CoNi MOF电催化氧化5-羟甲基糠醛选择性升级耦合高效析氢

Electrocatalytic Oxidation of 5-hydroxymethylfurfural via CoNi Two-Dimentional Metal-Organic Frameworks for Biomass Selective Upgrading Coupled with Efficient Hydrogen Evolution

  • 摘要: 电催化氧化5-羟甲基糠醛(HMF)为生物质资源高效利用提供了一条可行的途径,但现有电催化剂的催化活性与选择性不足的问题限制了该领域的进一步发展与应用。为了克服这一挑战,构建了二维双金属有机框架纳米片CoNi MOF电催化剂,用于碱性条件下选择性电氧化HMF制备2,5-呋喃二甲酸(FDCA)。电化学测试结果表明,CoNi MOF催化剂在HMF氧化反应(HMFOR)中展现出卓越的催化活性。在10 mA·cm−2的电流密度下,HMFOR较析氧反应(Oxygen Evolution Reaction,OER)所需电位降低230 mV,其HMF转化率达91%,FDCA产率稳定在86.6%,以及法拉第效率为86%。此外,在析氢反应中它还表现出较快的反应动力学,塔菲尔斜率为131 mV·dec−1,并具有良好的循环稳定性。研究表明,HMFOR过程中Ni3+活性中心的生成显著加速了活性物种与HMF之间的反应动力学。将析氢反应(Hydrogen Evolution Reaction,HER)与HMFOR耦合构建两电极体系时,驱动10 mA·cm−2的电流密度仅需要1.58 V,表明CoNi MOF可有效实现氢能和高附加值化合物的同时生产。本工作为高性能HMFOR电催化剂的发展提供了广阔的应用前景,有利于推动生物质的高效转化。

     

    Abstract: Electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) represents a promising strategy for the valorization of biomass resources. However, the limited catalytic activity and selectivity of existing electrocatalysts have hindered further development and practical application in this field. To address this challenge, a two-dimensional bimetallic metal-organic framework (MOF) nanosheet, CoNi MOF, was designed as an electrocatalyst for selective electrooxidation of HMF to produce 2,5-furandicarboxylic acid (FDCA) under alkaline conditions. Electrochemical evaluations revealed that the CoNi MOF catalyst exhibits outstanding catalytic performance in the HMF oxidation reaction (HMFOR). At a current density of 10 mA·cm−2, the operating potential for HMF oxidation is reduced by 230 mV compared to that required for oxygen evolution reaction (OER), achieving HMF conversion rate of 91%, a stable FDCA yield of 86.6%, and a Faradaic efficiency of 86%. Additionally, the catalyst exhibited favorable kinetics toward the hydrogen evolution reaction (HER), with a Tafel slope of 131 mV·dec−1, and excellent cycling stability. Mechanistic indicate that the formation of Ni3+ active sites significantly accelerates the reaction kinetics between active species and HMF during HMFOR. When coupling HER and HMFOR in a two-electrode system, a current density of 10 mA·cm−2 can be achieved at a cell voltage of merely 1.58 V, demonstrating the feasibility of CoNi MOF for the simultaneous production of hydrogen and high-value-added chemicals. This work provides broad prospects for the development of high performance HMFOR electrocatalysts and advances the efficient conversion of biomass.

     

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