Tandem Electro-Thermo-Catalysis for the Oxidative Aminocarbonylation of Arylboronic Acids to Amides from CO₂ and Water

Direct CO2 electroreduction to valuable chemicals is critical for carbon neutrality, while its main products are limited to simple C-1/C-2 compounds, and traditionally, the anodic O-2 byproduct is not utilized. We herein report a tandem electrothermo-catalytic system that fully utilizes both cathodic (i.e., CO) and anodic (i.e., O-2) products during overall CO2 electrolysis to produce valuable organic amides from arylboronic acids and amines in a separate chemical reactor, following the Pd(II)-catalyzed oxidative aminocarbonylation mechanism. Hexamethylenetetramine (HMT)-incorporated silver and nickel hydroxide carbonate electrocatalysts were prepared for efficient coproduction of CO and O-2 with Faradaic efficiencies of 99.3 % and 100 %, respectively. Systematic experiments, operando attenuated total reflection surface-enhanced Fourier transform infrared spectroscopy characterizations and theoretical studies reveal that HMT promotes *CO2 hydrogenation/*CO desorption for accelerated CO2-to-CO conversion, and O-2 inhibits reductive deactivation of the Pd(II) catalyst for enhanced oxidative aminocarbonylation, collectively leading to efficient synthesis of 10 organic amides with high yields of above 81 %. This work demonstrates the effectiveness of a tandem electrothermo-catalytic strategy for economically attractive CO2 conversion and amide synthesis, representing a new avenue to explore the full potential of CO2 utilization.