Selective and efficient oxidation of a certain hydroxyl group in biomass-derived polyols is quite appealing but challenging. We herein propose a new photoelectrochemical strategy for enhancing the selectivity and kinetics of the middle hydroxyl oxidation in glycerol molecules using Au/C₃N₄ catalyst. The introduction of illumination and usage of C₃N₄ are first demonstrated to have a direct bearing on enhancing the selectivity of middle hydroxyl oxidation on Au through the electron transfer and accelerating the kinetics by accumulating photogenerated holes with moderate oxidizability. By this strategy, the selectivity of glycerol to dihydroxyacetone and turnover frequency are achieved as high as 53.7% and unprecedented 4,619 h⁻¹. The synergy of electronic interaction, localized surface plasmon resonance effect, and photogenerated carriers dual injection is revealed to account for such high selectivity and kinetics of the middle hydroxyl oxidation during the photoelectrochemical process. Our results sheds light on the photoelectrocatalysis-driven selective hydroxyl oxidation in polyols.

生物质衍生多元醇中某个羟基的选择性和有效氧化非常有吸引力但具有挑战性。我们在此提出了一种新的光电化学策略，用于使用 Au/C ₃ N ₄催化剂提高甘油分子中中间羟基氧化的选择性和动力学。首次证明引入光照和使用 C ₃ N ₄直接关系到通过电子转移提高 Au 上中间羟基氧化的选择性，并通过积累具有中等氧化性的光生空穴来加速动力学。通过这种策略，甘油对二羟基丙酮的选择性和转换频率达到了高达 53.7% 和前所未有的 4,619 小时^-1。揭示了电子相互作用、局部表面等离子体共振效应和光生载流子双注入的协同作用，解释了光电化学过程中中间羟基氧化的高选择性和动力学。我们的结果揭示了多元醇中光电催化驱动的选择性羟基氧化。