A Plasmonic Biohybrid With an Intracellular Biogenic S‐Scheme Nano‐Heterojunction Toward Wide‐Spectrum Solar‐To‐Chemical Conversion Beyond Nature

ABSTRACT

Photosynthetic biohybrid systems (PBSs), which integrate microorganisms with inorganic semiconductors, offer a sustainable platform for solar‐to‐chemical conversion. However, most PBSs are hindered by the limited light absorption and inefficient charge separation of semiconductor. Herein, a biohybrid system featuring an intracellular in‐situ synthesized CuS/CdS plasmonic nano‐heterojunction (CuS/CdS@yeast) is developed for wide spectrum–driven photocatalysis. Regulated by the organism, biogenic CuS/CdS nano‐heterojunctions achieve efficient electron‐hole separation by forming an S‐scheme heterostructure, driven by a substantial electrostatic potential difference. Furthermore, in‐situ intracellular synthesis strategy enables a coupling between yeast cells and the nano‐heterojunction, allowing photoelectrons of the semiconductor to directly participate in bioenergetic pathways, resulting in a significant elevation of intracellular reduction equivalents (nicotinamide adenine dinucleotide [NADH]) and available energy (adenine nucleoside triphosphate [ATP]), which are essential to sustain microbial biosynthesis. By synergizing a heterojunction with biological components, this biohybrid achieves superior photocatalytic reduction under full‐spectrum illumination. Notably, it delivers an ammonia synthesis rate of 93.94 µmol·g ⁻¹ ·h ⁻¹ (without sacrificial agents) and a hydrogen production of 3803.47 µmol·g ⁻¹ , representing ∼13‐fold and ∼27‐fold enhancements over pure cells. This work presents novel insights into the rational design of efficient biohybrid systems for sustainable biomanufacturing.