p-d hybridized Single-atom Catalysts based on Covalent-bond-linked Fullerene Monolayer Network for CO2 Reduction

Abstract

The electrocatalytic carbon dioxide reduction reaction (CO2RR), which converts CO₂ into value-added chemicals and fuels aided by highly efficient catalytic systems, represents a promising pathway toward achieving carbon neutrality and sustainable development. In this work, we design a class of highly efficient p-d hybridized single-atom catalysts (p-d-SACs) for CO2RR, based on the recently synthesized quasi-hexagonal-phase covalently bonded fullerene monolayer network (qHP-C₆₀) [Hou et al., Nature (London) 606, 507 (2022)]. We demonstrated that transition metal single atoms from the 3d and 4d series can be stably anchored within the hollow sites of this C₆₀-based two-dimensional network, forming a series of TM1@qHP-C₆₀p-d-SACs. First-principles calculations reveal that these p-d-SACs exhibit excellent catalytic performance for CO₂ activation, attributed to strong p-d hybridization and the synergistic effects of charge and spin redistribution between the d-block transition metal centers and the p-block fullerene network. Furthermore, the competition between CO2RR and the hydrogen evolution reaction (HER) is systematically investigated. Strategies such as increasing the transition metal atom loading and encapsulating alkali metals within the fullerene cages are proposed to further improve CO2RR selectivity and efficiency, offering new insights for the rational design of high-performance carbon-based SAC platforms.