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

We report herein an electrocatalytic CO2 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 CO2 reduction reaction (CO2 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 CO2 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 S2- in the 0.1 M and 0.5 M S2- 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 CO2 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 CO2 RR system. Moreover, a sulfur separation approach has been proposed by using CO2 , which is efficient, environmentally friendly and cost effective with value-added NaHCO3 be obtained as the byproduct.