碳基纳米材料上析氢中心的构建及其电子传输性能的研究

Catalysts for hydrogen evolution play crucial roles on electrochemical or photochemical water splitting to generate hydrogen. The novel catalysts based on non-precious-metal-based molecules are promising and of great theoretical values and enormous application potentials. This project aims at integrating molecular catalysts onto such carbon nanomaterials as carbon quantum dots, graphene or graphitic carbon nitride to improve their stability and activity. The carbon nanomaterials-supported molecular catalysts will be further incorporated with inorganic semiconductors to fabricate seniconductor-nanocarbon-molecule ternary photocatalysts with enhanced performance. The integration of molecules onto carbon nanomaterials and the study of the role of carbon nanomaterials on capturing and transferring electrons will be the main missions of the project. Based on the characterization of the ternary catalysts and investigation of the mechanism of photocatalytic evolution of hydrogen, the synergetic effects of each component will be disclosed in details. The introduction of carbon nanomaterials will endow the composite catalysts with (1) enhanced stability, (2) improved dispersion of semiconductors and (3) efficient capturing and transferring electrons for higher catalytic performance of the catalysts. The results demonstrated in this project will shed light on developing high performance photocatalysts for efficient water splitting, reduction of carbon dioxide and nitrogen.

析氢催化剂在电解水或光解水制氢中具有重要作用。设计和制备非贵金属配合物析氢催化剂具有重要的理论价值和广阔的应用前景。本项目拟采用合成方法把具有析氢性能的过渡金属配合物分子催化剂键合到碳量子点、石墨烯或类石墨氮化碳上，以提高分子催化剂的稳定性和电子传输性能，并进一步与无机半导体纳米材料复合，构建高性能光解水制氢复合催化剂。重点研究在碳纳米材料上构建配合物析氢催化中心和探讨碳纳米材料在电子捕获和传输中的作用。通过对催化剂进行表征和光解水制氢反应机理的研究，揭示半导体-碳纳米材料-配合物三组分催化剂中各组分的协同作用。通过引入碳纳米材料，达到（1）提高分子催化剂的稳定性；（2）有利于分散半导体纳米材料，（3）有利于收集和传输光生电子，从而提高催化剂的光催化性能。本项目的成功实施将为光解水制氢、二氧化碳还原、氮还原等光催化过程提供理论基础和实践经验。

本项目用氮化碳、碳纳米材料或半导体材料与分子催化剂构建高性能光催化分解水制氢催化剂，并对所制备的复合催化剂进行表征、催化剂性能测试；研究配合物分子助催剂与半导体材料的结合方式、相互作用机制及对所制得的催化剂性能的影响。本项目完成了采用多种方法对氮化碳进行改性，以提高其产氢性能；通过引入小分子配位基团或者共聚物，更有效地与配合物分子结合构建高活性高稳定性的催化剂；通过引入纳米碳材料或无机化合物，提高了催化剂的电荷分离和传输性能。本项目的研究为研制高性能非贵金属催化剂并高效光解水制氢的应用打下了坚实的理论基础并积累丰富的实践经验。在催化、能源、界面和纳米材料相关学科重要学术期刊上发表了SCI论文20篇。