Low efficient transfer of photogenerated charge carriers to redox sites along with high surface reaction barrier is a bottleneck problem of photocatalytic H2O overall splitting. Here, in the absence of cocatalysts, H2O overall splitting has been achieved by single-atomic S vacancy hexagonal CdS with a spin polarization electric field (PEF). Theoretical and experimental results confirm that single-atomic S vacancy-induced spin PEF with opposite direction to the Coulomb field accelerates charge carrier transport dynamics from the bulk phase to surface-redox sites. By systematically tuning the spin PEF intensity with single-atomic S vacancy content, common pristine CdS is converted to a photocatalyst that can efficiently complete H2O overall splitting by releasing a great number of H2 bubbles under natural solar light. This work solves the bottleneck of solar energy conversion in essence by single atom vacancy engineering, which will promote significant photocatalytic performance enhancement for commercialization.

A g-C3N4 allotrope, a curved leaf-like graphitic C2N3 (g-C2N3) with an intrinsic spontaneous polarization electric field (ISPEF), has been constructed for efficient solar energy conversion into H2 energy via photocatalytic H2O splitting. The curved leaf-like π-delocalization g-C2N3 was composed of aromatic azide pentagons and normal triazine hexagons obtained by cycloaddition between −CN groups from dicyandiamide polymerization and azide from the heat-treated polypyrrole fibers. Under light irradiation (λ > 420 nm), photo-generated charges are driven to separate efficiently and transfer from bulk to active sites of the surface under ISPEF that is opposite to the Coulomb field. Consequently, without any cocatalyst, g-C3N4 allotrope demonstrates a very high H2-production activity of 14.9 mmol g–1 h–1 accompanied by a lot of H2 bubbles, which is 2.6 times of g-C3N4 loading with Pt. In comparison with the reported metal-free photocatalysts or those supported with noble metals, g-C3N4 allotrope (i.e., leaf-like g-C2N3) is confirmed to be the best metal-free photocatalyst for H2O splitting into H2 fuel so far. The contructed leaf-like g-C2N3 with SPEF supplies a suitable platform for solar energy conversion into H2 fuel, which actively contributes to clean energy production.

Low‐energy facets on CdS allomorph junctions with optimal phase ratio are designed to boost charge directional transfer for photocatalytic H2 fuel evolution. Fermi energy level difference between low‐energy facets as driving force promotes electrons directional transfer to hexagonal CdS(102) facet and holes to cubic CdS(111) facet. The optimal allomorphs CdS presents superior photocatalytic H2 evolution rate of 32.95 mmol g−1 h−1 with release in a large amount of visible H2 bubbles, which is much higher than single‐phase CdS with high‐energy facets and even supports noble metal photocatalysts. This scientific perspective on low‐energy facets of allomorph junctions with optimal phase ratio breaks the long‐held view of pursuing high‐energy crystal surfaces, which will break the understanding on surface structure crystal facet engineering of photocatalytic materials.

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