Anodic Product‐Derived Bi‐MOF as Pre‐catalyst for Cathodic CO2 Reduction: A Novel Strategy for Paired Electrolysis

The paired electrolysis coupling the reduction of CO2 to value‐added molecules like HCOOH with the oxidation of biomass‐derived 5‐hydroxymethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA) is one promising strategy of great economic and environmental benefits. Herein, a Ni(OH)2 anode for the selective oxidation of HMF to FDCA was fabricated, revealing the significant part of the membrane in electrocatalytic procedure. With the FDCA product as a di‐carboxylic acid ligand, one new bismuth‐based metal‐organic framework material was synthesized, which is capable of catalyzing the reduction of CO2 to HCOOH with over 95 % Faradaic efficiency (FE) and an average current density of 19.6 mA cm−2 at −1.2 V vs. reversible hydrogen electrode (RHE). With this inner relationship, paired electrolysis was conducted with cathodic potential fixed at −1.2 V vs. RHE, producing the HCOOH with 95.6 % FE and FDCA with 75 % FE in one single electrolyzer. One paired electrolysis system coupling the reduction of CO2 and oxidation of biomass‐based HMF has been constructed, where the obtained FDCA from the anodic oxidation reaction could be employed to synthesize one bismuth‐based metal‐organic framework, which could catalyze the electrochemical reduction of CO2 to HCOOH efficiently with over 95 % FE.