硒化钼基范德华异质结构电催化剂的设计、制备及优化

This proposal devotes to develop a new and facile hot-solution reflux coupling synthetic route rather than a hydrothermal and/or solvothermal process for the controllably epitaxial growth of molybdenum diselenide-based heteronanostructures. Especially, those targeting systems of MoSe2-X (X = Bi2Se3, CoSe2 etc) with typical features of van der Waals force-type heteronanostructures are selected to demonstrate the epitaxial growth in solution, and their epitaxial growth process will be intensively investigated and the growth mechanism in solution will be revealed on the basis of understanding of solution thermodynamics, crystal thermodynamics and growth kinetics in the synthetic solution system. Meanwhile, the composition, structure, microstructure, surface and interface structure in addition to the electronic structure of the heteronanostructures grown in the system will be characterized and determined intensively by in situ SRPES and UPS techniques along with various characterizations by XRD, SEM, TEM/HRTEM, SAED, EELS, EDX/EDX mapping, Raman, EPR, FTIR, XPS, etc. And also, the typical ectrocatalytic/catalytic performances including hydrogen evolution reaction (HER) and supercapacitor properties of the heteronanostructures will be investigated, revealed and further optimized by taking advantage of the optimized growth of the heteronanostructures with structure controlling and electronic modulations, experimentally and theoretically. In addition, the relations between the structures and catalytic properties of the heteronanostructures will be intensively investigated in the proposed project, which will be favorable for the understanding and the improvement of some fundamental nanophysics and nanochemistry, and the potential applications of these heteronanostructures in energy conversion areas besides HER and supercapacitor performances demonstrated in the present proposal.

本申请旨在设计和建立一种新颖的热液偶联外延合成方法用于实现二硒化钼基异质纳米结构的控制制备，侧重研究MoSe2-X（X = Bi2Se3、CoSe2）等典型的具有范德华力结合结构特征的二硒化钼基异质纳米结构的热液偶联路线异质外延生长，研究和探明该异质纳米结构在热液相中的外延生长机理和调控机理，实现其组成和结构可控制备与生长。同时，利用同步辐射光电子能谱和紫外光电子能谱等原位分析和研究手段，结合X射线衍射、电子显微镜、电子衍射与能谱、拉曼、电子顺磁共振、红外和X光电子能谱等多种表征方法，以及理论计算来研究和分析所制备的MoSe2-X异质纳米结构的组成、结构、微结构、表面/异质界面结构和电子结构，以及其催化/电催化性能及机理，研究和探明其组分、结构与催化性能间的内在关系与规律，为二硒化钼基异质纳米结构活性材料在新型非贵金属催化剂设计、催化及能量转换领域的拓展和应用提供基础。

硒化钼基及其同构类型的范德华异质纳米结构的温和路线设计和优化制备，可为非贵金属催化剂和电催化剂的设计和筛选提供些有效的可能性。在本项目研究执行中，建立和发展了多种硒化钼类型同构的范德华异质结构纳米材料的温和合成方法及制备路线。如具体利用热力学原理和动力学过程调控等手段分别设计了多种温和液相合成等方法，控制制备出Ag2Se/1T-WSe2、CoSe2/WSe2、O-MoSe2、FePSe3/C、g-C3N4/ReSe2、NiSe/ReSe2、NiCoP/g-C3N4和MnS0.5Se0.5/N-Gr等范德华异质结构电催化剂和电化学活性材料，研究分析了所制备异质结构的组成、结构/微结构和生长机理，并研究探索了其电化学析氢和电化学储能等性能，探明了其构效关系及其优化等相关基础和原理。同时，还拓展了Ga/GaSb和AgInTe2/Si等几种窄带半导体异质纳米结构和新型单晶材料的控制制备，比较细致地研究了其光电响应与探测性能。项目执行期间，取得了一些特色有趣的研究结果，部分研究成果已经发表在相关领域的学术期刊上，即发表研究论文共15篇。其中，含第一标注研究论文ACS Applied Nano Materials（3）、Nano Research（3）、ACS Applied Materials & Interfaces（2）、Advanced Functional Materials、Advanced Optical Materials、Journal of Alloys and Compounds、Journal of The Electrochemical Society和ChemistrySelect，共13篇；第二标注研究论文Journal of Materials Chemistry A和New Journal of Chemistry共2篇。此外，在研究执行期内还获得授权的国家发明专利11项；培养毕业博士研究生8名（含1名合作指导）、硕士研究生4名。