文献类型：期刊文献

英文题名：Surfactant Directionally Assembled at the Electrode-Electrolyte Interface for Facilitating Electrocatalytic Aldehyde Hydrogenation

作者：Zhang, Wenfei[1,2];Ge, Wangxin[2];Qi, Yanbin[2];Sheng, Xuedi[1];Jiang, Hongliang[1];Li, Chunzhong[1,2,3]

机构：[1]East China Univ Sci & Technol, Shanghai Engn Res Ctr Hierarch Nanomat, Sch Chem Engn, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Minist Educ, Sch Mat Sci & Engn, Key Lab Ultrafine Mat, Shanghai 200237, Peoples R China;[3]Shanghai Jiao Tong Univ, Sch Chem & Chem Engn, Dept Chem Engn, Shanghai 200240, Peoples R China

年份：2024

卷号：63

期号：31

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20242716596940);WOS:【SCI-EXPANDED(收录号:WOS:001257886200001)】；

基金：This work was supported by the National Natural Science Foundation of China (22222804 and U22B20143), the National Key R&D program (2022YFB3808400), the Science and Technology Commission of Shanghai Municipality (22dz1205900), and the Shanghai Municipal Science and Technology Major Project. The authors thank the Shanghai Synchrotron Radiation Facility (14W1, SSRF).

语种：英文

外文关键词：biomass upgrade; HMF electrocatalytic hydrogenation; electrode-electrolyte interface; surfactant; substrate enrichment

摘要：Electrocatalytic hydrogenation of unsaturated aldehydes to unsaturated alcohols is a promising alternative to conventional thermal processes. Both the catalyst and electrolyte deeply impact the performance. Designing the electrode-electrolyte interface remains challenging due to its compositional and structural complexity. Here, we employ the electrocatalytic hydrogenation of 5-hydroxymethylfurfural (HMF) as a reaction model. The typical cationic surfactant, cetyltrimethylammonium bromide (CTAB), and its analogs are employed as electrolyte additives to tune the interfacial microenvironment, delivering high-efficiency hydrogenation of HMF and inhibition of the hydrogen evolution reaction (HER). The surfactants experience a conformational transformation from stochastic distribution to directional assembly under applied potential. This oriented arrangement hampers the transfer of water molecules to the interface and promotes the enrichment of reactants. In addition, near 100 % 2,5-bis(hydroxymethyl)furan (BHMF) selectivity is achieved, and the faradaic efficiency (FE) of the BHMF is improved from 61 % to 74 % at -100 mA cm-2. Notably, the microenvironmental modulation strategy applies to a range of electrocatalytic hydrogenation reactions involving aldehyde substrates. This work paves the way for engineering advanced electrode-electrolyte interfaces and boosting unsaturated alcohol electrosynthesis efficiency. Quaternary ammonium cationic surfactant-modified electrode-electrolyte interfaces have been designed for cathodic catalytic conversion of 5-hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan. Under the application potential conditions, the surfactant undergoes a conformational transition from random distribution to directional assembly. This microenvironmental regulation strategy achieves efficient hydrogenation of HMF and inhibits hydrogen evolution reaction. image