Activation of the WS2 Inert Plane via W‐Site Regulation Promotes the H2 Evolution Reaction of the WS2/g–C3N4 Photocatalyst.

WS2, as a potential cocatalyst to enhance the activation of H*, is usually used for H2 evolution. However, the activity of W atoms in the sandwich WS2 structure is blocked by the surface S atoms. An in situ F‐induced W‐exposure method is developed to boost the W‐site of WS2 (Wexp‐WS). Wexp‐WS is anchored on the surface of the porous g‐C3N4, and then the Wexp‐WS/g‐C3N4 photocatalyst with efficient H* activation is obtained. Particularly, the W‐exposed structure ensures the W coordination number decreases from 5.92 in WS2 to 5.15 in Wexp‐WS, which improves the H* activation ability of the W‐site and then results in an optimized W‐site ΔGH* (−0.08 kJ mol−1). Meanwhile, the II‐type heterojunction promotes the directional transfer of photogenerated electrons from g‐C3N4 to Wexp‐WS. Thus, the H2 production rate of the Wexp‐WS/g‐C3N4 photocatalyst exhibits 11.97 mmol h−1 g−1, which is 12 times higher than that of the porous g‐C3N4. [ABSTRACT FROM AUTHOR]