Huang Bingji, Yan Jiabiao, Li Zhenhua, Chen Lisong, Shi Jianlin
State Key Laboratory of Petroleum Molecular and Process engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, China.
State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029, China.
Angew Chem Int Ed Engl. 2024 Oct 1;63(40):e202409419. doi: 10.1002/anie.202409419. Epub 2024 Sep 2.
The local acidity at the anode surface during electrolysis is apparently stronger than that in bulk electrolyte due to the deprotonation from the reactant, which leads to the deteriorated electrocatalytic performances and product distributions. Here, an anode-electrolyte interfacial acidity regulation strategy has been proposed to inhibit local acidification at the surface of anode and enhance the electrocatalytic activity and selectivity of anodic reactions. As a proof of the concept, CeO Lewis acid component has been employed as a supporter to load Au nanoparticles to accelerate the diffusion and enrichment of OH toward the anode surface, so as to accelerate the electrocatalytic alcohol oxidation reaction. As the result, Au/CeO exhibits much enhanced lactic acid selectivity of 81 % and electrochemical activity of 693 mA⋅cm current density in glycerol oxidation reaction compared to pure Au. Mechanism investigation reveals that the introduced Lewis acid promotes the mass transport and concentration of OH on the anode surface, thus promoting the generation of lactic acid through the simultaneous enhancements of Faradaic and non-Faradaic processes. Attractively, the proposed strategy can be used for the electro-oxidation performance enhancements of a variety of alcohols, which thereby provides a new perspective for efficient alcohol electro-oxidations and the corresponding electrocatalyst design.
电解过程中，由于反应物去质子化，阳极表面的局部酸度明显高于本体电解质中的酸度，这导致电催化性能和产物分布恶化。在此，提出了一种阳极 - 电解质界面酸度调节策略，以抑制阳极表面的局部酸化，并提高阳极反应的电催化活性和选择性。作为概念验证，采用CeO路易斯酸组分作为载体负载金纳米颗粒，以加速OH向阳极表面的扩散和富集，从而加速电催化醇氧化反应。结果表明，与纯金相比，Au/CeO在甘油氧化反应中表现出大大提高的81%的乳酸选择性和693 mA·cm的电流密度电化学活性。机理研究表明，引入的路易斯酸促进了阳极表面OH的传质和浓度，从而通过同时增强法拉第和非法拉第过程促进了乳酸的生成。吸引人的是，所提出的策略可用于提高多种醇的电氧化性能，从而为高效醇电氧化及相应电催化剂设计提供了新的视角。
