A high-efficient electrochemical synthesis of a low-nuclearity copper-cluster-based metal–organic framework for the size-selective oxidation of alcohols

It is highly desirable yet challenging to incorporate open micropores with mass transportation and open active metal sites into metal–organic frameworks (MOFs) for developing novel highly efficient catalysts. Herein, we report a catalyst of low-nuclearity copper-cluster-based micropore MOF, namely H-1e, incorporated with unsaturated Cu(II) centres as open active sites obtained via a highly efficient electrochemical synthesis within 20 minutes. The catalyst H-1e shows potential porosity with 1D open functionalized hexagonal channels for size-selective air oxidation as well as high stability. The electrochemically prepared H-1e exhibits excellent catalytic aerobic oxidation activity for the conversion of alcohols (mini-size) to aldehydes with over 99% selectivity and 99% yield under air conditions, showing excellent reusability and stability. The selective catalytic performances are found to be closely dependent on the suitable aperture size of the 1D channels in H-1e, which provided better beds for the oxidation transformations (confirmed by the computational DFT study). In this study, it offers a simple and potential strategy to construct microporous materials with open active metal sites to promote the catalytic efficiency of MOFs by electrochemical synthesis.