CO2‐Bridged Electrochemical Upcycling of Organic Pollutants to High‐Purity Formic Acid via Membrane Electrode Assembly

Abstract

Environmental pollution and energy shortage pose significant challenges to sustainable development. Conventional deep mineralization of organic pollutants not only increases carbon emissions but also causes the waste of carbon resources. Herein, a coupled electrocatalytic system that enables the selective conversion of various organic pollutants into high‐purity formic acid is constructed leveraging self‐supplied CO2 reduction as a bridge within a zero‐gap membrane electrode assembly electrolyzer. The Sb/SnO2‐PbO2 anode facilitates in situ CO2 generation for cathodic reduction, while a single‐atom Cu‐alloyed Bi cathode optimizes the adsorption strength of the key intermediates via the electron transfer from Cu to Bi, thereby boosting selective HCOOH production. The integrated electrolytic system achieves a formic acid yield of 62.48 µmol with a carbon utilization efficiency of 24.6% in 8 h. The underlying reaction mechanisms are revealed by in situ infrared spectroscopy, in situ Raman, online DEMS, which monitor the evolution of reaction intermediates and products, and the in situ X‐ray absorption fine structure spectroscopy that elucidates the dynamic chemical states of the catalytic sites. This work provides a novel strategy for the efficient resource utilization of wastewater containing complex components, demonstrating a sustainable pathway for the targeted synthesis of liquid fuels.