The production of high-value-added organics by the glycerol oxidation reaction (GOR) holds significant research importance for addressing the surplus production of glycerol and mitigating the energy crisis. In this study, we report a vacancy optimized coordination on nickel oxide for the selective electrocatalytic oxidation of glycerol. Using in situ Raman and electron paramagnetic resonance spectroscopy, the formation of vacancies was traced during the cationic leaching process. Subsequently, in situ attenuated total reflection surface-enhanced IR absorption spectroscopy and density functional theory calculations revealed a significantly enhanced adsorption capacity and optimized co-adsorption process of OH^– and organics. Consequently, NiCrO with vacancies (NiCrO-V_Cr,O) exhibited GOR performance with conversion, formic acid selectivity, and faradaic efficiency values of 99%, 98%, and 96%, respectively. Notably, the conversion and selectivity in the flow electrolyzer remained above 90% during long-time continuous electrolysis, highlighting its industrial applicability. This study provides constructive guidance for the design of electrocatalysts, the optimization of the catalyst ligand environment, and the development of high-performance, metal-based catalysts for glycerol electro-oxidation.

中文翻译：

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氧化镍上的空位优化配位用于甘油的选择性电催化氧化

通过甘油氧化反应（GOR）生产高附加值有机物对于解决甘油生产过剩和缓解能源危机具有重要的研究意义。在这项研究中，我们报告了氧化镍上的空位优化配位，用于甘油的选择性电催化氧化。利用原位拉曼和电子顺磁共振光谱，追踪了阳离子浸出过程中空位的形成。随后，原位衰减全反射表面增强红外吸收光谱和密度泛函理论计算表明，OH-和有机物的吸附能力显着增强，共吸附过程得到^优化。因此，具有空位的 NiCrO (NiCrO-V _Cr,O ) 表现出 GOR 性能，转化率、甲酸选择性和法拉第效率值分别为 99%、98% 和 96%。值得注意的是，流动电解槽在长时间连续电解过程中转化率和选择性均保持在90%以上，凸显了其工业适用性。该研究为电催化剂的设计、催化剂配体环境的优化以及甘油电氧化高性能金属基催化剂的开发提供了建设性指导。