The redox center of transition metal oxides and hydroxides is generally considered to be the metal site. Interestingly, proton and oxygen in the lattice recently are found to be actively involved in the catalytic reactions, and critically determine the reactivity. Herein, taking glycerol electrooxidation reaction as the model reaction, we reveal systematically the impact of proton and oxygen anion (de)intercalation processes on the elementary steps. Combining density functional theory calculations and advanced spectroscopy techniques, we find that doping Co into Ni-hydroxide promotes the deintercalation of proton and oxygen anion from the catalyst surface. The oxygen vacancies formed in NiCo hydroxide during glycerol electrooxidation reaction increase d-band filling on Co sites, facilitating the charge transfer from catalyst surface to cleaved molecules during the 2^nd C-C bond cleavage. Consequently, NiCo hydroxide exhibits enhanced glycerol electrooxidation activity, with a current density of 100 mA/cm² at 1.35 V and a formate selectivity of 94.3%.

过渡金属氧化物和氢氧化物的氧化还原中心通常被认为是金属位点。有趣的是，最近发现晶格中的质子和氧积极参与催化反应，并严格决定反应性。在此，我们以甘油电氧化反应为模型反应，系统地揭示了质子和氧阴离子（脱）插层过程对基本步骤的影响。结合密度泛函理论计算和先进的光谱技术，我们发现将Co掺杂到氢氧化镍中可以促进质子和氧阴离子从催化剂表面脱嵌。甘油电氧化反应过程中氢氧化镍钴中形成的氧空位增加d^{- 带填充在 Co 位点上，在第二}个CC 键断裂过程中促进电荷从催化剂表面转移到断裂分子。因此，NiCo 氢氧化物表现出增强的甘油电氧化活性，在 1.35 V 时电流密度为 100 mA/cm ²，甲酸盐选择性为 94.3%。