Covalent Phenanthroline-Porphyrin Polymer for Aminocarbonylation through Electro/Thermocatalytic Tandem Processes: Extending Chemical Valorization of CO₂

The covalent organic frameworks/polymers configurated with metal-N-4 conjugated structures offer an exceptional platform for efficient electrochemical CO2 reduction reaction (eCO(2)RR). However, understanding the impact of the structure-mediated local microenvironment and integrating CO2 electroreduction with follow-up utilization toward extending chemical valorization of CO2 are still far from sufficient. Herein, a set of covalent phenanthroline-porphyrin polymers are designed to decode the microenvironment modulation originating from built-in structures, and the optimized one delivered an extraordinary performance for eCO(2)RR with approximate to 100% Faradaic efficiency of CO under stabilized CO2-electrolysis of 70 h. The experimental and theoretical analyses suggest that the regulation of the Co-N-4 electronic structures and microenvironment convoys the stabilized formation of key reaction intermediate *COOH. Furthermore, through CO-mediated electro/thermocatalytic tandem processes, the aminocarbonylation of aryl iodides and amines with high yields has been convincingly implemented over the coordinated Pd sites, which is remarkably helpful to propel extending chemical valorization of CO2.