Precisely manipulating the local coordination of cobalt single-atom catalyst boosts selective hydrogenation of nitroarenes

Manipulating the local coordination environment holds immense potential in augmenting the catalytic performance of single-atom catalysts, which remains a great challenge. Through theoretical prediction, we find the catalytic properties of atomic Co centers towards selective hydrogenation of nitroarenes can be effectively manipulated by adjusting the coordinated number of P atoms, among which Co-N 2 P 2 configuration stands out. Accordingly, a single-atom Co 1 -N/P-C catalyst featuring Co-N 2 P 2 coordination was precisely fabricated through a sacrificial P-doped g-C 3 N 4 -template strategy. The optimal electronic structure of Co-N 2 P 2 enables favorable chemical affinities toward nitroarene and H 2, promoted heterolytic dissociation of H 2, and accelerated reaction kinetics. Consequently, the Co 1 -N/P-C catalyst exhibits outstanding catalytic activity (overall TOF of 241.5 h −1 ), selectivity (>99%), and exceptional stability towards the hydrogenation of various functionalized nitroarenes, far surpassing other coordination configurations and most reported non-precious metal catalysts. This work deepens our understanding of the relationship between coordination structure and catalytic performance, offering boosted single-atom catalysts for selective hydrogenation of nitroarenes.