CoxM1-xS2-yNy纳米线“自支撑”电极的构筑及其电催化析氢性能研究

According to the principal of structures and defects of the CoS2 nanomaterials determine their functions and then functions determine properties for materials design, a series of CoxM2-xS2-yNy nanowires based "free standing" electrodes will be prepared to reveal the scientific issues which are related to enhance electrocatalytic hydrogen evolution reaction which catalyzed by noble metal free materials. The main contents include that: firstly, the CoS2 nanowires based "free standing" substrate with uniform morphology, size and crystal will be synthesized. According to the d electronic effect of the metal atom and electronegativity of the nonmetal atom which have influence on the material activity. Then through the metal (Ni、Fe、Mo、W) doping, nonmetal (C、N、O、P) doping and metal-nonmetal co-doping to form CoxM2-xS2-yNy nanowires based "free standing" electrodes. Finally, the crystallization of the corresponding electrodes are adjusted by annealing method. We will foucus on investigating the relationship between structure of electrodes, defects and conductivity on the hydrogen evolution performance of electrodes. Meanwhile, the corresponding electrocatalytic hydrogen evolution reaction mechanism will be demonstrated according to the theoretical calculation. In addition, the target electrodes will be assemblied into electrolytic cells, their hydrogen evolution ability can also be concluded from the hydrogen evolution property evaluation parameters obtained. All these efforts will allow us making a noble metal free electrocatalytic hydrogen evolution electrode with high stability, high efficiency and low energy consumption. These results will provide the theoretic support and further guidance for the development of noble metal free hydrogen evolution catalysts.

基于不同结构、不同缺陷的CoS2析氢材料对电催化析氢反应的性能差异，本项目拟构筑系列CoxM1-xS2-yNy纳米线“自支撑”电极，用于研究提升非贵金属材料电催化析氢性能的相关科学问题。主要包括：首先合成形貌均一、尺寸和晶面可控的CoS2纳米线“自支撑”电极基体；然后依据金属原子的d电子效应和非金属原子电负性对材料活性的影响，通过金属原子(Ni、Fe、Mo、W)、非金属原子(C、N、O、P)单掺、共掺的方法制备系列CoxM1-xS2-yNy纳米线“自支撑”电极；再采用退火技术调整结晶度，探究结晶度与析氢性能之间的关系；重点研究结构、缺陷及导电性对目标电极析氢性能的影响；配合相关理论计算，探索构效关系，提出电催化析氢机理；最后，将目标电极组装成电解池，通过电解池参数的测定全面评价其析氢性能，以期获得高效、稳定、低能耗的非贵金属电催化析氢电极，为新型电催化析氢电极的发展提供实验基础和理论指导。

新型纳米结构电催化剂的设计合成对新能源的开发和利用具有重要的研究价值和现实意义。瞄准纳米结构中表界面形成过程难控制、作用机制不明确等难题，申请人以“离子诱导控制法”为核心，围绕表界面结构形成过程难控制、作用机制不明确等关键问题，开展过渡金属硫化物异质结构的合成研究。提出了异质金属硫化物晶面控制新策略；以“离子诱导控制法”为核心，完成系列异质硫化物纳米晶面结构的可控合成；实现了“硫-硫”、“氧-硫”等多种原子耦合异质界面的构筑；拓展了离子诱导控制策略在表面异质结构合成中的应用。.在本项目的支持下，今年得到了基金委优青项目的支持，在J. Am. Chem. Soc.（2篇）, Angew. Chem. Int. Ed.（2篇）, Adv. Mater.（1篇）, Adv. Funct. Mater.（3篇）, Nano Energy（1篇），ACS Nano（1篇）等相关领域著名学术期刊上发表SCI论文发表相关学术论文21篇，申请专利2项，参加学术会议12次并作邀请报告10次，同时邀请28人（次）来兰州大学进行学术交流。毕业博士研究生1名，硕士研究生2名，在读博（硕）研究生10名。.在本项目中，通过表界面调控、悬挂键引入和电子结构优化等手段，建立硫化物异质结控制合成新方法，合成高效、稳定的异质结构新材料。并将上述所合成无机功能材料用于电催化水分解能源转换过程研究中对于理解异质结构的本质、开创新型硫族化合物异质纳米结构合成方法有重要的意义。