新型高效石墨烯基全固态Z型光催化体系的构建及其分解水产氢研究

The core of the research on photocatalytic water splitting for hydrogen production is the development and application of photocatalyst with high solar energy conversation efficiency. Z-scheme photocatalytic system has provided an important and feasible technical route for promoting the application of traditional semiconductor photocatalyst in visible light photocatalytic water splitting. Here, we design and fabricate a new type of graphene-base all solid Z-scheme photocatalytic system by using multilayers graphene membranes as the photoinduced electrons conduction medium and the semiconductor catalyst carrier materials. By using a controlling growth area strategy, two kinds of different semiconductors nanorods arrays were selected growth on the surface and the interlayers of the multilayer graphene membranes to form PS I and PS II photocatalytic system. And then with suitable loaded of both hydrogen production and oxygen production cocatalysts on the surface of PS I and PS II, a novel all-solid-state Z-scheme photocatalytic system can be obtained. This novel all solid-state Z-scheme photocatalytic system can effectively promoted the photogenerated charge separation and realize the photoinduced electrons directional transmission through the graphene, which is promising to achieve a high solar energy conversation efficiency. This project aims at inventing a new kind of Z-scheme all-solid-state Z-scheme photocatalytic system which using graphene as the electrons conduction medium. This study would reveal the control factors during the photocatalytic water splitting process and provide a new strategy for the design and construction of the Z-scheme photocatalytic system.

光解水制氢技术研究的核心是可高效利用太阳能光催化剂的开发与应用，研究的首要目标是提高产氢效率。Z型光催化体系为可见光全分解水反应提供了一条重要的可行技术路线。本项目拟以具有多层结构的石墨烯整块体薄膜作为Z型光催化体系的电子传导介质及半导体催化剂载体材料，采用控制生长法分别在同一块石墨烯薄膜不同区域的表面以及多层石墨烯薄膜间原位生长两种不同的一维半导体纳米棒阵列，构成PS I和PS II系统。在此基础上，分别在两种半导体纳米棒阵列表面负载对应的产氢、产氧助催化剂，构成整块体石墨烯基全固态Z型光催化体系。该体系可实现光氧化-还原活性位点的空间分离，促进光生载流子定向传导，提高单位面积下太阳光利用效率及光催化分解水产氢效率。本项目旨在设计和开发一种以石墨烯为电子传导介体的新型Z型光催化体系，揭示该体系中反应速率的控制因素，为可高效利用太阳光分解水制氢Z型光催化体系的设计与开发提供新策略。

光解水制氢技术研究的核心是可高效利用太阳能光催化剂的开发与应用，研究的首要目标是提高产氢效率。本项目拟以具有多层结构的石墨烯等三维整块体薄膜作为Z型光催化体系的电子传导介质及半导体催化剂载体材料。在此基础上，分别在两种半导体纳米棒阵列表面负载对应的产氢、产氧助催化剂，实现光氧化-还原活性位点的空间分离，促进光生载流子定向传导，提高单位面积下太阳光利用效率及光催化分解水产氢效率。本项目旨在设计和开发新型光催化体系，揭示该体系中反应速率的控制因素，为可高效利用太阳光分解水制氢体系的设计与开发提供新策略。.依据申请书研究内容，按计划执行情况良好。主要完成了：多层石墨烯Z型光催化体系的构建及其可见光催化分解水产氢研究；创新设计并制备了以多层石墨烯薄膜为载体，负载ZnO、CdS等半导体纳米棒阵列拟构建新型全固态Z结构光催化体系。通过光生载流子在石墨烯薄膜上的有效传导，实现光氧化-还原活性位点的空间分离，提高催化体系在可见光下的光转化效率。.项目执行期内，发表SCI收录学术论文10余篇，其中在能源材料、环境、光催化方面的JCR 1区期刊 (Applied Catalysis B: Environmental; Chemical Engineering Journal; ChemSusChem; Journal of Material Chemistry A；Small Methodes等) 发表研究论文9篇；申请发明专利2项；毕业博士1人，硕士4人。.此外，申请人研究发现虽然基于多层石墨烯基底构建的整块体催化剂具有优异的光催化性能，但光催化制氢过程中产生的大量氢气气泡不利于该基底的长期催化稳定性，因此我们尝试将近年来在电催化领域研究广泛的多空泡沫金属材料替代多层石墨烯膜基底，研究表明，该类催化体系表现出新颖的“光助电”催化活性。此类催化剂同样展现了优异的光电耦合催化分解水产氢性能，达到了国内外领先水平。