Catalytically active atomically thin cuprate with periodic Cu single sites. Issue 1 (25th May 2022)

• Record Type: Journal Article
• Authors: Yang, Huimin; Xi, Shibo; Guo, Na; Wang, Mu; Liu, Lingmei; Lyu, Pin; Yu, Xiaolong; Li, Jing; Xu, Haomin; Hai, Xiao; Li, Zejun; Li, Xinzhe; Sun, Tao; Zhao, Xiaoxu; Han, Yu; Yu, Wei; Wu, Jie; Zhang, Chun; Fei, Honghan; Koh, Ming Joo; Lu, Jiong
• Is Part Of: National science review. Volume 10:Issue 1(2023)
• Publication Date: 2022-05-25
• Subjects: exfoliation -- nanosheet -- heterogeneous catalysis; Science -- Periodicals; 505
• DOI: 10.1093/nsr/nwac100
• Languages: English
• ISSNs: 2095-5138

Abstract

ABSTRACT: Rational design and synthesis of catalytically active two-dimensional (2D) materials with an abundance of atomically precise active sites in their basal planes remains a great challenge. Here, we report a ligand exchange strategy to exfoliate bulk [Cu4 (OH)6 ][O3 S(CH2 )4 SO3 ] cuprate crystals into atomically thin 2D cuprate layers ([Cu2 (OH)3 ] + ). The basal plane of 2D cuprate layers contains periodic arrays of accessible unsaturated Cu(II) single sites (2D-CuSSs), which are found to promote efficient oxidative Chan-Lam coupling. Our mechanistic studies reveal that the reactions proceed via coordinatively unsaturated CuO4 (II) single sites with the formation of Cu(I) species in the rate-limiting step, as corroborated by both operando experimental and theoretical studies. The robust stability of 2D-CuSSs in both batch and continuous flow reactions, coupled with their recyclability and good performance in complex molecule derivatization, render 2D-CuSSs attractive catalyst candidates for broad utility in fine chemical synthesis. Abstract : A ligand exchange strategy exfoliates bulk cuprate crystals into atomically thin 2D cuprate layers with periodic unsaturated copper single sites, which are found to promote efficient oxidative Chan-Lam coupling.