Non‐Metal Single‐Phosphorus‐Atom Catalysis of Hydrogen Evolution

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 Mo2C hexagonal nanosheet arrays with a (001) plane supported by carbon sheet (SAP‐Mo2C‐CS). The SAP‐Mo2C‐CS is structurally stable and shows exceptional electrocatalytic activity for the hydrogen evolution reaction (HER). A so‐called high‐active “window” based on the active sites of P atoms and their adjacent Mo atoms gives a ΔGH*close to zero for hydrogen evolution, which is the most ideal ΔGH*reported so far. Meanwhile, the moderate d‐band center value of SAP‐Mo2C‐CS can be also used as an ideal standard value to evaluate the HER performance in non‐metal‐based SACs.