高效双金属磷化物基析氢催化剂的控制合成及其构效关联研究

This proposal suggests to controllable synthesize a series of bimetallic phosphides using bimetallic oxides with typical nanostructures as precursor through in-situ phosphorization process. This strategy integrates two advantages including metal doping and typical nanostructure into one electrocatalyst, and aims at filtrating varieties of bimetallic phosphides based electrocatalyst with high and efficient electrochemical performance for hydrogen evolution reaction. In this proposal, the effect of reaction temperature, time, concentration and pH value on the morphology or composition of bimetallic oxides and phosphides will be investigated in detail. Based on these conclusion, we could optimize the experimental conditions and explore the best synthetic scheme to controlled synthesize bimetallic oxides or phosphides and assemble them with typical support. What’s more, the intrinsic active sites and catalytic mechanism of the obtained bimetallic phosphides nanomaterials will be discussed in detail. And the structure-activity relationship between the microstructure and electrocatalytic activity of the bimetallic phosphides nanomaterials will also be investigated. A number of bimetallic phosphides based electrocatalysts with excellent electrocatalytic activity and low price will be obtained in the end of this proposal.

本项目拟以具有不同形貌的双金属氧化物为前驱体，采用原位磷化的方法，集合金属掺杂和纳米结构可控两个优势，制备一系列双金属磷化物纳米材料，更进一步筛选数种高效、稳定的双金属磷化物基电解水析氢催化剂。系统研究反应温度、时间、浓度以及pH值等对双金属氧化物前驱体和双金属磷化物形貌及组成的影响，优化实验条件，探索最佳合成方案，实现双金属氧（磷）化物的可控合成及其与载体的可控组装。探索双金属磷化物纳米材料在催化电解水析氢反应过程中的本征活性位及作用机理， 揭示双金属磷化物基纳米材料的微观结构与电催化析氢性能之间的构效关系。在项目结束时得到数种性能优良、价格低廉的双金属磷化物基电解水析氢催化剂。

本项目针对过渡金属磷化物电催化剂暴露出来的活性位数量有限、导电性较差及其本身存在着催化活性阈值等问题，以过渡金属氧化物做为前驱体，利用原位磷化的方法，可控构筑了一系列具有不同形貌的双金属过渡金属磷化物纳米材料。通过改变合成条件，探索其合成机制，实现双金属磷化物纳米材料的可控合成，揭示了其微观纳米结构与电催化析氢性能之间的构效关联，并充分利用这种构效关系，优化双金属磷化物纳米材料的合成体系。本项目借助不同金属磷化物纳米材料之间的协同效应以及具有良好导电性的载体对活性组分的分散作用，充分利用氧化物做前驱体的原位磷化策略在形貌控制与产物催化活性方面存在的明显优势，实现高效、稳定、廉价的双金属磷化物电催化剂的设计与合成，为相关电解水催化剂的设计合成提供了理论依据和实验基础。此外，本项目还尝试利用新的合成方法，可控合成了贵金属纳米材料，并探索了其在能源存储与转换领域的应用。