Divergent Paths, Same Goal: A Pair‐Electrosynthesis Tactic for Cost‐Efficient and Exclusive Formate Production by Metal–Organic‐Framework‐Derived 2D Electrocatalysts

Abstract Electrosynthesis of formic acid/formate is a promising alternative protocol to industrial processes. Herein, a pioneering pair‐electrosynthesis tactic is reported for exclusively producing formate via coupling selectively electrocatalytic methanol oxidation reaction (MOR) and CO 2 reduction reaction (CO 2 RR), in which the electrode derived from Ni‐based metal–organic framework (Ni‐MOF) nanosheet arrays (Ni‐NF‐Af), as well as the Bi‐MOF‐derived ultrathin bismuthenes (Bi‐enes), both obtained through an in situ electrochemical conversion process, are used as efficient anodic and cathodic electrocatalysts, respectively, achieving concurrent yielding of the same high‐value product at both electrodes with greatly reduced energy input. The as‐prepared Ni‐NF‐Af only needs quite low potentials to reach large current densities (e.g., 100 mA cm −2 @1.345 V) with ≈100% selectivity for anodic methanol‐to‐formate conversion. Meanwhile, for CO 2 RR in the cathode, the as‐prepared Bi‐enes can simultaneously exhibit near‐unity selectivity, large current densities, and good stability in a wide potential window toward formate production. Consequently, the coupled MOR//CO 2 RR system based on the distinctive MOF‐derived catalysts displays excellent performance for pair‐electrosynthesis of formate, delivering high current densities and nearly 100% selectivity for formate production in both the anode and the cathode. This work provides a novel way to design advanced MOF‐derived electrocatalysts and innovative electrolytic systems for electrochemical production of value‐added feedstocks.