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 grand 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 an attractive catalyst candidate for broad utility in fine chemical synthesis.
|Original language||English (US)|
|Journal||National Science Review|
|State||Published - May 25 2022|
Bibliographical noteKAUST Repository Item: Exported on 2022-05-30
Acknowledgements: J.L. acknowledges the support from Ministry of Education of Singapore Grant (R-143-000-B47-114). J.L. and J.W. thank the support from National University of Singapore Flagship Green Energy Program (R-143-000-A55-646) and Agency for Science, Technology and Research (A*STAR) under its Advanced Manufacturing and Engineering Individual Research Grants Grant (A20E5c0096). C.Z. thanks the support of Ministry of Education of Singapore Grant (R-723-000-029-112), National University of Singapore Green Energy Program (R-143-000-A63-114) and National University of Singapore Graphene Center Computer Clusters. M.J.K. acknowledges the support form Ministry of Education of Singapore Academic Research Funds Tier 1 (R-143-000-B57-114). S.-B.X. acknowledges the support from the X-ray Absorption Fine Structure for Catalysis Beamline of Singapore Synchrotron Light Source and the National Supercomputing Centre, Singapore. X.-X.Z. thanks the support from the Presidential Postdoctoral Fellowship, Nanyang Technological University, Singapore (03INS000973C150).