MoS2纳米结构析氢活性的机理研究及优化

项目名称： MoS2纳米结构析氢活性的机理研究及优化

项目编号： No.21303237

项目类型： 青年科学基金项目

立项/批准年度： 2014

项目学科： 数理科学和化学

项目作者： 陈晓波

作者单位： 暨南大学

项目金额： 25万元

中文摘要： MoS2纳米颗粒是重要的低成本析氢催化剂，其催化性能仅次于贵金属。然而，与贵金属催化剂相比，MoS2纳米颗粒的有效活性位数量较少，过电位较高，导电性较差，进一步提升MoS2纳米颗粒的催化性能是当前析氢催化领域关键且极具挑战的课题。本项目采用第一性原理计算，通过分析反应自由能与前线分子轨道的关联，深入理解MoS2纳米结构的析氢催化机理，阐明S/Mo比率、活性位构型、阴阳离子掺杂、形状和衬底对催化性能的影响。在此基础上建立复合纳米结构的化学硬度模型和势能面分解模型，揭示支配MoS2纳米结构催化活性和导电性的关键电子态，提出进一步增加有效活性位密度，优化过电位、循环稳定性和导电性的方案，为新型纳米结构析氢催化剂的开发和改性提供具体的理论指导。

中文关键词： 二硫化钼；纳米结构；催化；析氢反应；第一性原理

英文摘要： MoS2 nanoclusters are important cost-effective catalyst for hydrogen evolution reaction (HER) with their catalytic ability inferior only to that of noble metals. Compared to the latter, however, MoS2 nanoclusters have scarce effective active sites, high overpotential, and poor electronic conduction. Currently, it is critical and challenging in the HER catalysis field to improve the catalytic performance of MoS2 nanoclusters. In this project the first-principles calculations are carried out to study the HER catalytic mechanism and the effect of S/Mo ratio, configurations of active sites, cation and anion doping, shape and substrate on the catalytic ability by analyzing the relationship between the reaction free energies and the frontier molecular orbitals of MoS2 nanoclusters. We aim to establish the chemical hardness model and the potential surface decomposition model for nanostructural composites and reveal the critical electronic states controlling catalytic activity and electric conduction. Finally, we will propose effective approaches to increase the density of effective active sites and optimize the overpotential, cycling stability and electronic conduction, providing theoretical insights for the development and modification of novel nanostructural catalysts.

英文关键词： MoS2；nanostructure；catalysis；hydrogen evolution reaction；first-principles