In this study, we present copper- and zinc-based metal–organic framework (MOF) integrated with highly ordered mesoporous carbons derived from guanine- and imidazolium-rich ionic liquids. The copper-MOF/guanine-rich ionic liquid-derived ordered mesoporous carbon (Cu-BTC@GIOMC) demonstrates suitable electrocatalytic performance for the CO₂ reduction reaction (eCO₂RR) in near-neutral aqueous media (pH 7.4), achieving high current densities at low overpotentials (onset potential approximately –0.35 V versus the reversible hydrogen electrode, RHE). The pronounced interfacial coupling between the MOF framework and the conductive carbon matrix, combined with uniformly dispersed copper active sites and a large accessible surface area, facilitates efficient charge transfer and enhances product selectivity toward C₁ species; namely, formic acid in the liquid phase and carbon monoxide in the gas phase; resulting in Faradaic efficiency of 56%. Concurrently, a zinc-MOF (Zn-APA) constructed from a nitrogen-rich linker, 5-aminoisophthalic acid, H 2 AIP, was electrochemically deposited onto an ionic-liquid-derived nano-fibrillated mesoporous carbon (IFMC). Although the nitrogen content doped into IFMC is substantially lower than that in GIOMC, the amine-functionalized H 2 AIP ligand partially compensates for this nitrogen deficiency at the MOF–carbon interface, thereby modulating the electronic environment and directing the selectivity of CO₂RR toward carbon monoxide formation, with a Faradaic efficiency of 61%. These results highlight the important role of the interaction among nitrogen chemistry, MOF composition, and carbon architecture in controlling CO₂ activation pathways. They also offer a versatile strategy for designing hybrid electrocatalysts for carbon-neutral energy conversion. • Cu and Zn-based MOF/mesoporous carbon hybrids were designed for efficient eCO 2 RR. • Cu-BTC@GIOMC shows a low onset potential of –0.35 V vs. RHE in neutral media. • Synergistic MOF-carbon interfaces enhance charge transfer and suppress HER. • Nitrogen-rich ligands and carbon structures modulate the catalytic microenvironment. • The hybrids achieved suitable Faradaic efficiencies of 56% and 61% for C 1 products.
Omidi et al. (Thu,) studied this question.