Orbital Hybridization in Dual‐Atom Embedded Siloxene Accelerate Sulfur Redox Reactions for Lithium–Sulfur Batteries

Abstract Promoting the sulfur reduction reaction (SRR) is crucial for improving the working efficiency of the lithium–sulfur (Li–S) battery. Inheriting the advantages of single‐atom catalysts (SACs), dual‐atom catalysts (DACs) have emerged as promising candidates with more flexible catalytic sites and better catalytic effect. Siloxene, a new encouraging polar 2D material for sulfur cathode, can effectively stabilize bimetallic atoms during electrochemical cycling. Herein, a series of transition metal dual‐atom embedded siloxenes (TM 1 TM 2 ‐DA) are constructed as the cathode in Li–S batteries via First‐principal calculations. The superior catalytic performance of sulfur reduction and Li 2 S oxidation reaction of FeNi‐DA is screened as the optimal catalysis, in addition to prominent electronic conductivity and favorable adsorption energies to polysulfides. The redistribution of d ‐electron density caused by Fe–Ni orbital hybridization is the key to improve the catalytic activity. Furthermore, easily‐obtained descriptors (D c and L s ) are selected for efficiently screening TM 1 TM 2 ‐DA catalysts with low SRR barriers. This work sheds light on DACs activation mechanisms and provides an efficient pathway to design cathode in Li–S batteries.