Despite advances of single-atom catalysts (SACs) in sodium–sulfur (Na–S) batteries, their symmetric coordination geometry (e.g., M–N₄) fundamentally restricts orbital-level modulation of sulfur redox kinetics. Herein, we demonstrate that hetero-diatomic Co–Y sites with Co–N₄–Y–N₄ coordination on N-doped carbon (Co–Y/NC) break the M–N₄ symmetry constraint through d–d orbital hybridization, which is confirmed by an implementation of advanced characterizations, including the high-angle annular dark-field scanning transmission electron microscopy and x-ray absorption fine structure spectroscopy. In practical operation, the Co–Y/NC@S cathode with 61% sulfur mass fraction delivers a superior capacity (1,109 mAh/g) at 0.2 A/g, outperforming that of Co or Y SAC and further setting a new benchmark of diatomic catalysts for Na–S battery systems. Furthermore, the theoretical calculations show a hybridization-induced d-band splitting energy (ΔE = 0.5 eV), which induces electron-deficient Y sites for polysulfide adsorption (Na₂S₆) and electron-rich Co sites for S–S scission (barrier energy = 0.28 eV) via the d-p orbital hybridization of an asymmetric configuration. Our work establishes a strategy based on rare-earth-transition metal orbital hybridization to design asymmetric active sites for promoting multielectron sulfur redox reactions.

The fabrication of efficient and stable catalysts to accelerate the kinetics of the hydrogen evolution reaction (HER) is a crucial step in the development of sustainable energy production. The structural design of Pt-based catalysts with efficient atom utilization remains a pivotal factor in the continued advancement of HER catalysts. In this work, we synthesized phosphorylated Mo-based particles embedded in P-doped carbon materials for the optimized loading of platinum nanoparticles (Pt/Mo-P@C). Theoretical results indicate that the catalytic efficacy of the materials can be enhanced by altering the electronic structure of Pt nanoparticles through the precise formation of Pt–Mo bond and multiple heterostructures. The catalysts exhibited exceptional mass activity after low-temperature reduction, achieving a current density of 100 mA·cm⁻² at 54.4 mV, which is lower than that of the commercial Pt/C catalyst. Furthermore, the mass activity of the main catalyst was 6.7 times greater than that of the commercial Pt/C catalyst at an overpotential of 50 mV.