An acid-tolerant metal-organic framework for industrial CO2 electrolysis using a proton exchange membrane

Industrial CO2 electrolysis via electrochemical CO2 reduction has achieved progress in alkaline solutions, while the same reaction in acidic solution remains challenging because of severe hydrogen evolution side reactions, acid corrosion, and low target product selectivity. Herein, an industrial acidic CO2 electrolysis to pure HCOOH system is realized in a proton-exchange-membrane electrolyzer using an acid-tolerant Bi-based metal-organic framework guided by a Pourbaix diagram. Significantly, the Faradaic efficiency of HCOOH synthesis reaches 95.10% at a large current density of 400 mA/cm2 with a high CO2 single-pass conversion efficiency of 64.91%. Moreover, the proton-exchange-membrane device also achieves an industrial-level current density of 250 mA/cm2 under a relatively low voltage of 3.5 V for up to 100 h with a Faradaic efficiency of 93.5% for HCOOH production, which corresponds to an energy consumption of 200.65 kWh/kmol, production rate of 12.1 mmol/m2/s, and an energy conversion efficiency of 38.2%. These results will greatly aid the contemporary research moving toward commercial implementation and success of CO2 electrolysis technology. This work develops an industrial-level CO2 electrolysis system for formic acid production by constructing a proton exchange membrane electrolyzer with an acid-tolerant Bismuth metal-organic framework.