稀土修饰型过渡金属化合物内封装于杂原子掺杂碳纳米管的碳基三维自支撑电极的可控构建与电催化产氢性能研究

针对粉体过渡金属及其化合物内封装型碳基电催化材料成分单一、活性位点分散度低、易团聚、易从电极表面脱落导致活性和稳定性不足的问题，本项目结合含氮有机物协同热解策略，通过金属前驱体辅助原位生长氮掺杂碳纳米管，在导电电极基底上原位构建稀土修饰型过渡金属化合物内封装于杂原子掺杂碳纳米管的碳基三维自支撑电极材料。系统研究电极材料的可控构筑、组成调变及电催化产氢性能；重点探索电极材料中稀土元素、过渡金属化合物和杂原子的种类、存在形式、表界面结构及相互耦合作用对其电催化产氢性能的影响，揭示稀土修饰对内封装过渡金属化合物以及杂原子掺杂碳纳米管碳基电催化剂性能的增强效应和调变规律；深入研究电极材料中各组分相互作用、价键特性、配位环境、表面态、电子结构，阐明稀土、过渡金属化合物、杂原子协同增强碳材料电催化产氢性能的作用机制，为设计新型、廉价、高效的稀土/过渡金属化合物杂化碳基电催化材料提供理论指导和材料范例。

To overcome the shortcomings of decreased electrocatalytic activity and stability caused by invariable chemical composition, low dispersed active sites, severe aggregation, and easy detachment from electrodes for powder carbon-based electrocatalysts encapsulating with transition metal compounds, this project intends to in-situ grow heteroatom-doped carbon nanotubes encapsulating with rare earth modified transition metal compounds on conductive substrates to construct three-dimensional self-supported carbon-based electrodes via a strategy of transition metal catalyzed to in-situ grow nitrogen-doped carbon nanotubes with the assistance of simultaneous pyrolysis of nitrogenous organic compounds. The controlled construction, structural modulation, and hydrogen evolution performance of the three-dimensional self-supported carbon-based electrodes will firstly be systematically studied. Then, the influences of species, existent state, surface/interface structure, and coupling interaction of rare earth, transition metals and their compounds, and heteroatoms in the electrodes on the electrocatalytic performance for HER will be mainly focused. Furthermore, the enhancement effects and modulation rules of the electrocatalytic performance of the three-dimensional self-supported carbon-based electrodes composed of heteroatom-doped carbon nanotubes encapsulating with rare earth modified transition metal compounds will be revealed. Meanwhile, the surface state, coordination environment, synergetic interaction, valence bond characteristic and electronic structure of each component of rare earth, transition metal compounds, doped heteroatom, and carbon nanotubes in the electrodes will be in-depth studied. Finally, the synergetic enhancement mechanism of the three-dimensional self-supported carbon-based electrodes for the electrocatalytic performance of HER arisen from the interactions among rare earth species, transition metal compounds, and heteroatom doped carbon nanotubes will be carefully clarified. This study will provide a valuable guidance and a model electrode material for design of novel, cheap, and efficient rare earth/transition metal -based hybrid carbon-based electrocatalytic materials.