Zhang Wenfei, Ge Wangxin, Qi Yanbin, Sheng Xuedi, Jiang Hongliang, Li Chunzhong
Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Chemical Engineering, East China University of Science and Technology, Shanghai, 200237, China.
Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, 200237, China.
Angew Chem Int Ed Engl. 2024 Jul 29;63(31):e202407121. doi: 10.1002/anie.202407121. Epub 2024 Jun 30.
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. 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.
将不饱和醛电催化氢化为不饱和醇是传统热工艺的一种有前景的替代方法。催化剂和电解质都会对性能产生深刻影响。由于电极 - 电解质界面的组成和结构复杂，设计该界面仍然具有挑战性。在此，我们采用5 - 羟甲基糠醛（HMF）的电催化氢化作为反应模型。典型的阳离子表面活性剂十六烷基三甲基溴化铵（CTAB）及其类似物被用作电解质添加剂来调节界面微环境，实现了HMF的高效氢化以及对析氢反应（HER）的抑制。在施加电势下，表面活性剂经历从随机分布到定向组装的构象转变。这种定向排列阻碍了水分子向界面的转移，并促进了反应物的富集。此外，实现了近100%的2,5 - 双（羟甲基）呋喃（BHMF）选择性，并且在 - 100 mA cm下，BHMF的法拉第效率（FE）从61%提高到了74%。值得注意的是，这种微环境调控策略适用于一系列涉及醛底物的电催化氢化反应。这项工作为设计先进的电极 - 电解质界面和提高不饱和醇的电合成效率铺平了道路。
