (1/D) in order to reveal
unambiguously no influence of the Pt metal particle size on
their catalytic activity. The examination of the W and TOF
values estimated for the Pt/C samples under consideration
(Table 1) demonstrates clearly that the rate of the glucose
oxidation over these catalysts is directly proportional to the
platinum surface area. In other words, no particle size
effect is observed for the synthesized Pt/C catalysts in the
glucose oxidation reaction.
As it was stated above, palladium catalysts exhibit
considerably higher activity towards the oxidation of glu-
cose in comparison with Pt/C ones. The identical rate of the
glucose oxidation over all studied Pd/C catalysts was
observed when the glucose:Pd molar ratio in the reaction
mixture was 750:1 (Table 2, lines 1–4). The glucose con-
version of 90% is achieved after 3.5 h of the reaction with
the selectivity to gluconic acid more than 95%. During the
following 3.5 h the reaction rate drops sharply down and
the substrate conversion is no more than 95%, while the
selectivity towards gluconic acid decreases to 90%.
The equality of the reaction rates registered for the Pd/C
catalysts with various dispersion of the metal particles may
arise from the diffusion control of the process under chosen
conditions. According to the mechanism of the catalytic
glucose oxidation proposed by Gallezot [30], the key stages
of the reaction are dehydrogenation of hemi-acetal form of
the carbohydrate on the metal surface yielding d-lacton, its
subsequent interaction with hydroxide ion and desorption.
Molecular oxygen is dissociatively adsorbed on the metal
and scavenges its surface by reacting with the residual
atomic hydrogen formed as a product of glucose dehy-
drogenation. Since the glucose concentration in the reac-
tion mixture is significantly higher than those of OH- and
O2 and the diffusion of hydroxide-ions aqueous media
passes rapidly via the relay-race mechanism, oxygen
transfer appears to be the rate controlling stage of the
reaction proceeding under the diffusion control [31].
In order to compare properly the activity of Pd/C cata-
lysts with various dispersion of noble metal particles, the
glucose:Pd molar ratio was increased. The variation in the
Pd/C-1 catalyst loading in the reaction mixture showed that
the rate of the glucose consumption starts to be limited by
mass-transport of reactants at glucose:Pd molar ratio lower
than 1000:1. The glucose oxidation is limited by processes
passing on the surface of palladium particles when the
glucose:Pd ratio is increased above 1000 (Fig. 4).
Selective Oxidation of Glucose
W (molGluconic acid*h-1*mol-1Pd )
6
4 an explanation of the observed phenomenon [32]. As it was
2
0 the gluconic acid formation are close. At the molar ratio
0,0 5,0x10-4
nPd /nGlu(mol/mol)
Fig. 4 The initial rate of the gluconic acid formation at various molar
ratio Pd:glucose. Glucose oxidation conditions: 2% Pd/C-1 catalyst,
t = 60 °C, pH = 9, [Glucose]0 = 0.6 M, V = 20 mL, the dioxygen
supply rate = 10 mL/min
Fast deactivation of the catalysts was observed in the
course of the glucose oxidation under the mode of kinetic
control. The formation of gluconic acid abandoned when
the glucose conversion over Pd/C-1 catalyst reached 70, 40
and 10% at the molar ratios glucose:Pd = 1500, 2000 and
6000, respectively (Table 2, lines 1, 5–8). The further
glucose conversion was determined to be connected with
its isomerization to fructose.
The kinetically controlled glucose oxidation over Pd/C-1,
Pd/C-3 and Pd/C-4 was studied at the molar ratio glu-
cose:palladium = 1500 (Table 2, no 6, 9, and 10). The
initial rates of the gluconic acid formation over Pd/C-1 and
Pd/C-3 (hdPd l i *3 nm) are equal while the deactivation of
palladium occurs at the substrate conversion of ca. 50%. The
initial reaction rate over Pd/C-4 catalyst (hdPd
l i *6 nm) is
insignificantly higher in comparison with those over more
dispersed Pd/C-1 and Pd/C-3 samples and the catalyst was
deactivated at ca. 70% glucose conversion.
The observed influence of the particle size of palladium
on its catalytic activity towards glucose oxidation is in
agreement with the results reported by Besson et al. [32]
who compared the performance of Pd/C catalysts with the
metal particle sizes of 3–10 and 1–2.5 nm. A higher
Fig. 5 Kinetics of the gluconic
acid formation at molar ratio
Pd:glucose = 1:1500 (a) and
1:750 (b). Open square Pd/C-4,
Closed square Pd/C-1. Reaction
conditions: 2% Pd/C catalyst,
t = 60 °C, pH = 9,
[Glucose]0 = 0.6 M,
V = 20 mL, the dioxygen
supply rate = 10 mL/min
tolerance of large palladium particles towards the formation
of strong surface Pd–O bonds leading to deactivation of the
catalyst in comparison with smaller ones was suggested as
already stated, the main differences in the progress of the
glucose oxidation over Pd/C catalysts with the 3 and 6 nm
mean metal particle sizes are the higher rates of deactivation
of more dispersed Pd nanoparticles, while the initial rates of
1,0x10-3 1,5x10-3 glucose:palladium = 1500, the yield of gluconic acid
amounts 12 and 16% after 0.5 h and 44 and 61% after 3.5 h
of the reaction progress over Pd/C-1 and Pd/C-4, respec-
tively. That indicates very fast deactivation of small palla-
dium particles due to the formation of strong Pd–O bonds
on their surface when the reaction is not limited by the
diffusion of reagents. On the other hand, the reaction rate
doesn’t depend on the dispersion of metal particles under
diffusion control when the concentration of reagents near
the surface of the active component of the catalysts is lower
than that in the reaction mixture. As a result, the catalyst
isn’t poisoned by dioxygen and fast deactivation of highly
dispersed Pd particles is avoided (Fig. 5). A resembling
‘‘diffusion stabilization of catalyst’’ method was suggested
by van Dam et al. [33, 34]. The oxidation rate of glucose
1-phosphate was limited by an increase of the catalyst sup-
port grain in size to decelerate diffusion of reagents through
pores [32]. Under diffusion control, the rate of gluconic acid
formation over fresh palladium catalysts described in the
present study amounts 430 molGluconic acid 9 h-1 9 mol-1 Pd
with selectivity over 95% at the glucose conversion of 90%.
It should be additionally mentioned that the loss of the
activity was observed for all Pd/C samples irrespective of
the metal dispersion and reaction mode. The drastic drop of
the glucose consumption and gluconic acid formation
occurs after ca. 3.5 h of the reaction in all Pd/C catalyzed
runs that indicates the blockage of the Pd0 active sites.
Indeed, according to XPS, the major part of the surface of
palladium particles is covered by Pd2? species after 7 h of
the glucose oxidation.
(a) (b)
100 100
Yield of gluconic acid (%)
Yield of gluconic acid (%)
75 75
50 50
25 25
0 0
0 2 4 6 8 0 2 4 6 8
Time (h) Time (h)
123

4 Conclusion
Comparative study of the catalytic activity and stability to
deactivation of carbon-supported platinum and palladium
catalysts for the selective oxidation of glucose was per-
formed. A dissimilitude of dependencies of the perfor-
mance of Pt/C and Pd/C catalysts on the dispersion and the
electronic state of active component was revealed using
XPS and TEM techniques.
According to XPS, ca. 40 at.% of the active component
of the Pt/C and Pd/C catalysts have the M2? electronic
state after contact with air. Reduction of the catalyst prior
to glucose oxidation results in a twofold increase in the
activity of Pd/C and has no effect on that of Pt/C. Hence,
we speculate that Pt2? is reduced directly by glucose to
produce Pt0 active sites, while the analogous reduction of
Pd2? does not take place under the employed experimental
conditions.
The TOF values (corrected for the dispersion of the
active component) for the Pt/C catalysts were found inde-
pendent of the mean platinum particle size in the 1–5 nm
range. Selectivity to gluconic acid over Pt does not exceed
80%. For Pd/C catalysts, an increase of noble metal par-
ticles in size from 3 to 6 nm was found to boost the TOF
values due to the deceleration of the oxidative deactivation
of the catalyst. Besides, the deactivation of finely dispersed
Pd/C catalysts is substantially slowed down when the
oxygen diffusion in the liquid is the rate-limiting step of the
process (molar ratio substrate:Pd \ 1000). Under these
conditions, the O2-diffusion controlled oxidation of glu-
cose over Pd/C occurs with the selectivity of gluconic acid
formation over 95% at the 90% conversion of the substrate.
Acknowledgments The authors are grateful to Dr. V. I. Zaikovskii
for TEM characterization of catalysts, Dr. R. I. Kvon and A.
V. Bukhtiyarov for XPS studies. The financial support of RFBR
(Grant No. 08-03-00823), the Federal Special Programm ‘‘Scientific
and Educational Cadres of Innovative Russia’’ via contracts NN
02.740.11.0265 and 02.740.11.5178 is gratefully acknowledged.
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