Mimicking Thylakoid Membrane with Chlorophyll/TiO₂/Lipid Co-Assembly for Light-Harvesting and Oxygen Releasing

There is a growing interest in the design and construction of artificial photosythetic materials for solar energy utilization and conversion. Inspired by the structure of thylakoid membrane, we present here a hybrid construct for light-harvesting and oxygen releasing. Our design conjugates chlorophyll to TiO₂ in a native-like membrane environment. The natural bilayer structure of lipids is utilized to localize the amphiphilic chlorophyll a and hydrophobic tetrabutyl titanate TBOT in the liposomal membrane during hydration process. The coassembled structure, which mimics the essential organization of the thylakoid membrane, is characterized using a combination of field emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectrometer (EDS), Ramam spectra, pressure (π)-area (Α) isotherms, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) analysis. Our results demonstrate successful insertation of chlorophyll a in the membrane and confirm the in situ formation of TiO₂ nanoshell confined at the lipid bilayer/water interface. We further show that the hybrid liposomes exhibit unambiguous photoactivity in visible light-harvesting and oxygen release, likely resulting from a larger specific surface area of the TiO₂ shell, an efficient interfacial conjugation of the chlorophyll molecules with the thin TiO₂ layer. The density functional theory (DFT) calculations were in accordance with the eletron injection processes.We expect that the present work will open a new insight into interfacial recombination between light-harvesting pigments and their sensitized photocatalysis, and develop a new kind of artificial photosynthetic materials with zero-cost of environmental degradation and high efficiency for the photocatalytic O₂ production.