Cao Qinxuan, Feng Jianning, Zhang Jinzhong, Xue Jie, Wang Kang, Yang Ye, Lu Haipeng
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon 999077, Hong Kong (SAR), China.
State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
Inorg Chem. 2024 Dec 9;63(49):23467-23474. doi: 10.1021/acs.inorgchem.4c04714. Epub 2024 Nov 25.
Direct utilization of solar energy by semiconductor nanocrystals for chemical transformations via photocatalysis has recently drawn a great deal of attention. While most photocatalytic reactions are mediated through photoredox events, the ultimate reaction scalability relies on the use of sacrificial agents. The imbalanced population of photogenerated electrons and holes often leads to catalyst degradation through photocorrosion. To circumvent this, we designed Ni-doped CsPbBr nanoplatelets (NPls) as a "redox-neutral" photocatalyst, where both oxidative and reductive cycles occur in one photocatalyst. We showed that surface Ni ions can act as an "electron shuttle" to reduce protons, generating clean-energy H gas, while the photogenerated holes can be used to oxidize diaryl hydrazines to afford valuable azobenzenes and derivatives. Compared with previous photocatalytic demonstrations, our catalysts show excellent reaction yields with a wide substrate scope, unity atomic efficiency, and enhanced stability and recyclability.
通过光催化利用半导体纳米晶体直接将太阳能用于化学转化最近引起了广泛关注。虽然大多数光催化反应是通过光氧化还原事件介导的，但最终的反应可扩展性依赖于牺牲剂的使用。光生电子和空穴的数量不平衡常常导致催化剂通过光腐蚀而降解。为了规避这一问题，我们设计了镍掺杂的CsPbBr纳米片（NPls）作为“氧化还原中性”光催化剂，其中氧化和还原循环在一种光催化剂中发生。我们表明，表面镍离子可以作为“电子穿梭体”来还原质子，生成清洁能源氢气，而光生空穴可用于氧化二芳基肼以得到有价值的偶氮苯及其衍生物。与先前的光催化演示相比，我们的催化剂在广泛的底物范围内显示出优异的反应产率、单位原子效率以及增强的稳定性和可回收性。
