School of Environment and Energy, State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, 510006, Guangzhou, Guangdong, China.
Department of Chemical Engineering, Pohang University Science and Technology, Pohang, Gyeongbuk, 37673, Republic of Korea.
Nat Commun. 2022 Jun 30;13(1):3777. doi: 10.1038/s41467-022-31484-0.
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 C-C bond cleavage. Consequently, NiCo hydroxide exhibits enhanced glycerol electrooxidation activity, with a current density of 100 mA/cm 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，最近晶格中的质子和氧被发现积极参与催化反应，并对反应性起着关键作用。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）插过程对基元步骤的影响。通过密度泛函理论计算和先进的光谱技术相结合，我们发现钴掺杂到氢氧化镍中会促进质子和氧阴离子从催化剂表面的脱插。在甘油电氧化反应过程中，NiCo 氢氧化物中形成的氧空位增加了 Co 位的 d 带填充，促进了在 2 C-C 键断裂过程中电荷从催化剂表面向断裂分子的转移。因此，NiCo 氢氧化物表现出增强的甘油电氧化活性，在 1.35 V 时的电流密度为 100 mA/cm，且甲酸盐选择性为 94.3%。
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