Asymmetric Cu−N−La Species Enabling Atomic‐Level Donor‐Acceptor Structure and Favored Reaction Thermodynamics for Selective CO₂ Photoreduction to CH₄

Abstract

Photocatalytic CO2 reduction into ideal hydrocarbon fuels, such as CH4, is a sluggish kinetic process involving adsorption of multiple intermediates and multi‐electron steps. Achieving high CH4 activity and selectivity therefore remains a great challenge, which largely depends on the efficiency of photogenerated charge separation and transfer as well as the intermediate energy levels in CO2 reduction. Herein, we construct La and Cu dual‐atom anchored carbon nitride (LaCu/CN), with La‐N4 and Cu‐N3 coordination bonds connected by Cu−N−La bridges. The asymmetric Cu−N−La species enables the establishment of an atomic‐level donor‐acceptor structure, which allows the migration of electrons from La atoms to the reactive Cu atom sites. Simultaneously, intermediates during CO2 reduction on LaCu/CN demonstrate thermodynamically more favorable process for CH4 formation based on theoretical calculations. Eventually, LaCu/CN exhibits a high selectivity (91.6 %) for CH4 formation with a yield of 125.8 μmol g−1, over ten times of that for pristine CN. This work presents a strategy for designing multi‐functional dual‐atom based photocatalysts.

Variable-valence element doping mediated photogenerated electron trapping for selective oxidation reactions

“…12–14 Meanwhile, the introduction of variable-valence elements, such as Cu with monovalent and divalent character, could not only generate an impurity state, but also offer a redox pair based on Cu( ii )/Cu( i ), as schematically illustrated in Scheme 1. 15–18…”

N vacancies modulated Zn single atoms for efficient H2O2 photosynthesis

“…MSAs/CN are effective in many catalytic reactions for molecules conversion. 10–14 However, highly efficient photosynthesis for H 2 O 2 production is not easy to be attained due to the decomposition of H 2 O 2 on several transition metal centers, low photogenerated charge transfer efficiency and sluggish kinetic process.…”