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

Abstract The paired electrolysis coupling the reduction of CO 2 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 CO 2 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.