Nanocavity-Confined Cu2O in Porphyrin-based MOF for Steering CO2 Electroreduction toward Hydrocarbons

Abstract

The electrocatalytic conversion of CO2 to hydrocarbon compound still faces fundamental challenges, including the high activation barrier of CO2 and insufficient selectivity toward C2+ products. This study constructs a composite catalyst (Cu2O@PCN-223) for efficient electrocatalytic CO2 reduction, utilizing the nanoconfinement of metal−organic framework (MOF) to regulate the dispersion of Cu2O and modulate reaction intermediates. Structural characterization confirms the uniform distribution of Cu2O within the lattice of PCN-223, with interfacial electronic interactions significantly enhancing charge transfer and catalytic activity. The optimized catalyst demonstrates remarkable hydrocarbon selectivity, delivering Faradaic efficiency (FE) of 38.7% for CH4 and 48.7% for C2H4 at −1.3 V vs. RHE, with a total hydrocarbon FE reaching 87.4%, which is 6-7 times higher than that of pristine Cu2O. DFT calculations demonstrates that MOF-confined microenvironment selectively promotes C2 production by stabilizing key intermediates (*CO and *CHO) and facilitating charge transfer during C-C coupling, establishing a strategic design paradigm for efficient CO2-to-hydrocarbon conversion