Coupling Nanoarchitectonics with S-scheme heterojunction engineering for high-efficiency semi-artificial...

Bio-photoelectrochemical systems represent an eco-friendly and sustainable power generation technology bridging natural photosynthesis with advanced energy conversion methods. However, sluggish interfacial electron transfer and insufficient biological loading severely hinder their performance. Herein, we propose a dual-optimization strategy that integrates structural nanoarchitectonics with electronic modulation via S-scheme engineering. Inspired by the natural stacked thylakoid architecture, we rationally designed a novel three-dimensional inverse opal TiO₂/WO₃ heterojunction bio-photoanode to anchor photosystem II (PSII). This IO architecture features interconnected macropores that maximize PSII loading and simultaneously amplify light harvesting via multiple scattering. Crucially, the formation of an S-scheme heterojunction-Rigorously confirmed by in situ kelvin probe force microscopy, in situ X-ray photoelectron spectroscopy under irradiation, and density functional theory calculations-Establishes an energetically favorable pathway that facilitates electron extraction from PSII while suppressing charge recombination. This synergistic design achieves superior direct electron transfer (∼34 μA·cm^-2) and mediated electron transfer (∼89 μA·cm^-2) photocurrent densities. This work furnishes a strategic blueprint for developing advanced artificial photosynthetic nanohybrids and lays the groundwork for the rational design of efficient biophotoelectric devices for solar energy conversion.