Kwak Minjoon, Bok Jinsol, Lee Byoung-Hoon, Kim Jongchan, Seo Youngran, Kim Sumin, Choi Hyunwoo, Ko Wonjae, Hooch Antink Wytse, Lee Chan Woo, Yim Guk Hee, Seung Hyojin, Park Chansul, Lee Kug-Seung, Kim Dae-Hyeong, Hyeon Taeghwan, Yoo Dongwon
Department of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University Seoul 08826 Republic of Korea
Center for Nanoparticle Research, Institute for Basic Science (IBS) Seoul 08826 Republic of Korea.
Chem Sci. 2022 Jun 20;13(29):8536-8542. doi: 10.1039/d2sc02174a. eCollection 2022 Jul 29.
Visible-light-driven organic transformations are of great interest in synthesizing valuable fine chemicals under mild conditions. The merger of heterogeneous photocatalysts and transition metal catalysts has recently drawn much attention due to its versatility for organic transformations. However, these semi-heterogenous systems suffered several drawbacks, such as transition metal agglomeration on the heterogeneous surface, hindering further applications. Here, we introduce heterogeneous single Ni atoms supported on carbon nitride (NiSAC/CN) for visible-light-driven C-N functionalization with a broad substrate scope. Compared to a semi-heterogeneous system, high activity and stability were observed due to metal-support interactions. Furthermore, through systematic experimental mechanistic studies, we demonstrate that the stabilized single Ni atoms on CN effectively change their redox states, leading to a complete photoredox cycle for C-N coupling.
可见光驱动的有机转化在温和条件下合成有价值的精细化学品方面具有极大的吸引力。非均相光催化剂和过渡金属催化剂的结合最近因其在有机转化方面的多功能性而备受关注。然而,这些半均相体系存在一些缺点,例如过渡金属在非均相表面上的团聚,阻碍了进一步的应用。在此,我们引入负载在氮化碳上的非均相单镍原子(NiSAC/CN)用于可见光驱动的具有广泛底物范围的C-N官能化。与半均相体系相比,由于金属-载体相互作用,观察到了高活性和稳定性。此外,通过系统的实验机理研究,我们证明了在CN上稳定的单镍原子有效地改变了它们的氧化还原状态,导致了用于C-N偶联的完整光氧化还原循环。