2D Porphyrin-Based Conjugated Hypercrosslinked Polymer Integrated with CuO for Efficient CO2 Electroreduction
Two-dimensional porphyrin-based hypercrosslinked polymers (TPP-HCPs) were synthesized via room-temperature interfacial polymerization using 5,10,15,20-tetraphenylporphyrin and 1,3,5-trioxane. The resulting TPP-HCPs exhibited a BET surface area of 548 m2 g-1 and a CO2 uptake of 7.97 wt% at 1 bar and 298 K. CuO/TPP-HCPs nanospheres were fabricated by thermal conversion of Cu(NO3)2·3H2O in DMF at 135 °C, using TPP-HCPs as dynamic templates. This in-situ strategy generated CuO nanoparticles within the conjugated porous matrix, facilitating electron transfer and enhancing CO2 access to catalytic centers. In CO2 electroreduction, the composite achieved a total gas Faradaic efficiency exceeding 90% at ~500 mA cm-2 (-1.4 V vs. RHE), with 40.9% for C2H4, 8.2% for CH4, 31.9% for CO, and 12.3% for H2. The catalyst maintained stability over 24 h in an H-cell. These results demonstrate that 2D conjugated polymer-templated catalysts can sustain high-rate CO2 conversion to value-added products, offering a viable route for industrial CO2 utilization.