Insights into bimetallic single-atom-doped g-C3N4 photo-catalysts for CO2 conversion to HCOOH: A DFT study

Developing low-cost, high-efficiency non-noble metallic photocatalytic materials is crucial for CO2 reduction. This paper investigates the substitution of noble metals dopant to a bimetallic non-noble Fe/Co dopant for g-C3N4 to enhance the photocatalytic CO2 reduction performance via density functional theory (DFT) calculations. This study examines the structure, electronic properties, CO2 adsorption configurations, and the transition states and Gibbs free energy of CO2 reduction to HCOOH on noble metal Pt/g-C3N4 doped, single-atom Fe/g-C3N4 doped, and bimetallic Fe/Co doped g-C3N4 catalysts, revealing the mechanisms of catalyst-mediated CO2 reduction. The results demonstrate that the introduction of Fe/Co bimetallic atoms leads to more efficient charge transfer, attributed to the synergistic and electronic effects of the bimetallic coupling, with a charge of 1.264, which is 2.2 and 1.2 times greater than that of Pt and Fe doped g-C3N4, respectively. Furthermore, the stronger adsorption energy of CO2 molecules on Fe/Co/g-C3N4 compared to pure g-C3N4, Pt/g-C3N4, and Fe/g-C3N4 indicates that adsorption on Fe/Co/g-C3N4 is more conducive to CO2 activation. The CO2 reduction reaction (CO2RR) calculations reveal that Fe/Co/g-C3N4 exhibits a lower reaction barrier of 0.789 eV compared to noble metal-doped Pt and single-atom Fe, due to the reduction of the reaction mechanism's energy barrier by the Fe/Co bimetallic doped g-C3N4, which facilitates a more effective reduction of CO2 to HCOOH. As a result, Fe/Co/g-C3N4 emerges as an effective alternative to noble metal-based photocatalysts. This study provides theoretical guidance for the preparation of efficient non-noble metal photocatalysts.