Intracellular Gold Nanocluster/Organic Semiconductor Heterostructure for Enhancing Photosynthesis

Abstract Photosynthetic microorganisms, which rely on light‐driven electron transfer, store solar energy in self‐energy carriers and convert it into bioenergy. Although these microorganisms can operate light‐induced charge separation with nearly 100 % quantum efficiency, their practical applications are inherently limited by the photosynthetic energy conversion efficiency. Artificial semiconductors can induce an electronic response to photoexcitation, providing additional excited electrons for natural photosynthesis to improve solar conversion efficiency. However, challenges remain in importing exogenous electrons across cell membranes. In this work, we have developed an engineered gold nanocluster/organic semiconductor heterostructure (AuNCs@OFTF) to couple the intracellular electron transport chain of living cyanobacteria. AuNCs@OFTF exhibits a prolonged excited state lifetime and effective charge separation. The internalized AuNCs@OFTF permits its photogenerated electrons to participate in the downstream of photosystem II and construct an oriented electronic highway, which enables a five‐fold increase in photocurrent in living cyanobacteria. Moreover, the binding events of AuNCs@OFTF established an abiotic‐biotic electronic interface at the thylakoid membrane to enhance electron flux and finally furnished nicotinamide adenine dinucleotide phosphate. Thus, AuNCs@OFTF can be exploited to spatiotemporally manipulate and enhance the solar conversion of living cyanobacteria in cells, providing an extended nanotechnology for re‐engineering photosynthetic pathways.