Mechanistic Insights into Electrocatalytic Nitrogen Reduction Reaction on the Pd‐W Heteronuclear Diatom Supported on C ₂ N Monolayer: Role of H Pre‐Adsorption

The electrocatalytic N2 reduction reaction (eNRR) is a potential alternative to the Haber–Bosch process for ammonia (NH3) production. Tremendous efforts have been made in eNRR catalyst research promote practical application of eNRR. In this work, by means density functional theory calculations and computational hydrogen electrode model, we evaluated performance 30 single metal atoms supported on C2N monolayer ([email protected]2N), designed new thermodynamically stable Pd-W hetero-metal diatomic protected]2N). We found that [email protected]2N prefers adsorb H over N2, then, pre-generated hydrogen-terminated selectively adsorbing behaves as actual functioning “catalyst” catalyze process, exhibiting excellent with low overpotential (0.31 V), an ultra-low NH3 desorption free energy (0.05 eV), high selectivity toward evolution (HER). Moreover, shows superior its monomer protected]2N) homonuclear diatom (W2@C2N) counterparts. revealed mechanism indicates preferential adsorption active site may not always hamper especially heteronuclear catalysts. This work encourages deeper exploration competition HER surfaces.