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

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 CuN4 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.