配体功能化的IIB族氧（硫）化物/Ti-MOF光催化剂的制备及电子传输机制

With the rapid development of economy，energy crisis and environment deterioration are the main environment problem with which our country is confronted, such as the hot topic of PM 2.5 emissions resulting from vehicle exhaust, and emissions from coal-fired power plants, etc. Harvesting solar energy to produce renewable, carbon free and cost effective hydrogen as an alternative energy source is easy to solve these problems. In order to developing the new photocatalysts with high activity for water splitting，in this foundation, a variety of synthesis techniques (such as dielectric-barrier discharge (DBD) plasma treatment, metal-organic chemical vapor deposition (MOCVD), fractional precipitation and coprecipitation method) are used to prepare IIB oxides (sulfides)/metal-organic frameworks (MOFs) composites. The synthesis routes of composite photocatalysts are studied by different compositions and structures. we may get nanophase with special morphologies, excellent surface chemical/physical and optical properties and farther achieve the controllable synthesis of composites. The transport mechanism of ligand-to-cluster charge-transfer (LCCT) and photogenerated carriers are conducted based on the related theories and experimental results. By different characterization methods, we would like to confirm the cooperation effect between MOFs and metallic oxide and demonstrate the unique gas transport and storage properties in the porous structure of MOFs materials for photocatalytic production of hydrogen. In our work, the aim is to recognize the formation process and growth mechanism of the composite photocatalysts in order to provide the theoretical and experimental evidence.

随着我国经济的快速发展，能源短缺及环境污染问题是我们亟待解决的重大问题，比如近年来大家热议的PM 2.5，其主要来源于机动车尾气排放、燃煤等。如果能利用太阳能开发出清洁可再生氢能源，将会很大程度上解决该类问题。因此，本项目以稳定的Ti-MOF材料作为构建单元，采用系统的实验方法制备IIB族氧（硫）化物/Ti-MOF新光催化剂，应用于分解水制氢研究。并研究不同组成、结构下催化剂的制备规律，调控制备条件以获得具有优异的表面物理化学性质及特殊形貌的复合材料，实现该类催化剂的可控合成。同时利用理论和实验相结合的方法，研究配体上不同取代基对合成材料带隙、电位影响，探讨电荷迁移机制，确定光催化机理。通过各种表征手段，确定组分之间的协同作用关系，揭示不同复合光催化材料的形成过程和生长机理，为该类催化剂的制备合成提供理论和实验依据。

本项目新型高效的光催化材料的构筑是有效利用太阳能的关键课题，将MOFs与金属氧化物复合并用于光催化反应过程是近年来光催化领域新兴的一个研究方向。以MOFs材料及配位聚合物材料为出发点，合成复合光催化材料或氧化物光催化材料，成果发表于《J. Mater. Chem. A》、《ChemElectroChem》等杂志4篇及几篇标志性成果，目前正在修改投稿中，如发现了通过Bi，Fe双金属MOFs烧结得到的铁酸铋光催化材料，发现该材料经历了一个奥斯特瓦尔德熟化的“吞吐过程”，又如通过Ti-MOF烧结得到的凹陷立方TiO2/C材料，提出了“不对称收缩机制”，这些工作的发现为今后研究都有非常重要的借鉴作用。