基于二维金属-硫醇配合物的疏水性调控糠醛电催化加氢性能研究

Due to the competition of electrocatalytic hydrogen evolution reaction (HER), the efficiency of the electrocatalytic hydrogenation (ECH) process is low. Therefore, the construction of ECH catalysts with high activity is the key to promote the application of green organic ECH synthesis. For the reaction on the catalyst surface, the activity and selectivity of the catalytic reaction can be effectively regulated by changing the properties of the catalyst surface, of which hydrophilicity and hydrophobicity are important surface parameters. This project intends to explore the furfural ECH reaction system. The ECH of furfural is regulated from the hydrophobic catalyst point of view. We first prepare of hydrophobic two-dimensional metal-thiolate complexes catalysts by the vapor phase hydro/solvothermal method, and explore the regulatory mechanism of furfural ECH affected by hydrophobicity of catalyst surface, then deepening the competition relationships between furfural ECH and HER. The structure-activity relationship between the hydrophobic surface structure of the catalyst and its ECH activity is established from the atomic point of view based on the structural characterization and theoretical calculation of the catalyst, and an efficient ECH system for furfural is developed. The implementation of this project will improve the understanding of basic scientific issues in the design of ECH catalysts and provide research ideas for promoting the development of new ECH synthesis systems.

由于电催化析氢的竞争作用会导致电催化加氢效率严重偏低，因此构筑高效的电催化加氢催化剂是推动绿色电催化加氢合成应用的关键。而对于催化剂表面进行的反应，通过改变催化剂表面的性质可有效调控催化反应的活性和选择性等，其中亲疏水性是一个很重要的表面参数。本项目拟选择糠醛电催化加氢反应为研究对象，从利用疏水性催化剂表面调控电催化加氢性能的角度出发，首先通过气相水热/溶剂热法可控制备疏水性的二维金属配合物催化剂，探究催化剂表面亲疏水性对电催化加氢活性和选择性的调控机制，揭示亲疏水性表面调控电催化糠醛加氢与电催化析氢之间竞争的作用机理；并结合催化剂结构表征与理论计算，从原子角度建立疏水性的催化剂表面结构与催化活性之间的构-效关系，最后发展高效的糠醛电催化加氢合成体系。本项目的实施将增进对电催化加氢催化剂设计中基础科学问题的理解，同时为促进新型电催化加氢合成体系的发展提供研究思路。

利用可持续清洁能源（如风能、太阳能）通过电化学方法将自然界的物质转化为高价值的燃料与化学品，为未来新型可再生清洁能源转换体系的建立，指明了发展方向。而电催化剂在这些清洁能源转换与储存技术中起到关键作用，因为它可以增加催化反应速率、增加能量转换效率与提高产物的选择性。本项目通过新颖的气相水热/溶剂热合成方法，将疏水性的二维金属-硫醇配合物催化剂原位生长在催化剂电极表面，并深入探究金属-硫醇配合物对糠醛、氮气、硝基苯电催化加氢性能（包括法拉第效率、转化率、产物产率与选择性等）影响，结合理论计算研究该类催化剂调节电催化加氢活性的机制，进一步发展新型的电催化加氢合成反应体系。