Universal Sub‐Nanoreactor Strategy for Synthesis of Yolk‐Shell MoS2 Supported Single Atom Electrocatalysts toward Robust Hydrogen Evolution Reaction

Abstract The coordination structure determines the electrocatalytic performances of single atom catalysts (SACs), while it remains a challenge to precisely regulate their spatial location and coordination environment. Herein, we report a universal sub‐nanoreactor strategy for synthesis of yolk‐shell MoS 2 supported single atom electrocatalysts with dual‐anchored microenvironment of vacancy‐enriched MoS 2 and intercalation carbon toward robust hydrogen‐evolution reaction. Theoretical calculations reveal that the “E‐Lock” and “E‐Channel” are conducive to stabilize and activate metal single atoms. A group of SACs is subsequently produced with the assistance of sulfur vacancy and intercalation carbon in the yolk‐shell sub‐nanoreactor. The optimized C−Co−MoS 2 yields the lowest overpotential (η 10 =17 mV) compared with previously reported MoS 2 ‐based electrocatalysts to date, and also affords a 5–9 fold improvement in activity even comparing with those as‐prepared single‐anchored analogues. Theoretical results and in situ characterizations unveil its active center and durability. This work provides a universal pathway to design efficient catalysts for electro‐refinery.