Phosphorene Dominated Integrative Dual-Electric Field Guiding Charge Flow and Active Centers for Vapor-fed Photocatalytic Hydrogen Evolution

Manipulating the oriented electron flow and tailored reaction microenvironments in radial-unguided 2D phosphorene remains challenging. Herein, Rh-decorated 2D/2D violet/black phosphorus (VP/BP-Rh) is engineered using integrative dual-electric fields (DEF) generated through cooperative phase electric field (PEF) and fringing electric field (FEF) to guide oriented charge flow and accurate catalytic centers. While the DEF establishes a powerful intrinsic charge driving force and edge charge ordering, its full potential is optimally unleashed in a vapor-fed gas–solid system. This unique system minimizes interfacial diffusion barriers and solvent shielding effects, allowing the DEF to steer photoelectrons and synergize with H₂O molecules exclusively and efficiently at the edge-located Rh active centers. Experimental and theoretical analyses reveal that the integrative DEF not only strengthens polarization but also ingeniously overcomes the water dissociation barrier at the gas-solid interfaces, significantly reducing the Gibbs free energy barrier for the vapor-to-hydrogen conversion. The resulting VP/BP-Rh achieves a record H₂-generation rate of 5218.7 µmol g⁻¹ h⁻¹ under simulated sunlight, marking ca. 2.4-fold improvement over conventional liquid–solid systems. This study highlights the key role of synergy between the integrative DEF and the gas–solid reaction microenvironment in solving the kinetic bottlenecks of 2D phosphorene-based photocatalysts for efficient solar-driven vapor-to-hydrogen conversion.