多元过渡金属磷化物/氮化碳光催化剂的构筑及其分解水制氢性能研究

Semiconductor-based photocatalysis harvest and convert of solar energy through water splitting to produce clean hydrogen energy is considered as a powerful strategy to settle increasing the global energy crisis and environmental issues. In this project, we will centralize the advantages from co-catalyst, metal organic framework template method, the in-situ fabrication technique, and the surface mount technology, select cheap and highly efficient multiple transition metal phosphides (MNP = FeNiP, NiCoP, Mo-NiCoP et al) and graphite-like carbon nitride (g-C3N4) to fabricate the photocatalysts, in-depth study the effects of the types of metal organic framework, reaction conditions on the growth of the structures of nanocomposites; the effects of the characteristics of basic units on the visible-light-driven photocatalytic hydrogen production of nanocomposites; the controllable regulation and kinetic (or thermodynamic) law of excitation, migration and transformation of photon-generated carrier of heterostructures during the process of visible-light-driven photocatalytic hydrogen production, realize the selection and optimization of high-efficiency photocatalytic technology for hydrogen production, establish a steady theoretical foundation and provide a suitable structure system for the development of ideal photocatalytic technology with water splitting for hydrogen production.

半导体光催化分解水制氢技术被认为是解决能源危机和环境污染问题的理想途径。本课题旨在集中助催剂以及金属有机骨架模板法、原位生长和表面组装技术的优点，拟选用廉价高效的多元过渡金属磷化物（MNP）与石墨相氮化碳（g-C3N4）设计制备多元过渡金属磷化物（FeNiP，NiCoP，Mo-NiCoP等）修饰g-C3N4光催化体系，深入研究金属有机骨架材料种类、反应条件对复合光催化剂结构形成和生长过程的影响规律；系统研究复合光催化剂构筑单元特征（如表面性质、生长取向、复合比例及方式）对其可见光分解水制氢效果的影响规律；深入研究复合光催化剂光解水过程中的催化机制以及光生电子-空穴对的激发、迁移与转换过程的调控规律及其反应热力学与动力学规律。实现复合光催化剂的调控和优化，为开发具有实际应用价值的可见光分解水催化剂奠定坚实的理论基础。

基于光/电/化学技术在分解水和储能方面的广泛应用，我们通过原位构建g-C3N4基异质体系和MOFs衍生金属化合物、钒酸铋光电体系、非金属掺杂、原子结构等催化体系，实现了系列光/电/化学转换体系的构建及优化。探索了催化体系材料生长方式及复合方式对构筑异质体系的调控规律；深入研究了不同体系中纳米结构和电子结构对其光/电/化学性能的影响规律；提出了目标体系的光/电/化学过程机理和构效关系；进一步提出了实现高效光/电/化学转换的构效模型，为下阶段工作的开展积累了扎实的研究基础和系统的理论指导。目前已发表与本项目相关的论文60余篇，申请国家和欧洲发明专利3项。已培养博士毕业生2名，硕士毕业生3名，指导在读博士1名，在读硕士4名。