Work

Heterometallic Polarization Enabling Precise Intermediate Regulation for Selective CO 2 Photoreduction

Year: 2026

Type: article

Abstract: ABSTRACT Achieving high selectivity in photocatalytic CO 2 reduction remains a fundamental challenge, as competing pathways share similar thermodynamic potentials but differ in their intermediate adsorption behavior. Here we introduce a heterometallic polarization strategy based on bimetallic metal–organic frameworks (MOFs), where asymmetric charge redistribution between distinct metal centers tailors the local electronic structure and modulates CO* binding energetics. Taking MIL‐88A(Fe/Ni) as a model system, the incorporation of Ni induces intermetallic electronic coupling, creating polarized Fe─Ni sites that synergistically enhance CO 2 activation and charge transfer. As a result, MIL‐88A(Fe/Ni 2.5 ) achieves a CO production rate of 1517.4 µmol g −1 h −1 —10.8 times higher than MIL‐88A(Fe/Ni 0 )—with a selectivity of 97.9%. Increasing the Ni content strengthens CO* adsorption, thereby steering the reaction from CO evolution to deep hydrogenation toward CH 4 . MIL‐88A(Fe/Ni 7.5 ) delivers a CH 4 production rate of 255.0 µmol g −1 h −1 —28.3 and 14.5 times that of MIL‐88A(Fe/Ni 0 ) and MIL‐88A(Fe/Ni 2.5 ), respectively—with an electron selectivity of 81.3%. These results demonstrate that heterometallic polarization provides a powerful design principle for regulating intermediates and achieving tunable product selectivity in photocatalytic CO 2 conversion.

Source: Angewandte Chemie International Edition

DOI: 10.1002/anie.7635932