Heterometallic Polarization Enabling Precise Intermediate Regulation for Selective CO2 Photoreduction
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Updated: Nov 7, 2026

Synthesis and Performance Evaluations of ZnCoS/ZnCdS with Twin Crystal Structure for Multifunctional Redox Photocatalysis in Energy Applications
Published on: July 25, 2025
Xiaohong Li1,2, Huiyi Li1, Qinglong Wu1
1Hefei National Research Center for Physical Sciences At the Microscale, iChEM, University of Science and Technology of China, Hefei, Anhui, China.
Abstract:
Achieving high selectivity in photocatalytic CO2 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 CO2 activation and charge transfer. As a result, MIL-88A(Fe/Ni2.5) achieves a CO production rate of 1517.4 µmol g-1 h-1-10.8 times higher than MIL-88A(Fe/Ni0)-with a selectivity of 97.9%. Increasing the Ni content strengthens CO* adsorption, thereby steering the reaction from CO evolution to deep hydrogenation toward CH4. MIL-88A(Fe/Ni7.5) delivers a CH4 production rate of 255.0 µmol g-1 h-1-28.3 and 14.5 times that of MIL-88A(Fe/Ni0) and MIL-88A(Fe/Ni2.5), 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 CO2 conversion.
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