Abstract Geminal-site catalysts (GSCs) are prospective candidates to fulfill the goal of aqueous electrochemical reductive cross-coupling reactions (ERCR) at near-stoichiometric yields. Nevertheless, the problem lies in lacking the synthetic route of GSCs with few single sites. Here we report a defect-accompanying strategy for synthesizing GSCs containing metal-defect catalytic pairs (M-D GSCs), and thereinto, Fe-D GSCs can realize the electrochemical synthesis of cyclohexanone oximes (CHO) from high concentrations (0.5 M) of nitrites (NO2−) and cyclohexanone (CYC) at near-stoichiometric yields (the Faradic efficiency or yieldC/N: 91.3%). Multiple in/ex-situ characterizations demonstrated that metal-citrate complexes were converted to metal-defect catalytic pairs via the liberation of gaseous carbon/nitrogen species during pyrolysis. Furthermore, we developed an innovative cathodic oxime-alkali process, where high concentration NaNO2 and CYC can be electrochemically converted to high purity products including NaOH and CHO. This work showcases the enormous potential of M-D GSCs in achieving near-stoichiometric conversion for ERCR reactions.
Wu et al. (Thu,) studied this question.