Phosphorus Regulates Coordination Number and Electronegativity of Cobalt Atomic Sites Triggering Efficient Photocatalytic Water Splitting

Optimizing the local electronic structure of a single-atom catalyst (SAC) is crucial for efficient photocatalytic hydrogen evolution reactions. This study synthesized a Co-P4/g-C3N4 heterostructure by selective phosphidation of the Co metal-organic framework/graphitic carbon nitride (Co-MOF/g-C3N4), converting the Co-O6 configuration into a highly electronegative, coordinatively unsaturated Co-P4 configuration anchored to a carbon matrix. P-doping induces strong charge redistribution, shifting the d-band center toward the Fermi level, transforming the Co sites from an electron-deficient state to an electron-rich state, and resulting in a significant reduction in the free energy barrier for HER to -0.08 eV. The Co-P4/g-C3N4 heterostructure demonstrated a HER rate of 13.51 mmol g-1 h-1, approximately 4.82-8.35 times greater than those of photocatalysts loaded with noble metals. The apparent quantum efficiency (AQE) was 28.45% at 380 nm. The synergistic effect of the low coordination number and high electronegativity metal sites significantly enhances the photocatalytic HER performance.