石墨烯构建Z型载流子转移通道的复合型光催化制氢材料

Photocatalytic hydrogen production as a direct route for converting solar energy to clean energy - hydrogen has been widely attracted researchers' attentions. In photocatalysts, the hybrid photocatalysts with a Z-scheme carrier transport route possess a significant advantage in improving photocatalytic activity via a lower energy carrier combination and then holding photoexcited electrons/holes with strong reducibility and oxidability. However, it is difficult in achieving a desired photoexcited carrier transport route in a hybrid photocatalyst. In the item, a hybrid photcatalyst with a Z-scheme carrier transport channel constructed by graphene is designed for dominating photoexcited carrier transport routes based on the energy band engineering, where the surface atom states and the ratio of C/O in graphene are modified for improving the carrier transport. The item will aim at developing a basic method to construct a Z-scheme carrier transport channel and exploring photoexcited carrier states and dominated conditions in a hybrid photocatalyst. And then the photocatalytic hydrogen activity will be further investigated. The results will promote the design of hybrid photocatalysts with high hydrogen production efficiency.

光催化制氢作为一种将太阳能转化为清洁能源-氢能的有效途径，日益受到科研工作者的广泛关注。在光催化材料中，虽然以Z型载流子转移为基础的复合型光催化材料可通过低能量光生载流子的转移复合保留强氧化还原能力的空穴和电子从而获得较高光催化制氢效率,然而在直接复合催化材料中载流子转移不可控，光催化效率难以提高。本项目将从调控复合型光催化材料中光生载流子转移出发，以能级结构匹配为基础，采用石墨烯在组元相间构建一个Z型的载流子转移通道，并调控组元相表面和界面的原子组态以及石墨烯的C/O比以获得高效的光催化制氢材料。该项目旨在研究复合型光催化材料中构建Z型载流子转移通道的基本方法，并探索复合光催化材料中载流子迁移状态和控制因素，以及深入研究其光催化制氢性能，为发展高效的复合型光催化制氢材料提供科学依据。

为了提高异质结构材料的光催化制氢效率，我们通过石墨烯（氧化石墨烯、还原氧化石墨烯）在异质结构组元相间构建Z型载流子迁移通道，增强异质组元相界面处的协同效应，使光催化制氢性能得到较大幅度提升。同时通过调控组元相的形貌结构以及表面原子组态，构建一系列的ZnO-CdS/RGO异质结构以及其他新型异质结构材料，实现了石墨烯增强Z型载流子迁移效率，达到了提升光催化活性和稳定性的研究目标。进一步优化石墨烯的量、组元相比例、氧化石墨中的C/O比、助催化剂等，使异质结构光催化材料的产氢速率普遍提升到mmol h-1（100 mg）级。此外，在材料制备上，发展和创新了光诱导生长以及微电化学诱导生长光催化材料的方法。在学术论文发表方面，我们已在Chem. Commun.、Carbon、J. Coll. Interf. Sci.等国际期刊发表与项目紧密相关的第一作者和通信作者（项目负责人）SCI论文7篇，其中影响因子大于6的2篇，已远超出了申请书设定4篇SCI论文的研究目标。该项目在采用石墨烯构建异质结构载流子迁移通道上所取得科研成果以及发展的材料制备方法将可用于新型光催化制氢材料的设计与合成，促进光催化制氢材料研究的向深度和广度发展。