中国科学院大连化学物理研究所吴忠帅团队报道了，泡沫镍负载的Cu掺杂NiCo合金上甘油高效电催化氧化生成甲酸酯及硝酸盐还原。相关研究成果发表在2024年8月12日出版的《德国应用化学》。

生物质衍生甘油的电氧化被认为是工业生物柴油生产的主要副产品，是一种生产增值化学品的创新策略，但目前表现出缓慢的动力学、有限的法拉第效率和不清楚的催化机制。

该文中，研究人员报道了在与硝酸盐还原配对的耦合系统中，通过负载在泡沫镍（Cu-NiCo/NF）上的铜掺杂NiCo合金催化剂将甘油高效电氧化为甲酸盐。设计的Cu-NiCo/NF在10mA cm^-2下仅有1.23 V vs.RHE，甲酸盐的法拉第效率创纪录地达到93.8%。

优异的性能归因于NiIII OOH和CoIII OOH的快速产生以及表面*O与反应性中间体的良好偶联。使用Cu-NiCo/NF作为双功能催化剂，耦合系统同步产生NH₃和甲酸盐，比析氢反应的耦合低290 mV，长期稳定性高达144小时。

该项工作为生物质衍生电化学精炼从催化剂设计到系统耦合，提供了新的指导方针和可靠的策略。

附：英文原文

Title: Efficient Electrocatalytic Oxidation of Glycerol to Formate Coupled with Nitrate Reduction over Cu-doped NiCo Alloy Supported on Nickel Foam

Author: Chenyang Li, Hao Li, Bo Zhang, Huan Li, Yi Wang, Xiao Wang, Pratteek Das, Yuejiao Li, Xianhong Wu, Yifan Li, Yi Cui, Jianping Xiao, Zhong-Shuai Wu

Issue&Volume: 2024-08-12

Abstract: Electrooxidation of biomass-derived glycerol which is regarded as a main byproduct of industrial biodiesel production, is an innovative strategy to produce value-added chemicals, but currently showcases slow kinetics, limited Faraday efficiency, and unclear catalytic mechanism. Herein, we report high-efficiency electrooxidation of glycerol into formate via a Cu doped NiCo alloy catalyst supported on nickel foam (Cu-NiCo/NF) in a coupled system paired with nitrate reduction. The designed Cu-NiCo/NF delivers only 1.23 V vs. RHE at 10 mA cm-2, and a record Faraday efficiency of formate of 93.8%. The superior performance is ascribed to the rapid generation of NiIII-OOH and CoIII-OOH and favorable coupling of surface *O with reactive intermediates. Using Cu-NiCo/NF as a bifunctional catalyst, the coupled system  synchronously produces NH3 and formate, showing 290 mV lower than the coupling of hydrogen evolution reaction, together with excellent long-term stability for up to 144 h. This work lays out new guidelines and reliable strategies from catalyst design to system coupling for biomass-derived electrochemical refinery.

DOI: 10.1002/anie.202411542

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202411542