Construction of Six-Oxygen-Coordinated Single Ni Sites on g-C₃ N₄ with Boron-Oxo Species for Photocatalytic Water-Activation-Induced CO₂ Reduction.

Abstract

The configuration regulation of single-atom photocatalysts (SAPCs) can significantly influence the interfacial charge transfer and subsequent catalytic process. The construction of conventional SAPCs for aqueous CO₂ reduction is mainly devoted toward favorable activation and photoreduction of CO₂ , however, the role of water is frequently neglected. In this work, single Ni atoms are successfully anchored by boron-oxo species on g-C₃ N₄ nanosheets through a facile ion-exchange method. The dative interaction between the B atom and the sp² N atom of g-C₃ N₄ guarantees the high dispersion of boron-oxo species, where O atoms coordinate with single Ni (II) sites to obtain a unique six-oxygen-coordinated configuration. The optimized single-atom Ni photocatalyst, rivaling Pt-modified g-C₃ N₄ nanosheets, provides excellent CO₂ reduction rate with CO and CH₄ as products. Quasi-in-situ X-ray photoelectron spectra, transient absorption spectra, isotopic labeling, and in situ Fourier transform infrared spectra reveal that as-fabricated six-oxygen-coordinated single Ni (II) sites can effectively capture the photoelectrons of CN along the BO bridges and preferentially activate adsorbed water to produce H atoms to eventually induce a hydrogen-assisted CO₂ reduction. This work diversifies the synthetic strategies for single-atom catalysts and provides insight on correlation between the single-atom configuration and reaction pathway.