掺杂型过渡金属磷化物纳米材料的控制合成及其电催化析氢性能研究

Doping element into transition metal phosphides nanomaterials, which is the research hotspots around the world, is an efficient strategy to synthesize earth-abundant electrocatalysts with high activity for hydrogen evolution reaction. In this project, a series of sulfur or nitrogen doped transition metal phosphides nanomaterials will be synthesized using transition metal oxides with different morphologies as precursors through in-situ phosphorization, followed by in-situ sulfidation or nitridation process at low temperature. In addition, new active phase will be build and the influence of synthesis conditions on their growth rhythm will be studied, thus realizing the controllable synthesis of doped transition metal phosphides nanomaterials. What’s more, the structure-activity relationship between their electrocatalytic performance and nanostructrues will be discussed in detail. Based on these, the catalytic mechanism in essence will be investigated. Several electrocatalysts with typical nanostructures and excellent performances for hydrogen evolution reaction will be obtained by sifting through the as-prepared doped transition metal phosphides in the end of this proposal.

基于元素掺杂来提高过渡金属磷化物基纳米材料的催化性能是一种制备高活性、高地球丰度的电催化析氢催化剂的有效手段，也是目前世界范围内的研究热点。本项目以不同形貌的过渡金属氧化物为前驱体，将其原位磷化后，再采用原位硫化或氮化的方法，构建新活性相，制备一系列硫、氮掺杂的过渡金属磷化物，考察其在不同合成条件下的生长规律，实现掺杂型过渡金属磷化物纳米材料的可控合成，探索其微观纳米结构与电催化析氢性能之间的构效关联，揭示其催化反应本质。在项目结束时，对可控合成的掺杂型过渡金属磷化物纳米材料进行筛选，得到几种结构独特、性能优异的电化学析氢催化剂。

过渡金属磷化物是一类相当具有潜力的析氢催化剂，但其暴露出来的活性位数量有限、本征催化活性存在阈值，并且其优化机制并不十分明确。本项目以过渡金属磷化物纳米材料为研究目标，通过掺杂异金属和构筑异质结构来丰富活性物种种类和发挥各活性组分协同效应。然后，通过进一步掺入杂原子（C、N、S等）提高材料导电性并增加新的活性位点。同时，定向调制催化剂的形貌（中空、多壳层、多孔等纳米结构），增大固/液界面的接触面积，促进更多活性位点参与催化反应。通过以上策略，本项目可控构筑了一系列具有较高催化活性的掺杂型过渡金属复合纳米材料，揭示了掺杂型过渡金属纳米材料的纳微结构与其电催化性能之间的构效关系，对过渡金属磷化物基电催化剂的可控合成及性能提升具有理论指导意义。