二维材料限域单原子电催化电极的离子辐照原位制备与性能研究

Hydrogen is a clear and high-efficient energy source. In this project, facing to the urgent demand for the high-efficient and low-cost catalysts for water splitting to produce hydrogen and the main neck-bottle problems in this field, we plan to prepare high quality 2D materials, using ion beam irradiation to produce numerous vacancies in 2D materials and anchoring novel or non-novel metal atoms into the surface of the 2D materials through in-situ deposition in ion implanter target chamber by magnetron sputtering. The purpose of this project is to fabricate high metal-loaded single atom 2D catalysts with high activity, low cost, high stability. By engineering the electron structure of 2D material through single atom doping, the increase of reactive active cites and conductivity, the decrease of reactive energy barrier can be achieved. This work will also provide a new method to fabricate single atom catalysts. The interaction between irradiation ion and 2D materials and the influence of irradiation to the 2D materials will be studied. Moreover, the synergistic effects between the doped single atoms and 2D materials will systematically analyzed in the atomic scale through both experiments and DFT simulation aiming to figure out the relationship between catalytic activity and microstructure, and the mechanisms for the enhanced performance. This work will also benefit for developing new catalysts for water splitting both on experimental and theoretical sides.

氢气是一种重要的清洁高效能源。本项目针对当前对用于电解水制氢的高性能、低成本催化材料的迫切需求以及遇到的主要瓶颈问题，拟制备高质量二维电催化分解水电极材料，利用离子束技术的独特优势产生高密度单空位，用原位长程磁控溅射沉积方法对二维材料表面进行高负载单原子掺杂，优化和调控二维材料电子结构，增加反应活性位点数目、增强导电性能、降低反应能垒等，获得高活性、低成本、高稳定性的二维材料限域单原子电催化(2D-SAC)材料并提供一种新方法。在此基础上研究二维材料与离子束相互作用过程及辐照效应机理，运用球差矫正电子显微学、X射线吸收精细结构谱学等先进方法结合第一性原理理论计算分析单原子掺杂对二维材料电子结构的影响及两者的协同相互促进作用，揭示单原子催化电极微结构与催化反应性能之间的构效关系，掌握单原子掺杂二维材料增强电催化性能机理，为开发新型高性能二维材料限域单原子电催化制氢材料提供实验方法和理论参考。

氢能是重要的清洁能源，通过光催化/光电催化/电催化是制备绿氢的重要方式。然而当前制氢催化剂存在催化性能低、价格高、稳定性差等问题。开发高效、低成本、高稳定性的工业级催化剂是当前的重要任务。项目组进行了g-C3N4、MoSe、FeNiOOH、MoS2、Fe-Ni3S2等多种二维材料的制备，利用离子束技术的特点和优势开展了上述二维材料的离子辐照和催化性能改性研究，在此基础上开展了单原子二维材料的制备和催化性能改性研究。.项目制备的多种催化电极材料具有优异的性能，在工业级高电流密度下过电势低、稳定性好，具备工业化应用前景。如：NiO/NiFe2O4异质结催化剂在100 mA·cm-2下稳定性高于450 h；离子辐照MoSe2纳米片在1000 mA·cm-2下稳定性高于120 h；Fe-Ni3S2纳米片在500 mA cm-2的水和尿素分解测试中，双电极电解槽的最长测试时间可达500 小时以上。.项目执行期间总体完成了研究目标，在Advanced Energy Materials (IF=29.698)、Applied Physics Reviews (IF=19.53)、Small (IF=15.15)、Journal of Physical Chemistry C (IF=6.89)、International Journal of Hydrogen Energy (IF=7.139)、Solar RRL (IF=9.17)、Electrochimica Acta (IF=7.34)、Applied Surface Science (IF=7.392)等期刊上发表SCI论文10篇（其中一区论文5篇，IF>7论文7篇），申请发明专利1件，在国际著名系列学术会议上作邀请报告1次，项目培养毕业博士研究生4名/硕士研究生2名，正在培养博士研究生3名/硕士研究生2名/科研助理1名。