Abstract
Manipulating oriented electron flow and tailored reaction microenvironments in radial-unguided two-dimensional phosphorene remains challenging. Here, we show that Rh-decorated violet/black phosphorus heterostructures, engineered with integrative dual-electric fields from cooperative phase and fringing electric field, enable efficient vapor-fed photocatalytic hydrogen production. This dual-electric field establishes a strong intrinsic charge driving force and edge charge ordering. The vapor-fed gas-solid system minimizes interfacial diffusion barriers and solvent shielding, allowing the field to steer photoelectrons and interact with H2O molecules at the edge-located Rh active centers. Analyses reveal that the integrative dual-electric field strengthens polarization and overcomes the water dissociation barrier at the gas-solid interface. The optimized catalyst achieves a H2-generation rate of 5218.7 μmol g-1 h-1 under simulated sunlight, roughly 2.4 times conventional liquid-solid systems. This work demonstrates that synergy between integrative dual-electric fields and the gas-solid microenvironment overcome the kinetic limitations of phosphorene-based photocatalysts for efficient solar-driven hydrogen conversion.