Rh掺杂的Cu纳米线催化剂促进5-羟甲基糠醛电催化加氢  

Rh-dispersed Cu nanowire catalyst for boosting electrocatalytic hydrogenation of 5-hydroxymethylfurfural

作　　者：张文飞 齐宴宾 赵渊 葛胜鑫 董磊 沈建华 江宏亮 李春忠 Wenfei Zhang;Yanbin Qi;Yuan Zhao;Wangxin Ge;Lei Dong;Jianhua Shen;Hongliang Jiang;Chunzhong Li(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)

机构地区：[1]Shanghai Engineering Research Center of Hierarchical Nanomaterials,School of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China [2]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

出　　处：《Science Bulletin》2023年第19期2190-2199,M0004,共11页科学通报（英文版）

基　　金：the National Key R&D Program of China(2022YFB3808400);the National Natural Science Foundation of China(22222804 and U22B20143);the Science and Technology Commission of Shanghai Municipality(22dz1205900);the Shanghai Municipal Science and Technology Major Project。

摘　　要：生物质是世界上广泛存在的可再生资源,可以转化成高价值燃料和化学品.基于可再生能源产生的电力,将生物质衍生的5-羟甲基糠醛(HMF)电催化转化为2,5-呋喃二甲醇(BHMF)具有重要的研究意义和应用价值.HMF在电转化过程中容易发生二聚反应,从而导致BHMF的选择性较低,产物分离难度大.因此,探索获得高选择性BHMF的高效催化体系极为重要.在此,本文报道了Rh掺杂的Cu纳米线催化剂,其在HMF电还原为BHMF反应中表现出较高的转化率,且有效抑制了二聚反应的发生.动力学实验和原位光谱研究表明,Rh的引入可以有效促进水解离形成活性氢物种,促进5-羟甲基糠醛电催化加氢并抑制其二聚.此催化剂设计策略可以拓展到其他生物质衍生分子的电催化转化过程中.Electrocatalytic conversion of biomass-derived 5-hydroxymethylfurfural(HMF)to 2,5-bis(hydroxymethyl)furan(BHMF)presents a compelling strategy for the production of premium chemicals via the utilization of renewable energy sources.Exploring efficient catalytic systems to obtain highly selective BHMF has remained a giant challenge.A design strategy is proposed here to regulate active hydrogen(Hads)production in rhodium(Rh)nanoparticles grown on Cu nanowires(RhCu NWs)catalyst,which achieves a faradaic efficiency(FE)of 92.6%in the electrocatalytic reduction of HMF to BHMF at-20 mA cm-2 with no degradation in performance after 8 cycles.Kinetic investigations and electron spin resonance(ESR)spectroscopy reveal that the incorporation of Rh accelerates the water dissociation and facilitates the generation of Hads.In situ attenuated total reflection surface enhanced infrared absorption spectroscopy(ATR-SEIRAS)further demonstrates that the Rh component boosts the proportion of ordered weakly hydrogen-bonded water molecules on the catalyst surface,which is much easier to dissociate.The construction of an interfacial Hads-rich environment promotes the HMF intermediates binding with Hads to BMHF,thereby suppressing the formation of undesired dimers.This work demonstrates the promise of altering the interfacial water environment as a strategy to boost the electrosynthetic properties of biomass-derived products toward value-added outcomes.

关 键 词：催化剂设计 高选择性 活性氢 水解离 HMF 可再生能源 可再生资源 催化转化 

分 类 号：TQ426[化学工程] TK6[动力工程及工程热物理—生物能]