Rational Regulation of Electronic Structure in Layered Double Hydroxide Via Vanadium Incorporation to Trigger Highly Selective CO₂ Photoreduction to CH₄

Abstract

To realize excellent selectivity of CH₄ in CO₂ photoreduction (CO₂ PR) is highly desirable, yet which is challenging due to the limited active sites for CH₄ generation and severe electron-hole recombination on photocatalysts. Herein, based on the theoretically calculated effects of vanadium incorporation into the laminate of layered double hydroxides (LDHs), V into NiAl-LDH to synthesize a series of LDHs with various V contents is introduced. NiV-LDH is revealed to afford a high CH₄ selectivity (78.9%), and extremely low H₂ selectivity (only 0.4%) under λ > 400 nm irradiation. By further tuning the molar ratio of Ni to V, a CH₄ selectivity of as high as 90.1% is achieved on Ni₄ V-LDH, and H₂ is completely prohibited on Ni₂ V-LDH. Fine structural characterizations and comprehensive optical and electrochemical studies uncover V incorporation creates the lower-valence Ni species as active sites for generating CH₄ , and enhances the generation, separation, and transfer of photogenerated carriers.