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.