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Non-metal-based single-atom catalysts (SACs) offer low cost, simple synthesis methods, and effective regulation for substrates. Herein, we developed a simplified pressurized gas-assisted process, and report the first non-metal single-atom phosphorus with atomic-level dispersion on unique single-crystal Mo2 C hexagonal nanosheet arrays with a (001) plane supported by carbon sheet (SAP-Mo2 C-CS). The SAP-Mo2 C-CS is structurally stable and shows exceptional electrocatalytic activity for the hydrogen evolution reaction (HER). A so-called