Designing C3N-supported single atom catalysts for efficient nitrogen reduction based on descriptor of catalytic activity

The two-step strategy screening based high throughput calculation is an effective method to search for highly active single atom catalysts (SACs) for efficient nitrogen reduction reaction (NRR), sharing a common feature of active metal centers MN4. However, this method faces the lack of descriptor for designing SACs due to limited data. Herein we proposed a robust empirical rule to estimate 312 credible limiting potentials for NRR over 104 C3N-supported SACs. It is found that the limiting potential scales clearly with the adsorption free energies of two key reaction intermediates (*N2H and *NH2), which are significantly dependent on the structure relating descriptor 4, and the activity of SACs with and without N coordination exhibits similar catalytic efficiency. We identified four high-performance SACs having moieties of CrC2N2, CrC4, MnC4 and OsC4 with high selectivity towards NRR and competitive limiting potentials of -0.40, -0.45, -0.53 and -0.54 V, respectively. The 4 values for these four SACs are around 19-25 which fall within its optimal ranges of 20-25 validating its prediction fidelity. This work broadens the discovery of two-dimensional carbon-nitrides supported SACs free of N coordination towards efficient N-2 reduction and opens a new route of descriptor-guided design of efficient SACs for electrocatalysis process. (C) 2021 Elsevier Ltd. All rights reserved.

Automated summary

A robust empirical rule was proposed to estimate credible limiting potentials for NRR over 104 C3N-supported SACs, showing a clear scaling relationship with adsorption free energies of key reaction intermediates. High-performance SACs with moieties of CrC2N2, CrC4, MnC4 and OsC4 were identified with competitive limiting potentials.