非贵金属助催化剂修饰介孔黑二氧化钛体系的构建及光催化产氢性能研究

In view of the low sunlight utilization, the poor charge separation efficiency and low interfacial catalytic activity of TiO2 photocatalysts, as well as the use of expensive noble metal co-catalysts, this project proposes the in situ construction of non-noble metal co-catalyst/mesoporous black titania photocatalysts. The cooperative assembly and sol-gel methods are intended to controllably synthesize high surface area, opened porous structure and metal ion-doped mesoporous TiO2, to increase the number of photocatalytic reaction sites and facilitate mass transfer. Next, the surface disorder layer (or non-metal heteroatom-doped layer) will be introduced into the surface of mesoporous TiO2 framework by surface-controlling strategies, leading to the formation of mesoporous black TiO2, thereby improving the absorption of visible and near-infrared light. Meanwhile, the black mesoporous titania surface of the skeleton is introduced in situ high activitive (in atomic level) non-noble metal co-catalyst (e.g., Ni, Co, NiOx, CrOx, CoOx, NiSx, MoSx etc.) will be in situ formed and tightly anchored on black TiO2 surface. Finally, their catalytic performance in photocatalytic hydrogen evolution, along with the structure-performance relationship, will be studied.

针对二氧化钛光催化剂的太阳光利用率低、光生电荷分离效率差、界面催化活性低以及需要昂贵的铂基助催化剂等问题，本项目拟设计原位构非贵金属助催化剂修饰的介孔黑二氧化钛光催化剂。拟采用共组装法、溶胶凝胶法制备具有高表面积、开放孔道、金属离子掺杂的介孔二氧化钛，增加光催化反应活性位点和物质的传输。然后利用表面调控策略引入无序非晶层或非金属离子掺杂的非晶层，提高其可见光和近红外光的吸收。同时，在介孔黑色二氧化钛骨架表面原位引入高活性（原子级层面）非贵金属助催化剂（如，Ni、Co、NiOx、CrOx、CoOx、NiSx、MoSx等），构建紧密界面。最后将重点研究这类介孔复合体光催化剂的光催化产氢性能，探索催化剂的构效关系。

针对二氧化钛光催化剂的太阳光利用率低、光生电荷分离效率差、界面催化活性低以及需要昂贵的铂基助催化剂等问题，提出了配位调控聚合物胶束定向组装合成策略，创制了具有开放孔道、高比表面积、可调组成的介孔二氧化钛相结材料；发展了孔道限域表面调控方法，制备了介孔黑色二氧化钛相结光催化剂；建立了核壳结构介孔材料合成新方法，构筑了核壳结构串联异质结光催化剂和金属硫化物核壳结构可见光光催化剂；揭示介孔二氧化钛基复合光催化剂性能与结构关系，从光催化剂与非贵金属助催化剂体系的角度出发，为设计高效可见光光催化剂提供依据。