• • The hybrid system of alkalized and Cu-doped g-C3N4 with Chlorella achieved a 3.7-fold increase in hydrogen production compared to bare Chlorella, demonstrating the efficacy of extracellular electron supply.
• • Hydrothermal alkalization and copper ion doping of g-C3N4 expanded its light absorption range and enhanced photoresponse, optimizing the electronic structure for improved electron transfer.
• • The g-C3N4 serves as an extracellular electron source independent of PSII, providing an alternative electron pathway to hydrogenase, which is critical under nutrient stress conditions where PSII activity is inhibited.
• • This cell nanofunctionalization strategy offers a feasible route to enhance biological hydrogen production efficiency by regulating non-living components, with potential for scalable application in renewable energy.
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