Matching Bidentate Ligand Anchoring: an Accurate Control Strategy for Stable Single‐Atom/ZIF Nanocatalysts

Abstract Improving metal loading and controlling the coordination environment is nontrivial and challenging for single‐atom catalysts (SACs), which have the greatest atomic efficiency and largest number of interface sites. In this study, a matching bidentate ligand (MBL) anchoring strategy is designed for the construction of CuN ₄ SACs with tunable coordination environments (Cu loading range from 0.4 to15.4 wt.%). The obtained Cu SA/ZIF and Cu SA/ZIF* (0.4 wt.%) (ZIF and ZIF* = Zeolitic imidazolate framework with Matching bidentate N‐ligands) nanocomposites exhibit superior performance in homo‐coupling of phenyl acetylene under light irradiation (TON = 580, selectivity > 99%), which is 22 times higher than that of Cu SA/NC‐800 (NC = N‐doped porous carbon). Experiments and density functional theory calculations confirmed that the specific Cu five‐membered ring formed using the MBL anchoring strategy is the key to the immobilization of isolated Cu atoms. This strategy provides a basis for the construction of M SA/MOF, which has the potential to narrow the gap between experimental and theoretical catalysis, as further confirmed by the successful preparation of Fe SA/ZIF and Ni SA/ZIF.