Applied Catalysis A: General 297 (2006) 17 www.elsevier.

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Aerobic oxidation of glucose II. Catalysis by colloidal gold

Paolo Beltrame a,*, Massimiliano Comotti b, Cristina Della Pina b, Michele Rossi b,**
b

Dipartimento di Chimica Fisica ed Elettrochimica, Via Golgi 19, 20133 Milano, Italy Dipartimento di Chimica Inorganica, Metallorganica e Analitica, ISTM e CIMAINA, via Venezian 21, 20133 Milano, Italy Received 18 July 2005; accepted 21 August 2005 Available online 12 October 2005

Abstract The selective oxidation of D-glucose to D-gluconic acid was performed in aqueous phase at atmospheric pressure, controlled pH value and different glucose and oxygen concentrations, in the temperature range from 303.2 to 333.2 K, using a colloidal metal gold catalyst (average gold diameter 3.5 nm). Initial rate was measured as a function of glucose and oxygen concentration: in the experimental conditions it was found that gluconic acid is produced together with hydrogen peroxide, which later decomposes in a fast way, due to the presence of alkali. The measurements were interpreted by considering different models based on different reaction pathways. Among the considered models, the experimental data t with an EleyRideal mechanism where a glucose molecule, adsorbed on the catalyst, interacts with an oxygen molecule coming from the liquid phase. The model includes a kinetic parameter kcat and the equilibrium constant KG for the adsorption of glucose on the gold surface. The activation energy for kcat was found to be 47.0 1.7 kJ mol1. It has been observed that KG decreases when temperature is increased, but the experimental uncertainty did not allow to obtain a precise value of the adsorption enthalpy. The values of the rate parameters here calculated for the colloidal gold catalyst have been compared with those previously obtained using the homogeneous enzymatic catalyst Hyderase under similar experimental condition. Considering geometric constraints, the specic activity of gold catalysis resulted quite similar to the enzymatic one. # 2005 Elsevier B.V. All rights reserved.
Keywords: Gold catalyst; Glucose oxidation; Kinetic models; EleyRideal mechanism; Activation energy

1. Introduction The behaviour of small metal particles, at the border between molecular and bulk dimensions, is of great interest because sudden changes in physical and chemical properties can be observed. In the case of catalytic applications, it has been found that gold exhibits catalytic activity in gas phase and liquid phase oxidation only in the form of supported particles having few nanometers size [1]. Although carbon was found to be the support of choice for liquid phase oxidation of alcohols and aldehydes to the corresponding carboxylates [26], it was recently found that unsupported gold particles in aqueous solution (average diameter: 35 nm) show a surprisingly high activity in the aerobic oxidation of glucose, not far from that of enzymatic
* Corresponding author. Fax: +39 02 503 14300. ** Corresponding author. Fax: +39 02 503 14424. E-mail addresses: paolo.beltrame@unimi.it (P. Beltrame), Michele.rossi@unimi.it (M. Rossi). 0926-860X/$ see front matter # 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2005.08.029

systems. Moreover, a linear correlation between activity and number of exposed gold atoms was demonstrated [7]. In order to derive more information on the respective reaction mechanisms we have carried out a study on the kinetics of enzymatic and inorganic catalysis applied to the oxidation of glucose to gluconic acid under similar experimental conditions. In the rst part of this work the kinetic parameters and the activation energies for the main steps of the enzymatic catalysis have been determined and compared with previous investigations [8]. In this second paper, kinetic investigations using a colloidal gold sol having a mean diameter of 3.5 nm are reported. Taking into consideration that hydrogen peroxide has been found as the reduction product of O2 in the reaction catalysed by gold, kinetic models for tting the experimental data are critically discussed, whereas a comparison between H2O2 and O2 as reagents for glucose oxidation will be discussed in a forthcoming paper. The evaluation of the activation energy of the slower step of the reaction is also reported.

P. Beltrame et al. / Applied Catalysis A: General 297 (2006) 17

2. Experimental 2.1. Reagents and apparatus Gold sponge of 99.9999% purity from Fluka and Vulcan XC72R carbon from CABOT (surface area of 254 m2 g1, pore volume of 0.19 mL g1) were used. D-Glucose monohydrate (99% pure) and d-gluconolactone (99% pure) from Fluka were used as reagent and reference compound without further purication. NaOH (Merck) was 99.9% pure and stored under nitrogen. Gaseous oxygen and nitrogen (SIAD) were 99.99% pure. MilliQ1 water obtained by an Academic A-10 Millipore apparatus was used as solvent for all experiments. 2.2. Catalytic system 2.2.1. Preparation procedure A colloidal dispersion of gold was prepared in a similar way as already reported [7], by treating a 1.25 104 mol L1 aqueous solution of Au (as HAuCl4) with a freshly prepared solution of NaBH4 (NaBH4:Au = 5 mol mol1) under N2 atmosphere, in the presence of a large excess of glucose (0.35 mol L1). 2.2.2. Colloid preparation: stability and reproducibility To obtain informations about the reproducibility of our preparation method and the stability of the prepared gold colloids, several tests have been done. In a rst series of experiments, the mean diameter (dm) of gold particles and its relationship with the storage time and preparation temperature has been checked. In a second series of tests, several identical colloidal gold solutions have been prepared to check their reproducibility. Results are reported in Section 3.1. 2.2.3. Catalyst characterization The mean diameter of the gold particles (dm) was mainly calculated after deposition of the colloidal solution on carbon XC72R, by XRD technique (Rigaku D III-MAX horizontalscan powder diffractometer with Cu Ka radiation) using the Scherrer equation, as previously reported. TEM determination on a drop of gold sol deposited on copper grid gave results similar to XRD (3%) [7]. 2.3. Procedure for kinetic studies 2.3.1. Oxidation of glucose All the experiments were carried out in a semi-batch reactor (50 mL) at controlled temperature (0.1 K), pH value (0.1) and magnetic stirring (1700 rpm), by using a 751 GPD Titrino (Metrohm) equipped with NaOH as titration reagent. Oxygen and nitrogen (total ow 100 Ncm3 min1) were mixed in different ratios using mass ow instruments (Brooks 5850E controlled by a Brooks 5878 gas controller) and bubbled at atmospheric pressure through the aqueous solution of glucose at different concentrations. A constant gold concentration of 1.41 105 mol L1 was used in all experiments. The

activation energy was evaluated in the temperature range from 303.2 to 333.2 K (DT = 10 K). Glucose oxidation was started by adding the colloidal gold solution, prepared and stored at the reaction temperature, to the gas saturated solution of glucose under stirring at the desired temperature value, while NaOH was automatically added to neutralize the reaction product, gluconic acid, at pH 9.5. 2.3.2. Evaluation of reaction rate Gluconic acid concentration versus time plots were derived from the NaOH addition rate. After an initial induction period (0 20 s) due to the rst NaOH addition, the plots of DCGluconic versus time were linear (R  0.991) up to 50% fractional conversion, allowing the use of the initial rate method. The zero time was taken after 30 s from the colloidal gold solution addition. The reaction has been usually monitored for 200 s: during this time 20 analytical points were collected, in most cases with nal fractional conversion of glucose between 3 and 15%. 2.3.3. Oxygennitrogen ratio The solubility of oxygen in the reacting solution was mainly dependent on temperature and less on glucose concentration (from 0.050 to 0.500 mol L1 of glucose). Therefore, different oxygen molar fractions in the gas phase, calculated according to the previously reported smoothing equation and related table [8,9], have been used at different temperatures. A direct determination of dissolved oxygen was performed with an AMEL instrument equipped with an AMEL 332/P electrode, as previously reported [8], as a control test. 2.3.4. Diffusional effects In order to avoid gas mass transfer control during glucose oxidation, stirring rate, oxygen ow and colloidal gold concentration were optimized at the highest temperature investigated (333.2 K) and using a 0.100 M glucose solution. Over 1500 rpm, no rate control by oxygen mass transfer was found using more than 50 Ncm3 min1 of O2 and gold concentration below 4.5 105 mol L1. Therefore, the standard kinetic experiments were carried out at 1700 rpm, with a total gas ow of 100 Ncm3 min1, and using a gold concentration of 1.41 105 mol L1. 2.4. Effect of the glucose and oxygen concentration on the reaction rate To evaluate the effect of the glucose concentration on the reaction kinetics, a rst set of runs was carried out at constant oxygen concentration (8.82 104 mol L1), different glucose concentration (0.050, 0.075, 0.200, 0.300 and 0.500 mol L1) and different temperature values (303.2, 313.2, 323.2 and 333.2 K). In a second set of experiments, the effect of the oxygen concentration on the reaction kinetics has been evaluated. In these runs, two different O2 concentrations (8.82 104 and 4.41 104 mol L1) have been used for two different temperatures values (303.2 and 323.2 K) and ve different glucose concentrations (0.050, 0.075, 0.100, 0.350 and 0.500 mol L1).

P. Beltrame et al. / Applied Catalysis A: General 297 (2006) 17

2.5. Analysis of products Analysis was performed by HPLC on a Varian 9010 instrument equipped with a Varian 9050 UV (210 nm) detector. An Alltech OA-1000 column (300 mm 6.5 mm) was used with aqueous H2SO4 0.01 M (pH 2.1) (0.4 ml/min) as the eluent. The product of glucose oxidation was identied as gluconic acid by comparison with the standard compound as also previously reported [4]. Hydrogen peroxide was detected and quantied in the reaction products according to the following procedure: a solution (4 ml of 0.38 M glucose, 2.5 105 M Au) saturated with O2 at 303.2 K was left to react and samples withdrawn at different times. Each sample was titrated with KMnO4 (2 102 M) in the presence of MnSO4 (103 M) and H2SO4 at pH = 1.8 0.1, in order to oxidise only H2O2 in the presence of a large amount of glucose. Blank experiments on glucoseH2O2 solutions of similar concentrations showed an acceptable reproducibility (2%): hydrogen peroxide was correctly determined independently of the quantity of glucose present in the system. 3. Results and discussion 3.1. Gold colloids: reactivity, stability and suitability Unsupported colloidal gold particles were recently used for the aerobic glucose oxidation, showing catalytic activity comparable with the supported Au/C catalyst and an enzymatic system [7]. This result, beside practical applications, could be of interest for determining the oxidation mechanism. In fact, the catalytic role of the support is difcult to evaluate being often speculative as, for example, during CO oxidation [1]. In the case of unsupported metal particles information derived from kinetic studies could be more easily associated to a molecular model. For this reason and also for evaluating the competition of pseudo-homogeneous colloidal gold particles and the enzymatic system actually used for the industrial production of gluconic acid we have undertaken a comparative study under similar experimental conditions. In the rst part of this work we have carried out deep investigation on an enzymatic system composed by glucose oxidase and catalase [8]. A simplied version of the reaction mechanism and the activation energy concerning the main steps of the reaction have been proposed and calculated. First of all, in the present work, some preliminary tests under xed conditions (CAu = 1.25 104 mol L1; CGlu = 0.35 mol L1; NaBH4: Au = 5 mol mol1; T = 303.2 K; P = 101 KPa; nitrogen atmosphere) were performed to check the stability of the gold sol and the reproducibility of the preparation method. The mean diameter of the metal gold particles remained unchanged, according to evaluations every 20 min (dm = 3.6 0.1 nm), at least for 140 min, that is the time required for a group of kinetic runs. For 10 different preparation lots, the particle size showed only slight random differences (dm = 3.4 0.1 nm), proving that the use

of different gold colloids for the same set of runs cannot misrepresent the results. Finally, similar preparations have been carried out at different temperature values (from 303.2 to 333.2 K) to get more informations about the thermal stability of our catalytic system and the effect of temperature during the generation of colloidal gold. The mean diameter of the gold particles resulted independent of temperature and storage time. 3.2. Kinetic models and their application Kinetic measurements have been performed in a similar manner to the previously reported enzymatic oxidation [8] at the xed pH value of 9.5 by using an automatic apparatus that allowed the titration in real time of the gluconic acid produced. Several runs were carried out for a set of experimental conditions where temperature (from 303.2 to 333.2 K) and glucose concentration (from 0.050 to 0.500 M) have been chosen in order to allow comparisons with previous work on the enzymatic catalysis [8] and carbon supported gold catalyst [10]. Initial rates (r0) were obtained from the average slope of the titration plots. Accurate determination of hydrogen peroxide in the initial part of the reaction showed that this compound is formed, beside gluconic acid, as the primary product of oxygen reduction; hydrogen peroxide accumulates up to 102 M concentration and disappears owing to decomposition. Under the conditions described in 2.5 the concentration of H2O2 resulted 6 103 M (100 s), 1.1 102 M (400 s), 5 103 M (900 s) and <104 M (1900 s), to be compared with 9.9 103, 3.1 102, 5.5 102 and 7.0 102, respectively, as calculated for a 1:1 ratio of H2O2/gluconic acid. The dependence of the rate (r0) on glucose and oxygen concentrations was the main object of the experimental work. Runs were carried out at different oxygen concentrations 0 (8.82 104 and 4.41 104 mol/L) and xed values of CG . The results (Table 1 and Fig. 1) showed that the rate was proportional to the oxygen concentration. Several runs were carried out at constant oxygen concentration, in order to determine the dependence of the rate on the glucose concentration. The values of the rate (Table 1) were always 0 increasing versus CG , but tending to an asymptote, that is to a 0 zero-order reaction (with respect to glucose) at large CG values. This is apparent in the data sequences in Table 1 and is graphically represented, for a typical case, in Fig. 2. A reaction mechanism able to interpret the results was then looked for. A dehydrogenation mechanism can be represented by Eq. (1) and (2),
k1

G 2s !L 2Hs ;

2 r1 k1 CG Cs

(1)

2Hs O2 !H2 O2 2s ;

k2

2 r2 k 2 C H s Co2

(2)

where G is the hydrated form of glucose, s an active centre on the surface of the Au catalyst and L the gluconate product.

P. Beltrame et al. / Applied Catalysis A: General 297 (2006) 17

Table 1 Initial reaction rate under different glucose and oxygen concentrations, at the given temperature values (CAu = 1.41 105 mol L1) T (K) CO2 mol L1 First set of runs
0 CGlu

Second set of runs r0 (mol L 0.0959 0.1083 0.1165 0.1320 0.1425 0.1502 0.1793 0.1983 0.2312 0.2358 0.2918 0.3548 0.3958 0.4657 0.4783 0.4849 0.5899 0.6259 0.7405 0.7548
1

mol L

h )

0 mol L1 CGlu

r0 (mol L1 h1) 0.1020 0.1196 0.1382 0.1440 0.1472 0.0490 0.0629 0.0715 0.0746 0.0790 0.2856 0.3556 0.4144 0.4288 0.4392 0.1421 0.1782 0.2112 0.2307 0.2384

303.2

8.82 104

0.050 0.075 0.100 0.300 0.500 0.050 0.075 0.100 0.300 0.500 0.050 0.075 0.100 0.300 0.500 0.050 0.075 0.100 0.300 0.500

0.050 0.075 0.200 0.350 0.500 0.050 0.075 0.200 0.350 0.500 0.050 0.075 0.200 0.350 0.500 0.050 0.075 0.200 0.350 0.500

4.41 104

313.2

8.82 104

323.2

8.82 104

4.41 104

333.2

8.82 104

The dehydrogenationoxidation mechanism is similar to that for the enzymatic oxidation of glucose [8]. However, this mechanism corresponds to a kinetic equation compatible with the rst order with respect to oxygen only by assuming that step 2 is rate determining, the reaction being of zero-order with respect to glucose. This has not been observed. Moreover, in the case of oxidations over platinum group metals, this mechanism

is also supported by a quantiable conversion of the reagent into the expected product in the absence of O2 [11], while we have to outline that, in our case, no reaction took place in the absence of O2. A further mechanism considered was of LangmuirHinshelwood type, characterised by adsorption of glucose in its hydrated form and associative adsorption of oxygen, and

Fig. 1. Plots of initial rate vs. oxygen concentration for the second set of runs at two different temperature values for different glucose concentrations.

P. Beltrame et al. / Applied Catalysis A: General 297 (2006) 17

0 this model mental results, because in a plot of r0 versus CG foresees a maximum instead of an asymptote (Fig. 2). Finally, an EleyRideal mechanism, characterised by the adsorption of glucose, in its hydrated form, on gold, with equilibrium constant KG, followed by reaction with oxygen coming from the liquid phase, according to Eqs. (6) and (7), can justify the results.

G s !Gs !L H2 O2 s ; Gs O2
Fig. 2. Example of a plot of initial rate vs. initial glucose concentration. The curve calculated by model ER (parameter values from Table 2) is compared with the one of the LangmuirHinshelwood model (Eq. (5); optimised parameters: kcatKGKO2 CO2 = 2.8 105 L mol1 h1; KG = 4.02 L mol1). The latter curve shows a maximum not present in the experimental points.
ks

KG

(6)

(7)

r ks uG CO2 kcat CAu uG CO2 This mechanism gives rise to the rate Eq. (8), which justies both the rst-order with respect to oxygen and the decreasing order with respect to glucose, tending to zero for large values of CG. The detection of a relevant quantity of hydrogen peroxide, close to the stoichiometric amount with respect to gluconic acid, L, provides further experimental support. kcat KG CAu CG CO2 (8) r 1 KG CG This kinetic model was labelled ER. It contains two parameters, kcat (kinetic coefcient of the rate determining step) and KG (adsorption constant of glucose on the catalyst). The parameter values were determined for each group of runs, at constant 0 temperature and CO2 and different CG values, by an optimisation procedure [14]. The objective function to be minimized was o o F Srexptl rcalcd 2 =np n, where np is the number of experimental points and n the number of parameters to be optimised. The order of magnitude of the minimized function F was from 106 to 104. The standard error s of the estimate of initial rates [s = F 1/2] represented from 2 to 4% of ro for runs at the higher oxygen concentration, from 2 to 6% of ro for runs at the lower oxygen concentration. From the initial rate values (Table 1) the values of kcat and KG shown in Table 2 were obtained. Model ER gives a good interpretation of the kinetics at all the investigated temperatures and reactant concentrations. The two sets of runs gave kcat and KG values reasonably similar at a given temperature. The differences fall into experimental uncertainty in the determination of the rates for separate sets of

having a rate determining surface reaction between adsorbed reactants, as in Eq. (3). G s O 2 s ! L H 2 O 2 2s (3)

A mechanism of this type, but including dissociative adsorption of oxygen, has been suggested for the oxidation of a sorbose derivative by oxygen over a Pt/C catalyst [12]. Associative adsorption of oxygen and peroxide-like intermediates have been proposed in the literature for oxidations catalysed by supported gold [13]. In our case, a Langmuir Hinshelwood mechanism would give rise to a rate equation with the form of Eq. (4); neglecting the term in the denominator which refers to oxygen adsorption, in order to justify the rst order reaction with respect to oxygen experimentally observed, the simplied Eq. (5) can be applied. r kcat KG KO2 CAu CG CO2 1 KG CG KO2 CO2 2 kcat KG KO2 CAu CG CO2 1 KG CG 2 (4)

(5)

However, this LangmuirHinshelwood model has a weak point: 0 the dependence of r0 on CG does not correspond to experiTable 2 Evaluation of the parameters for model ER, from the rates in Table 1 T (K) CO2 mol L1 8.82 104 4.41 104 8.82 104 4.41 104 8.82 104 4.41 104 8.82 104 4.41 104 First set of runs kcat (L mol 303.2 313.2 323.2 333.2
1

Second set of runs KG (L mol ) 37.0 31.2 28.1 32.5

1

h )

kcat (L mol1 h1) 1.24 10 7 1.33 10 7 3.76 10 7 4.10 10 7

KG (L mol1) 41.3 33.5 35.6 27.3

1.19 10 7 2.05 10 7 4.17 10 7 6.52 10 7

P. Beltrame et al. / Applied Catalysis A: General 297 (2006) 17

Fig. 4. Arrhenius plot for the kcat coefcient, with points from both sets of runs (CAu = 1.41 105 mol L1).

Fig. 3. Plots of initial rate vs. initial glucose concentration for runs at CO2 = 8.82 104 mol L1. The curves are separately calculated for the two sets of runs by model ER.

intervention of gaseous O2 [16,17]. Also in the case of other catalysts, mainly metals of the platinum group, whenever an oxidation mechanism of the EleyRideal type is reported, it is meant as a reaction of adsorbed oxygen with other molecules coming from the gas or liquid phase. To our knowledge, an opposite role of the reactants has been only reported for the oxidation SO2 + O2 over activated carbon, where a reaction of two adsorbed SO2 molecules with oxygen from the gas phase has been proposed [18]. However, the fact that the present study has evidenced a rst-order dependence on oxygen concentration, while other oxidations on gold catalysts [1517] show very low reaction order with respect to oxygen, indicates that the oxidation of glucose on gold is quite different from other cases. 3.3. Comparison between enzymatic and inorganic catalysis It has been found that inorganic gold nanoparticles and Oxidase enzyme share the common stoichiometric reaction producing gluconate and hydrogen peroxide, that is: C6 H12 O6 O2 H2 O ! C6 H12 O7 H2 O2 followed in both cases by decomposition of hydrogen peroxide either through alkali promoted decomposition, in the present case, or Catalase promoted decomposition [8]. Although their reaction mechanisms appear quite different, a numerical comparison of rates in our experimental conditions can be made considering the MichaelisMenten equation of Part I [8], written in the equivalent form of Eq. (9), and Eq. (8) of the present ER model, at 303.2 K, where experimental data are available for both catalysts. 0 o k1 CE CG r0 (9) 0 1 k1 =kC CG The parameters in the denominator of Eq. (9), for the enzyme, and Eq. (8), for gold, show similar values: in the enzymatic catalysis, (k1/kc) has the value of 42.5 L mol1 [8], while KG for the gold catalysis has the value of 37.0 L mol1 (Table 2). As to the numerators of Eqs. (8) and (9), the kinetic coefcient k1 in

runs. This is better shown in Fig. 3, where it can be outlined that the deviations of one set with respect to the other have opposite sign at the two temperatures. The values of kcat at different temperatures from the two sets of runs were correlated by an Arrhenius plot (Fig. 4) showing an activation energy of 47.0 1.7 kJ mol1, with ln A equal to 35.0 0.6 (with A in L mol1 h1). To measure the dependence on temperature of KG proved difcult, because the values obtained by the ER model in different runs are affected by a rather large uncertainty: one can realize this by looking at Table 2. This parameter tends to decrease when the temperature is increased, as expected from an adsorption constant, but the dependence is scarce. Therefore, the value of DHads for glucose on our catalyst is negative, but quite low. Examining the reaction mechanisms previously proposed for other oxidations on gold catalysts, one realizes that the mechanism underlain by model ER is far from common. A fundamental reaction in this eld is the oxidation of hydrogen to give water: a recent paper [15] reports a rate equation compatible with a mechanism in which the rate determining step is the reaction of H2 from the gas phase with an adsorbed OOH and a free surface site; the apparent reaction order with respect to oxygen was found to be very low. Another well studied reaction is the oxidation of CO to give CO2: on several supported gold catalysts very low values of the reaction order with respect to oxygen have been reported, excluding the

P. Beltrame et al. / Applied Catalysis A: General 297 (2006) 17

Eq. (9) has to be compared with the product kcatKGCO2 in Eq. (8). The last product, in our conditions (CO2 = 8.82 104 mol L1), has a value of 0.39 106 L mol1 h1; for enzyme catalysis, taking into account the molar content of FAD in the Hyderase [8], the value k1 = 28.1 L g1 h1 becomes equivalent to 21.6 106 L mol1 h1, suggesting that the enzyme is 55 times more active than the gold sol. Concerning this point, two considerations have to be done: rst of all, in glucose oxidase all the avineadenine dinucleotide units are active catalytic sites, whereas in gold particles only the peripheral atoms behave as active sites (30% of the gold atoms in 3.5 nm particles) [7]; more in particular, due to the size difference between glucose molecules and gold atoms, one expects that the number of available atoms is only a fraction of the total surface atoms owing to steric hindrance of the adsorbed glucose. These considerations bring to consider gold catalytic sites almost as active as the enzymatic ones. Finally, the activation energy values for the rate coefcients k1 (enzyme catalysis) and kcat (gold sol catalysis) can be considered. They resulted very similar, being 49.6 4.4 and 47.0 1.7 kJ mol1, respectively. They are both very low values, a reasonable fact because the measured values of coefcients k1 and kcat are both quite high, corresponding to easy reactions. The close values of these activation energies, however, has no signicance of similar reaction mechanisms. About a previous investigation on glucose oxidation catalysed by a supported gold catalyst (0.48 wt.% Au on carbon) [10], we can observe that the rate equation suggested by the authors corresponds to a dehydrogenationoxidation mechanism, where Au is the dehydrogenating agent and its re-oxidation is a fast step. However, these authors did not investigate the dependence of the rate on CO2 . Considering initial rates, their rate equation can, to a good approximation, be written as Eq. (10), neglecting the adsorption of gluconic acid because of its minor weight, particularly in the early stages of the reaction.
0 kox Ccat CG 0 1 KG CG

important cooperative effects and diffusion constraints produced by the support. 4. Conclusions Gold catalysis and Oxidase + Catalase catalysis promote the fast and selective aerobic oxidation of glucose according to a similar stoichiometry involving the formation of transient hydrogen peroxide. However, it is not surprising that completely different catalytic systems adopt different reaction mechanisms. This investigation shows that, in the case of enzymatic catalysis, the rate-determining step is the oxidation of glucose by the enzyme, which is converted into its reduced form. This latter is re-oxidized by oxygen in faster steps: the reaction order with respect to oxygen is close to zero. In the case of colloidal gold catalysis, the rate equation can be interpreted by a mechanism where the rate determining step is the oxidation of glucose, easily adsorbed on the metal, by oxygen dissolved in the liquid phase: the reaction is rst order with respect to oxygen. Although the reaction mechanisms are different, the catalysts showed close values of the activation energy for the respective rate determining steps. Acknowledgments We thank professor Geoffrey Bond for fruitful discussion and helpful suggestions. We gratefully acknowledge the nancial support provided by the EC project AURICAT Research Training Network (HPRN-CT 2002-00174). References
[1] G.C. Bond, D. Thompson, Catal. Rev. -Sci. Eng. 41 (1999) 319. [2] F. Porta, L. Prati, M. Rossi, S. Coluccia, G. Martra, Catal. Today 61 (2000) 165. [3] C. Bianchi, F. Porta, L. Prati, M. Rossi, Topics Catal. 13 (2000) 231. [4] S. Biella, G.L. Castiglioni, C. Fumagalli, L. Prati, M. Rossi, Catal. Today 72 (2002) 43. [5] T. Mallat, A. Baiker, Chem. Rev. 104 (2004) 3037. [6] C.L. Bianchi, S. Biella, A. Gervasini, L. Prati, M. Rossi, Catal. Lett. 85 (2003) 91. [7] M. Comotti, C. Della Pina, R. Matarrese, M. Rossi, Angew. Chem. Int. Ed. 43 (2004) 5812. [8] P. Beltrame, M. Comotti, C. Della Pina, M. Rossi, J. Catal. 228 (2004) 282. [9] D.R. Lide (Ed.), Handbook of Chemistry and Physics, 72 ed., 1991, p. 63. nal, S. Schimpf, P. Claus, J. Catal. 223 (2004) 122. [10] Y. o rgi, T. Mallat, A. Baiker, J. Catal. 211 (2002) 244. [11] C. Keresszegi, T. Bu [12] L. Nondek, D. Zdarova, J. Malek, V. Chvalovsky, Collect. Czech. Chem. Commun. 47 (1982) 1121. [13] S. Golunski, R. Rajaram, N. Hodge, G.J. Hutchings, C.J. Kiely, Catal. Today 72 (2002) 107, and references therein. [14] G. Buzzi Ferraris, Ing. Chim. Ital. 4 (1968) 171. [15] D.G. Barton, S.G. Podkolzin, J. Phys. Chem. B 109 (2005) 2262. [16] G.C. Bond, D.T. Thomson, Catal. Rev.-Sci. Eng. 41 (1999) 319. [17] H. Liu, A.I. Kozlov, A.P. Kozlova, T. Shida, Y. Iwasawa, Phys. Chem. Chem. Phys. 1 (1999) 2851. s, A. Linares-Solaro, Carbon 39 ero, D. Cazorla-Amoro [18] E. Raymundo-Pin (2001) 231.

r0

(10)

However, with the KG value reported by these authors, the 0 product KGCG in the denominator of Eq. (10) results of the 8 order of 10 . Being the unity completely negligible, Eq. (10) behaves as a zero-order equation. In our opinion, parameters kox and KG in Eq. (10) are so strongly correlated that they cannot be separately determined, and the mechanism suggested by these authors [10] is not really proved. In any case, considering the region where the zero-order kinetics is approximately valid, that is close to the asymptotic 0 portion of the plots of r0 versus CG , Table 1 shows, for 4 T = 323.2 K and CO2 = 8.82 10 mol L1, a value r0 of ca. 0.48 mol L1 h1, while a four times lower value of 0.12 mol L1 h1 can be evaluated for Au/C [10] in similar conditions. On the other hand, tests on glucose oxidation with unsupported and carbon supported gold particles having the same geometry indicated an almost identical activity for both catalytic systems [7], suggesting the absence of kinetically