Wang Yan, Fan Guilan, Wang Sibo, Li Yunxiang, Guo Yan, Luan Deyan, Gu Xiaojun, Lou Xiong Wen David
School of Chemical and Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, Singapore, 637459, Singapore.
School of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, 010021, P. R. China.
Adv Mater. 2022 Oct;34(42):e2204865. doi: 10.1002/adma.202204865. Epub 2022 Sep 22.
Despite suffering from slow charge-carrier mobility, photocatalysis is still an attractive and promising technology toward producing green fuels from solar energy. An effective approach is to design and fabricate advanced architectural materials as photocatalysts to enhance the performance of semiconductor-based photocatalytic systems. Herein, metal-organic-framework-derived hierarchically ordered porous nitrogen and carbon co-doped ZnO (N-C-ZnO) structures are developed as nanoreactors with decorated CoO nanoclusters for CO -to-CO conversion driven by visible light. Introduction of hierarchical nanoarchitectures with highly ordered interconnected meso-macroporous channels shows beneficial properties for photocatalytic reduction reactions, including enhanced mobility of charge carriers throughout the highly accessible framework, maximized exposure of active sites, and inhibited recombination of photoinduced charge carriers. Density functional theory calculations further reveal the key role of CoO nanoclusters with high affinity to CO molecules, and the CoO bonds formed on the surface of the composite exhibit stronger charge redistribution. As a result, the obtained CoO /N-C-ZnO demonstrates enhanced photocatalysis performance in terms of high CO yield and long-term stability.
尽管光催化存在电荷载流子迁移率低的问题,但它仍是一种利用太阳能生产绿色燃料的极具吸引力和前景的技术。一种有效的方法是设计和制造先进的结构材料作为光催化剂,以提高基于半导体的光催化系统的性能。在此,金属有机框架衍生的分级有序多孔氮和碳共掺杂ZnO(N-C-ZnO)结构被开发为具有修饰的CoO纳米团簇的纳米反应器,用于可见光驱动的CO到CO的转化。具有高度有序互连的介观-大孔通道的分级纳米结构的引入对光催化还原反应显示出有益的特性,包括在高度可及的框架中增强电荷载流子的迁移率、活性位点的最大暴露以及光生电荷载流子复合的抑制。密度泛函理论计算进一步揭示了对CO分子具有高亲和力的CoO纳米团簇的关键作用,并且在复合材料表面形成的CoO键表现出更强的电荷重新分布。结果,所获得的CoO/N-C-ZnO在高CO产率和长期稳定性方面表现出增强的光催化性能。