Reversing the Nucleophilicity of Active Sites in CoP2 Enables Exceptional Hydrogen Evolution Catalysis

Precisely constructing the local configurations of active sites to achieve on-demand catalytic functions is highly critical yet challenging. Herein, an anion-deficient strategy to precisely capture Ru single atoms on the anion vacancies of CoP2 (Ru-SA/Pv-CoP2) is developed. Refined structural characterizations reveal that the Ru single atoms preferably bind to the anion vacancy sites and consequently build a superior catalytic surface with neighboring Co-P and Co-Ru coordination states for the hydrogen evolution reaction (HER) catalysis. The prepared Ru-SA/Pv-CoP2 nanowires exhibit an unprecedented overpotential of 17 mV at 10 mA cm(geo)(-2), and the corresponding mass activity is 52.2 times higher than the benchmark Pt/C catalyst at the overpotential of 50 mV. Theoretical analysis illustrates that the introduced Ru-SAs can reverse electrons state distribution (from nucleophilic P sites to electrophilic Ru sites) and boost the activation of water molecules and hydrogen production. More importantly, such a construction strategy is also applicable for Pt single atom coupling, suggesting its generality in building catalytic sites. The capability to precisely construct active sites offers a powerful platform to manipulate the catalytic performance of HER catalysts and beyond.