Erbium Single Atom Composite Photocatalysts for Reduction of CO₂ under Visible Light: CO₂ Molecular Activation and 4<i>f</i> Levels as an Electron Transport Bridge

Abstract

It is still challenging to design a stable and efficient catalyst for visible-light CO₂ reduction. Here, Er³⁺ single atom composite photocatalysts are successfully constructed based on both the special role of Er³⁺ and the special advantages of Zn₂ GeO₄ /g-C₃ N₄ heterojunction in the photocatalysis reduction of CO₂ . Especially, Zn₂ GeO₄ :Er³⁺ /g-C₃ N₄ obtained by in situ synthesis is not only more conducive to the tight junction of Zn₂ GeO₄ and g-C₃ N₄ , but also more favorable for g-C₃ N₄ to anchor rare-earth atoms. Under visible-light irradiation, Zn₂ GeO₄ :Er³⁺ /g-C₃ N₄ shows more than five times enhancement in the catalytic efficiency compared to that of pure g-C₃ N₄ without any sacrificial agent in the photocatalytic reaction system. A series of theoretical and experimental results show that the charge density around Er, Ge, Zn, and O increases compared with Zn₂ GeO₄ :Er³⁺ , while the charge density around C decreases compared with g-C₃ N₄ . These results show that an efficient way of electron transfer is provided to promote charge separation, and the dual functions of CO₂ molecular activation of Er³⁺ single atom and 4f levels as electron transport bridge are fully exploited. The pattern of combining single-atom catalysis and heterojunction opens up new methods for enhancing photocatalytic activity.