Chlorophyll(a)/Carbon Quantum Dot Bio-Nanocomposite Activated Nano-Structured Silicon as an Efficient Photocathode for Photoelectrochemical Water Splitting

Solar-driven water splitting is considered as a futuristic sustainable way to generate hydrogen and chemical storage of solar energy. Further, considering the technological competence, silicon is one of the potential materials for developing large-scale and cost-effective photocathodes (PCs), but it lacks efficacy and stability. Here, we show that chlorophyll­(a)/carbon quantum dots (Chl/CQDs) bio-nanocomposite (b-NC)-decorated Si-nanowires (SiNWs) as PC can surpass the reported efficiency for photoelectrochemical (PEC) hydrogen generation along with stability. The optimized heterojunction (Chl/CQDs_SiNW) significantly enhances broad-band solar absorption and protects Si surface from corrosion. Further, the appropriate band alignment enforces efficient photogenerated charge separation and possesses directional exciton transport property via the Förster resonance energy transfer (FRET) mechanism. This synergic effect demonstrates an ∼18 times increase in photocurrent density (26.36 mA/cm²) compared to pristine SiNW PC at 1.07 V vs reversible hydrogen electrode (RHE). The efficiency reaches ∼7.86%, which is comparably the highest reported for hybrid Si-based photocathodes. Hydrogen evaluation rate was measured to be ∼113 μmol/h at 0.8 V vs RHE under 1 sun illumination. With Si-process line compatibility, this new finding opens a new direction toward the development of Si-based efficient and stable PCs at a large scale for commercial applications.