钼基过渡金属磷化物纳米结构的可控制备与电催化/光电催化性能研究

Low-cost non-noble metal catalyst has become a hot topic in water-splitting for hydrogen evolution reaction (HER) in recent years. Although MoP performs high conductivity and HER activity, the difficulties in controlled nanostructure synthesis limit further enhancing its activity. The key scientific topic of this project is to perform the design and synthesis of novel Mo based nanostructured transition metal phosphides (TMPs) with high catalytic activity and their applications in electrocatalytic HER process. One/two-dimensional nanostructured MoP are prepared first by tailoring the metal precursor and phosphidation reaction conditions. And then, metal element is introduced to MoP to form hybrid or alloy multimetallic phosphide catalysts, so as to further tailor both the morphology and intrinsic catalytic activity to achieve enhanced catalytic performances. The growth mechanism and electrochemical HER performance of catalysts are characterized. Especially, the effects of catalyst morphology and composition on the HER performance should be investigated in detail via electrochemical test and analysis, so as to disclosing catalytic sites and synergistic mechanism in catalysts. The relationship between catalyst composition, morphology and electrochemical performance will be studied. Finally, high efficient TMPs catalysts will be prepared. This project targets to prepare non-noble metal catalyst with high activity and stability by tailoring both the morphology and chemical composition of MoP, which shows good novelty and potential applicationins.

非贵金属产氢催化剂是目前分解水制氢领域的研究热点。磷化钼（MoP）由于具有良好的导电性和催化活性受到了关注，但其形貌可控性差的缺点限制了催化活性的进一步提高。本项目的核心科学问题是新型钼基过渡金属磷化物纳米结构的设计合成、性能调控及电催化应用研究，拟通过对前驱体种类与结构、磷化方法等制备条件的设计，合成一维/二维纳米结构MoP，引入金属掺杂或合金化进一步调控其形貌与本征催化活性制备双金属磷化物催化剂，研究其生长机理与电催化活性；结合电化学测试与分析重点研究催化剂形貌、组成对于催化性能的影响及机理，揭示材料组成、结构与性能之间的关系；优化条件最终制备高性能过渡金属磷化物产氢催化剂。本项目提出通过对钼基金属磷化物形貌和化学组成的调控提高其催化性能，制备高活性、高稳定性的产氢催化剂，具有很强的创新性和应用前景。

低成本、高性能的非贵金属催化剂是能源催化领域的研究重点之一。本项目从催化剂形貌与化学组成调控两方面入手，围绕过渡金属磷化物催化剂纳米形貌调控及多元异质催化剂的设计制备与催化性能研究开展了系列研究工作。通过合成方法的优化制备了一维纳米线、二维纳米片、三维大孔结构等系列纳米结构磷化钼及磷化镍催化剂，利用纳米结构大的比表面积暴露更多的活性位点，与体相材料相比获得了显著增强的产氢催化活性，并发展了简单、普适并适用于大面积电极制备的磷化物合成方法；引入金属掺杂构建了Co-Mo-P双金属磷化物纳米片、双金属复合氧化物纳米片等双金属异质催化剂，利用多元组分的协同作用进一步调控其形貌及电子结构而提高其本征催化活性，制备的富缺陷杂化纳米片获得了显著增强的电催化活性；设计制备了系列半导体基多元异质纳米催化剂，利用异质组分的协同作用获得了增强的电/光电催化分解水及二氧化碳还原性能；系统研究了催化剂形貌、组成对于催化性能的影响以及多元组分协同催化机理。项目的研究结果表明多元组分异质催化剂的构建是调控形貌并改善其本征催化活性的有效策略，为高效催化剂的设计制备提供了方法和思路。