Unraveling the Catalytic Performance of the Nonprecious Metal Single-Atom-Embedded Graphitic s‑Triazine-Based C₃N₄ for CO₂ Hydrogenation

Graphitic carbon nitride (g-C₃N₄) is regarded as a promising potent photoelectrocatalyst for CO₂ reduction. Here, extensive first-principles calculations and ab initio molecular dynamics (AIMD) simulations are performed to systematically explore the structural and electronic properties of nonprecious metal single-atom-embedded graphitic s-triazine-based C₃N₄ (M@gt-C₃N₄, M = Mn, Fe, Co, Ni, Cu, and Mo) monolayer materials and their catalytic performances as the single-atom catalysts (SACs) for CO₂ hydrogenation to HCOOH, CO, and CH₃OH. It is found that the atomically dispersed non-noble metal Mn, Fe, Co, and Mo sites anchored on gt-C₃N₄ can efficiently activate both H₂ and CO₂, and their coadsorbed state serves as a precursor to the hydrogenation of CO₂ to different C1 products. Among these SACs (M@gt-C₃N₄, M = Mn, Fe, Co, and Mo), Co@gt-C₃N₄ was predicted to have the best catalytic performance for CO₂ hydrogenation to C1 products, although their mechanistic details are somewhat different. The predicted energy barriers of the rate-determining steps for the conversion of CO₂ into HCOOH, CO, and CH₃OH on Co@gt-C₃N₄ are 0.58, 0.67, and 1.19 eV, respectively. The desorption of products is generally energy-demanding, but it can be facilitated remarkably by the subsequent adsorption of H₂, which regenerates M@gt-C₃N₄ for the next catalytic cycle. The present study demonstrates that the catalytic performance of gt-C₃N₄ can be well regulated by embedding the non-noble metal single atom, and the porous gt-C₃N₄ is nicely suited for the construction of high-performance single-atom catalysts.