A. Taketoshi et al. / Applied Catalysis A: General 468 (2013) 453–458
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(
0.5) by titrating with 1 M L−1 NaOH aqueous solution. The con-
version of glucose was calculated from the total amount of NaOH
added. The reaction mixture was filtrated to remove the catalyst
and the filtrate was evaporated. The residue was analyzed by 1H
NMR (JEOL 300 MHz, D2O) to compare with authentic sample of
sodium gluconate.
3.1. Combination effect of enzyme and gold catalysts on glucose
oxidation
Table 1 shows the catalytic activity of glucose oxidase combined
with gold NPs supported on a variety of metal oxides and on car-
bons. The initial rate, which was calculated from the slope of the
straight part of conversion vs reaction time, shows the initial cat-
alytic activity, whereas the conversion of glucose after 1 h reaction
reflects the stability property of the catalytic systems. In the case
of several representative gold catalysts, they were prepared by 2–5
times by the same method under the same conditions and were
subjected to glucose oxidation (entries 1, 2, 4, 7, 10 and 12).
Supported gold NPs catalysts can be classified into two groups.
The first one showed increases in both initial rate of reaction
and conversion of glucose after 1 h reaction by the combination
with glucose oxidase. They are, in the order of decreasing catalytic
activity, Au/ZrO2, Au/ND, Au/La2O3, Au/Al2O3, Au/CeO2, Au/SnO2,
Au/MnO2, and Au/Co3O4 (entries 1–9). The second one showed
decreases in both initial rate of reaction and conversion after 1 h
and is composed of Au/Fe2O3, Au/SiO2, Au/TiO2, Au/ZnO, Au/V2O5,
Au/NiO, Au/CuO, and Au/KB (entries 11–18). There seems to be no
clear correlations between the kind of metal oxide supports and the
enhancing effect on the catalytic activity for glucose oxidation. It is
likely that synergy between supported gold catalysts and glucose
oxidase may depend on the biological compatibility rather than on
physicochemical properties of the support materials.
Fig. 2. Conversion–time curves for glucose oxidation in neutral aqueous solution at
30 ◦C with GOx and Au/ZrO2. Reaction conditions: 2 wt% aqueous glucose solution
(31 mL), GOx (0.13 g L−1), 0.5 wt% Au loading catalyst (8.0 mg), glucose/Au = 15,000
(mol/mol), O2 (60 mL min−1), 30 ◦C, pH 7. The pH of the solution was kept at 7 by
the titration with 1 M NaOH aqueous solution. Conversion was calculated by the
amount of NaOH added. (᭹) GOx + Au/ZrO2; (ꢀ) GOx; (ꢀ) GOx + ZrO2; (ꢁ) Au/ZrO2.
without gold deposition, ND, ZrO2, Al2O3, and KB, only NanoDi-
amond presented higher conversion of glucose after 1 h reaction
(entries 19–22).
Fig. 1 shows that glucose oxidase alone could not attain 100%
conversion because of the deactivation by H2O2 formed during
reaction. The combination with KB without gold deposition yielded
lower conversions than with Au/KB, suggesting that gold NPs could
facilitate the decomposition of H2O2. In fact, Table 2 shows that
deposition of gold NPs or Pt NPs on ZrO2, Al2O3, ND, and KB
increased the rate of H2O2 decomposition (entries 1–9). In con-
trast, the combination with ND without gold deposition yielded a
little higher conversion than glucose oxidase alone. Because H2O2
decomposition on ND was moderately fast similar to KB, it can be
assumed that the co-presence of ND enhances gluconic acid pro-
duction by glucose oxidase. Deposition of gold NPs on ND enabled
glucose oxidase to transform glucose with 100% conversion. This
It is interesting to note that two carbon materials show opposite
effect on the catalytic activity. Gold NPs deposited on KetjenBlack
having mesopores reduced the initial oxidation rate with glucose
oxidase by half, while gold NPs on NanoDiamond which were non-
porous enhanced the initial rate by 17%. Among supports alone
Fig. 1. Conversion–time curves for glucose oxidation in neutral aqueous solution
at 30 ◦C with GOx and Au/carbon supports. Reaction conditions: 2 wt% aqueous
glucose solution (31 mL), GOx (0.13 g L−1), 0.5 wt% Au loading catalyst (8.0 mg), glu-
cose/Au = 15,000 (mol/mol), O2 (60 mL min−1), 30 ◦C, pH 7. The pH of the solution
was kept at 7 by the titration with 1 M NaOH aqueous solution. Conversion was cal-
culated by the amount of NaOH added. (᭹) GOx + Au/ND; (ꢀ) GOx + ND; (ꢀ) GOx;
(ꢁ) GOx + Au/KB; (ꢁ) GOx + KB.
Fig. 3. Conversion–time curves for glucose oxidation in neutral aqueous solution at
30 ◦C with GOx and Au/Al2O3. Reaction conditions: 2 wt% aqueous glucose solution
(31 mL), GOx (0.13 g L−1), 0.5 wt% Au loading catalyst (8.0 mg), glucose/Au = 15,000
(mol/mol), O2 (60 mL min−1), 30 ◦C, pH 7. The pH of the solution was kept at 7 by the
titration with 1 M NaOH aqueous solution. Conversion was calculated by the amount
of NaOH added. (᭹) GOx + Au/Al2O3; (ꢀ) GOx; (ꢀ) GOx + Al2O3; (ꢁ) Au/Al2O3.