层状双金属氢氧化物缺陷位锚定Pt催化剂用于电氧化生物质耦合电解水制氢

Compared with the oxygen evolution reaction, the oxidation potential of 5-hydroxymethyl furfural (HMF) is lower and the added value of product is higher. Although HMF oxidation and coupled with hydrogen evolution reaction (HER) improves the efficiency of hydrogen production, the electrocatalyst for HMF oxidation still faces the problems of high electrocatalytic potential and low activity. Therefore, it is very important to develop and design highly active electrocatalysts for HMF oxidation and HER. Combining with the advantages of nickel-iron layered double hydroxides (NiFe-LDHs) with good electrocatalytic activity for HMF oxidation and Pt with excellent electrocatalytic activity for HER, this project selected NiFe-LDHs as model catalyst. Constructing oxygen defect sites, bivalent nickel defect sites and trivalent iron defect sites in NiFe-LDHs explore the structure-activity relationship between defect types and electrocatalytic HMF oxidation properties. By anchoring Pt atoms at defect sites of NiFe-LDHs, the electronic structure of NiFe-LDHs can be regulated, the HMF electrooxidation properties of the catalysts can be enhanced, the types of catalytic sites will be enriched and high HER properties of electrocatalyst will be endowed. Further exploring the structure-activity relationship between different kinds of defect-anchored Pt electrocatalysts and the properties electrocatalytic HMF oxidation and HER, respectively. Combining in-situ tracking technology with theoretical calculation, the mechanism and reaction path of electrocatalytic reaction will be clarified.

相比氧析出反应，5-羟甲基糠醛（HMF）氧化反应电位低，氧化产物附加值较高。耦合HMF氧化电解水产氢，虽然提高了产氢效率，但是HMF氧化电催化剂仍然面临着电催化电位高和活性低的问题。因此，开发和设计高活性的HMF氧化和氢析出反应（HER）电催化剂至关重要。结合镍铁层状双金属氢氧化物（NiFe-LDHs）良好的HMF氧化活性和Pt优异HER催化活性的优势，本项目以NiFe-LDHs为模型催化剂选择性构筑氧缺陷位、二价镍缺陷位和三价铁缺陷位，探索缺陷位类型与电催化HMF氧化性能的构效关系；利用缺陷位高表面能和活泼的特性，原位锚定的Pt原子，调控NiFe-LDHs的电子结构，改善其HMF电氧化性能，同时丰富催化位点种类，赋予其高的HER性能，探索不同种类缺陷位锚定Pt电催化剂与催化HMF氧化和HER的构效关系；结合原位跟踪技术和理论计算明确电催化反应机理和反应路径。

氢能是替代化石能源实现碳中和的重要选择。电催化水产氢的决速反应是氧析出反应（OER），其动力学缓慢，所需过电势较高。因此，设计高效OER电催化剂降低电解制氢能耗至关重要。另外，亲核试剂氧化反应（NOR）如5-羟甲基糠醛具有更低的电化学氧化起始电位，且其氧化产物2, 5-呋喃二羧酸（FDCA）具有较高附加值，NOR替代OER能进一步降低制氢能耗和效率。申请人从电催化剂表面电子结构动态演化入手，探究了电催化剂的表界面基础科学问题：（一）揭示了金属氧化物电催化剂表面动态反应机制及构效关系，明晰了真实催化活性位；（二）发展了原子掺杂、颗粒及基团修饰缺陷位等调控策略，提升了催化剂氧析出反应和亲核试剂电氧化反应的本征活性；（三）建立了电催化剂表面重构过程与催化性能之间的构效关系，提出了活性位点动态循环及强化策略。基于以上研究内容，申请人发表高水平论文8篇，包括1篇Angew. Chem.、1篇Chem、1篇Adv. Mater.、1篇Energ. Environ. Sci.、3篇J. Energy Chem.和1篇Chinese J. Catal.。其中3篇论文入选ESI高倍引论文。申请人获2022全球高倍引科学家，湖南省杰出青年基金和湖南省自然科学一等奖（排名2）。

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