Coupling Electrochemical Sulfion Oxidation with CO2 Reduction over Highly Dispersed p‐Bi Nanosheets and CO2‐Assisted Sulfur Extraction

Abstract We report herein an electrocatalytic CO 2 reduction‐coupled sulfion oxidation system for the co‐productions of valuable formate and sulfur at much enhanced atom utilization. Specifically, an organic ligand‐assisted two‐step reconstruction approach has been developed to fabricate the highly dispersed p‐Bi nanosheets (p‐Bi NSs) for cathodic CO 2 reduction reaction (CO 2 RR), and meanwhile porous Co−S nanosheets (Co−S NSs) was applied for anodic sulfion oxidation reaction (SOR). Significantly high Faradaic Efficiencies of about 90 % for formate production by CO 2 RR in a wide potential range from −0.6 V to −1.1 V, and excellent SOR performances including an ultra‐low onset potential of about 0.2 V and recycle capacity of S 2− in the 0.1 M and 0.5 M S 2− solutions, have been simultaneously achieved. In the meantime, both the structure transformation of the catalysts and the reaction pathways are explored and discussed in detail. A two‐electrode CO 2 RR||SOR electrolyzer equipped with above electrocatalysts has been established, which features as low as about 1.5 V to run the electrolyzer at 100 mA cm −2 , manifesting extremely lowered electricity consumption in comparison to conventional CO 2 RR system. Moreover, a sulfur separation approach has been proposed by using CO 2 , which is efficient, environmentally friendly and cost effective with value‐added NaHCO 3 be obtained as the byproduct.