Transition metal single atom anchored C3N for highly efficient formic acid dehydrogenation: A DFT study

Formic acid (HCOOH) is a promising hydrogen carrier. Developing efficient and low-cost catalysts is significant for the application of HCOOH in clean and renewable energy. In this work, a series of single-atom catalysts composed of twelve transition metal single atoms (Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag and Au) supported on a novel carbon-nitrogen material (C3N) were designed and the catalytic performance for HCOOH dehydrogenation was demonstrated using density functional theory. By evaluating the binding strength of TM atoms, the adsorption stability of HCOOH and the hydrogen evolution performance of H species, Ni@C3N, Pd@C3N and Pt@C3N were finally screened out as candidates, on which the HCOO-dehydrogenation pathway is the most preferred. Judging from energetic span, Pd@C3N (0.60 eV) owns the best catalytic activity, while Ni@C3N (1.02 eV) and Pt@C3N (1.12 eV) are also appreciable alternatives compared with Pd( 111) (1.23 eV). Through the analysis of catalytic mechanism and electronic structure, the factors influencing reaction activity were revealed. This work enlightens the advantage of C3N-based materials and provides a novel approach for rationally designing high-performance catalysts for hydrogen production from HCOOH.

Automated summary

This study developed a series of single-atom catalysts supported on a novel carbon-nitrogen material and evaluated their catalytic performance for formic acid dehydrogenation using density functional theory. Ni@C3N, Pd@C3N, and Pt@C3N were identified as candidates, with Pd@C3N exhibiting the best catalytic activity. Factors influencing reaction activity were revealed through analysis of catalytic mechanism and electronic structure.