Efficient base-free direct oxidation of glucose to gluconic acid over TiO₂-supported gold clusters

The transformation of renewable natural resources is an appealing and sustainable protocol to minimize fossil fuel consumption. Here, a simple incipient wetness protocol is developed to prepare ultrasmall gold clusters, immobilized on TiO2 (particle size: 1.2-1.7 nm), using anthranilic acid as a stabilizing agent. The Au clusters can be reduced to metallic Au0 (Au/TH-150 and Au/TH-200) during 150 and 200 °C annealing in the presence of H2 gas, while the Au clusters are converted to Auδ+ species in air at 200 and 500 °C (Au/TA-200 and Au/TA-500), a conclusion supported by XPS and low-temperature (-150 °C) Operando-DRIFTS analysis. Au/TA-200 and Au/TA-500 showed inactivity in the base-free direct oxidation of glucose. For comparison, Au/TH-150 and Au/TH-200 exhibited salient catalytic performance (87-92% conversion and 95-97% selectivity for gluconic acid), revealing that glucose oxidation occurs preferentially on the Au0 species. The turnover frequency (TOF) of Au/TH-150 reaches 1908 molreacted glucose molAu-1 h-1, which is much higher than that of commercial Pd-Bi/C under alkaline conditions (TOF: 1298 molreacted glucose molPd-1 h-1, pH 9.5). The apparent activation energies are 37 (over Au/TH-150) and 47 kJ mol-1 (Au/TH-200), comparable to the unsupported Au colloids, indicating that the oxidation should occur at the Au surface rather than at the perimeter interface between the Au clusters and the supports.