Solar-driven photocatalytic nitrogen fixation on transition metal-doped covalent organic frameworks: First-principles study

Designing highly efficient single-atom catalysts for converting nitrogen into ammonia under ambient temperature conditions holds significant importance. Current research predominantly focuses on electrocatalytic nitrogen fixation, but compared to that, photocatalytic nitrogen fixation requires only sunlight as an energy source, making it more environmentally friendly and cost-effective. Developing efficient nitrogen reduction reaction (NRR) photocatalysts presents a promising yet highly challenging task. Two-dimensional (2D) covalent organic frameworks (COFs) have garnered interest because of their elevated surface area and regular pore structure. This study employs density functional theory calculations to investigate the potential of NRR photocatalysts using the 2D COF TMT-TFPT-COF (TT-COF) supported with 18 different transition metal atoms (TM = Rh, Nb, Os, Mo, Ru, Pt, Ni, Co, V, Cu, Fe, Re, W, Cr, Ta, Mn, Pd, Ti). Through a four-step selection process, the most promising photocatalyst is identified. The results indicate that a single Re atom loaded onto TT-COF (Re@TT-COF) displays the optimal nitrogen fixation performance, demonstrating excellent catalytic activity and selectivity with a limiting potential of only −0.30 V. Furthermore, its good light absorption efficiency, suitable band edge position, and significant photo-generated electron potential enable spontaneous nitrogen fixation. Our study provides useful guidance for the rational design of COF-based NRR photocatalysts with high activity, stability, and selectivity.