Regulating the p orbital structure of nonmetal active sites is a potential strategy to optimize hydrogen adsorption. However, existing modification ideas primarily focus on the total energy of the p orbitals, while overlooking the crucial spatial information of the multiple projected px, py, and pz orbitals, causing a random and nondirectional orbital modification. Herein, we propose a spatial orbital-selective modulation engineering to realize precise and efficient optimization of H adsorption on a core-shell NiSe@ReS2+ x cocatalyst. Theoretical calculations find that the H adsorption intrinsically originates from the selective hybridization between individual S pz and H 1s orbitals (pz-s), which unlocks a most direct approach to optimize H adsorption. Based on this, we demonstrate that H adsorption on S sites is directionally weakened by selectively charging spatial S pz from NiSe to produce electron-rich pz δ- orbitals. This process increases the projected antibonding-orbital occupancy, weakens the spatial pz-s hybridization, and lowers the H2-formation energy barrier of ReS2+ x, ultimately achieving an improved H2-evolution activity. This work offers spatial orbital-level insights into precisely designing effective catalysts for artificial photosynthesis.
Gao et al. (2026) studied this question.