低维3d过渡金属基化合物材料电学行为调控及其在电催化析氧中的应用研究

For the sake of the development and application of alternative energy technology, like metal-air battery, electrochemical water splitting and so on, it is of great significance to design efficient and low-cost oxygen evolution reaction (OER) electrocatalysts. In this project, to overcome the drawback of 3d transition-metal-based OER electrocatalysts, like poor active site exposure yield and low electrical conductivity, we plan to investigate low-dimensional 3d transition-metal compounds, and utilize brand-new methods, including electron-delocalize method, doping element, introducing cluster defect and hybrid composite, to regulate their electrical behavior. Based on their rich active sites exposure in low-dimensional materials, we regulate their charge density in electron structural aspect effectively, since their specific d-electron orbit structure effect, intending to prepare low-dimensional 3d transition-metal-based materials with comparatively higher electric conductive performance without lowing catalytic active sites, and develop the general method to regulate the electrical behavior of low-dimensional materials. Moreover, we would probe deeply into the relation between the electrical behavior of low-dimensional 3d transition-metal-based materials and their electrocatalytic oxygen evolution properties, and build a new class of highly efficient oxygen evolution electrocatalysts. Implementation of the project could guide us in searching for high-efficient OER electrocatalysts theoretically and technically, and provide material base for enhancing alternative energy technology.

设计高效廉价的析氧电催化剂对于金属-空气电池和电解水产氢等新能源技术的发展和推广应用具有重要的意义。针对当前已发展的3d过渡金属基的析氧电催化剂活性位点暴露少及导电性差的特点，本项目拟以低维3d过渡金属化合物为研究对象，采用电子去局域化法、元素掺杂、团簇缺陷的引入和复合杂化等电学行为调控新手段，在保持低维材料可以暴露较多活性位点的特性基础上，利用低维3d过渡金属化合物中特殊的d电子轨道结构效应，在电子结构层次中对低维材料中的电荷密度进行有效的调控，拟在不牺牲催化剂活性位点暴露的前提下，制备出具有较高导电性能的低维3d过渡金属化合物材料，发展调控低维材料电学行为的普适性方法。在此基础上，进一步探索低维3d过渡金属化合物材料电学行为和电催化析氧性能之间的关系，构建具有高效电催化析氧性能的电催化剂。该项目的实施有望为发展高效的析氧电催化剂提供理论和方法指导，并为发展新能源技术提供材料基础。

本课题针对目前发展的3d过渡金属基电催化剂活性位点暴露少及导电性差的特点，提出发展高导电性的电催化剂，探究材料电学行为与电催化活性之间的关联性，发展新调控策略调控电催化剂的电子结构及表界面结构进一步提升高导电性电催化剂的活性。在三年的实验过程中，本课题将具有高导电性的硒化物、磷化物、氮化物等材料作为研究载体，系统的研究了镍硒化合物材料电学行为与析氧活性之间的关联性，提出金属非氧化物的OER电催化性能是由其电学行为及表面氧化难易程度所共同决定的；利用碱性电解液中更易发生电化学表面氧化促进 OER 活性物种生成的特点，发展了促进金属态预催化剂表面电催化活性物种生成的通用策略，成功地实现了中性电解水析氧活性的显著提高；提出了利用阴离子改性高导电性金属磷化物合金材料的新方法，实现了碱性电催化析氢电极材料中水解离能和氢吸附自由能的协同调控；发展了氧等离子体刻蚀改性高导电性金属非氧化物材料的普适性方法，精准控制了金属氧化物/金属非氧化物界面的构筑，实现了对碱性HER电催化电极材料催化活性的显著提高。上述研究成果为发展高效的析氧析氢电催化剂提供了理论和方法指导，并为发展金属-空气电池，电解水产氢等新能源技术提供了更多的潜在材料。

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