articleJournal of the American Chemical SocietyFeb 2, 2026Closed access

Site-Specific Asymmetric Coordination Engineering in Defective Metal–Organic Frameworks Stabilizes Cu(I) Active Sites for Selective CO 2 -to-Methanol Photocatalysis

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Abstract

Solar-driven CO2 reduction by means of single-atom photocatalysis holds great promise for simultaneously addressing carbon neutrality and producing valuable chemicals. The coordination-field engineering of a single-atom (SA) site essentially provides an intriguing strategy to steer the CO2 reduction pathway. We report herein the site-specific confinement of Cu SA with an asymmetric coordination microenvironment in defective MIL-125-NH2 to facilitate photocatalytic CO2-to-CH3OH conversion. This is achieved by precisely anchoring a flexible N-heteromacrocyclic ligand of tetraxetan (DOTA) on unsaturated Ti-oxo clusters to repair the missing-linker defect in heat-treated MIL-125-NH2, followed by Cu-DOTA chelation…

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