In this work, we open an avenue toward rational design of potential efficient catalysts for sustainable ammonia synthesis through composition engineering strategy by exploiting the synergistic effects among the active sites as exemplified by diatomic metals anchored graphdiyne via the combination of hierarchical high-throughput screening, first-principles calculations, and molecular dynamics simulations. Totally 43 highly efficient catalysts feature ultralow onset potentials (|U_onset| ≤ 0.40 V) with Rh-Hf and Rh-Ta showing negligible onset potentials of 0 and −0.04 V, respectively. Extremely high catalytic activities of Rh-Hf and Rh-Ta can be ascribed to the synergistic effects. When forming heteronuclears, the combinations of relatively weak (such as Rh) and relatively strong (such as Hf or Ta) components usually lead to the optimal strengths of adsorption Gibbs free energies of reaction intermediates. The origin can be ascribed to the mediate d-band centers of Rh-Hf and Rh-Ta, which lead to the optimal adsorption strengths of intermediates, thereby bringing the high catalytic activities. Our work provides a new and general strategy toward the architecture of highly efficient catalysts not only for electrocatalytic nitrogen reduction reaction (eNRR) but also for other important reactions. We expect that our work will boost both experimental and theoretical efforts in this direction.

An efficient preparation and local coordination environment regulation of isolated single-atom sites catalysts (ISASC) for improved activity is still challenging. Herein, we develop a solid phase thermal diffusion strategy to synthesize Mn ISASC on highly uniform nitrogen-doped carbon nanotubes by employing MnO₂ nanowires@ZIF-8 core-shell structure. Under high-temperature, the Mn species break free from core-MnO₂ lattice, which will be trapped by carbon defects derived from shell-ZIF-8 carbonization, and immobilized within carbon substrate. Furthermore, the poly-dispersed Mn sites with two nitrogen-coordinated centers can be controllably renovated into four-nitrogen-coordinated Mn sites using NH₃ treatment technology. Both experimental and computational investigations indicate that the symmetric coordinated Mn sites manifest outstanding oxygen reduction activity and superior stability in alkaline and acidic solutions. This work not only provides efficient way to regulate the coordination structure of ISASC to improve catalytic performance but also paves the way to reveal its significant promise for commercial application.