Catalytically active atomically thin cuprate with periodic Cu single sites

Huimin Yang; Shibo Xi; Na Guo; Mu Wang; Lingmei Liu; Pin Lyu; Xiaolong Yu; Jing Li; Haomin Xu; Xiao Hai; Zejun Li; Xinzhe Li; Tao Sun; Xiaoxu Zhao; Yu Han; Wei Yu; Jie Wu; Chun Zhang; Honghan Fei; Ming Joo Koh; Jiong Lu

doi:10.1093/nsr/nwac100

Catalytically active atomically thin cuprate with periodic Cu single sites

Natl Sci Rev. 2022 May 25;10(1):nwac100. doi: 10.1093/nsr/nwac100. eCollection 2023 Jan.

Authors

Huimin Yang¹, Shibo Xi², Na Guo³, Mu Wang¹, Lingmei Liu⁴, Pin Lyu¹, Xiaolong Yu⁵, Jing Li¹, Haomin Xu¹, Xiao Hai¹, Zejun Li¹, Xinzhe Li¹, Tao Sun¹, Xiaoxu Zhao⁶, Yu Han⁴, Wei Yu¹, Jie Wu¹, Chun Zhang^{1

3

7}, Honghan Fei⁸, Ming Joo Koh¹, Jiong Lu^{1

7}

Affiliations

¹ Department of Chemistry, National University of Singapore, Singapore 117543, Singapore.
² Institute of Chemical and Engineering Sciences, Singapore 627833, Singapore.
³ Department of Physics, National University of Singapore, Singapore 117542, Singapore.
⁴ Advanced Membranes and Porous Materials Center, King Abdullah University of Science and Technology, Thuwal 23955-6900, Kingdom of Saudi Arabia.
⁵ SDU-ANU Joint Science College, Shandong University, Weihai264209, China.
⁶ School of Materials Science and Engineering, Peking University, Beijing 100871, China.
⁷ Centre for Advanced 2D Materials and Graphene Research Centre, National University of Singapore, Singapore 117546, Singapore.
⁸ Department of Chemistry, Tongji University, Shanghai200092, China.

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][O₃S(CH₂)₄SO₃] 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.

Keywords: exfoliation; heterogeneous catalysis; nanosheet.