合理构建适用全pH高效稳定的非贵金属基双功能催化剂是目前电催化水分解领域的前沿课题。本项目针对二维MoS2基面活性弱、稳定性差及催化功能和工作环境受限问题，以可深入功能化的体型核壳MoSx原创工作为基础，借助密度泛函理论，高效耦合独特结构和多元组分优势，合理设计并逐级构筑双功能全pH电催化材料。首先，以优化超分子封装的核壳MoSx为基础，借助热诱导技术，原位构筑层间距和氧掺杂梯度可调的第一级活化超结构材料。其次，借助第一性原理建立异质配位模型，探究引入异质金属及其氧化物引起电子结构和热力学反应势垒调变情况，指导催化基面的二级活化，合理构筑杂原子和金属原子共修饰的MOz@MoMySxO2-x/C异质材料。最后，考察杂化材料双功能全pH催化反应的“构-效关系”，阐明各组分协同增强机制。本项目涉及MoSx微结构逐级可控调制与理论计算，为经济、高效和稳定双功能全pH催化剂的合理设计提供思路。

Constructing efficient and durable bi-functional catalysts for hydrogen and oxygen evolution in all pH ranges is considered frontier project in electrochemical water splitting fields. Against issues of weak basal planes, poor stabilities and limitation of catalytic functions as well as working environment of 2D MoS2, this proposal will efficiently couple advantages of unique structures and multivariate compositions of our developed 3D core-shell MoSx that possess potentials to be deeply functionalized, rational design and stepwise construct bi-functional pH-universal electrocatalysts with guidance of DFT calculations. Firstly, we will prepare superstructural materials with gradient modulated interlayer spacing and oxygen doping in-situ from supermolecules encapsulated core-shell MoSx to complete first-stage activity, based on thermal-inducible techniques. Secondly, we will build hetero-coordination models through first principles, and investigate the modulations of electron structures and thermodynamic catalytic reaction barrier after introducing hetero-metal and oxides into super cell, thus guiding second-stage activated process and scientifically preparing hetero and metal atoms co-doped MOz@MoMySxO2-x/C hybrids. Finally, we will explore the “structure-activity relationships” of bi-functional hybrids in catalytic reactions in all pH ranges, and illuminate synergistic enhancement mechanism. This proposal involves stepwise and controllable tailoring microstructure and theoretical simulations of MoSx, and will provide a new concept to rational design economic, efficient and durable bi-functional pH-universal catalysts.