Electrophile-Nucleophile Paired Heteronuclear Dual-Site for Selective CO₂ Photoreduction to Ethanol via Oxygen-Tethered Asymmetric C-C Coupling.

Authors

Tianyi Huang, Jianyu Han, Bingzhang Lu, Yafeng Wu, Yuanjian Zhang, Songqin Liu

Published in

Angewandte Chemie (International ed. in English). Pages e3999411. Jul 02, 2026. Epub Jul 02, 2026.

Abstract

Photocatalytic CO₂ reduction to valuable multicarbon products like ethanol is a promising strategy for solar energy conversion, yet remains challenged by kinetically constrained C-C coupling and competitive C-O cleavage toward ethylene. Herein, an electrophile-nucleophile pairing strategy is developed by constructing atomically Cu-Zr heteronuclear dual sites within a porphyrinic framework, which can simultaneously reduce repulsion for C-C coupling and strengthen the C-O bond. The electron-deficient Zr, as a strong oxygen-affixed anchor, stabilizes critical *OCH intermediates via O-coordination, while adjacent electron-rich Cu sites drive *CO adsorption-inducing charge asymmetry between *OCH and *CO for kinetically favored dimerization. Subsequent hydrogenation selectively proceeds toward ethanol due to enhanced Zr-O stabilization that prevents C-O scission. The optimized catalyst achieved a near-unity ethanol selectivity at 87.8 µmol·g^-1·h^-1 using water as a scavenger under a CO₂ pressure of 0.5 MPa, which further increased to 195.1 µmol·g^-1·h^-1 at 1.5 MPa. This work establishes mismatched electrophile-nucleophile pairs as a versatile design principle for steering photocatalytic CO₂ reduction toward value-added multicarbon products.

PMID:
42390814
Bibliographic data and abstract were imported from PubMed on 02 Jul 2026.

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