Phosphorene dominated integrative dual-electric field guiding charge flow for vapor-fed photocatalytic hydrogen evolution

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. Integrative dual-electric fields in Rh-decorated phosphorene heterostructures enable directional charge transfer for efficient vapor-fed hydrogen production, overcoming kinetic barriers of two-dimensional phosphorene in solar-driven water splitting.