School of Materials Science & Engineering, Shaanxi Normal University, Xi'an 710062, China.
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, Shaanxi Normal University, Xi'an 710119, China.
ACS Appl Mater Interfaces. 2021 Mar 10;13(9):11461-11469. doi: 10.1021/acsami.0c21662. Epub 2021 Feb 26.
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 TiO in a native-like membrane environment. The natural bilayer structure of lipids is utilized to localize the amphiphilic chlorophyll 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 in the membrane and confirm the in situ formation of TiO 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 TiO shell, an efficient interfacial conjugation of the chlorophyll molecules with the thin TiO 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 O production.
人们对于设计和构建用于太阳能利用和转化的人工光合作用材料越来越感兴趣。受类囊体膜结构的启发，我们在这里提出了一种用于光捕获和氧气释放的混合结构。我们的设计将叶绿素与 TiO 在类似于天然的膜环境中进行共轭。利用脂质的天然双层结构，在水合过程中将两亲性叶绿素和疏水性四丁基钛酸盐 TBOT 定位在脂质体膜中。通过场发射扫描电子显微镜（SEM）、透射电子显微镜（TEM）、能量色散 X 射线光谱仪（EDS）、拉曼光谱、压力（π）-面积（A）等温线、循环伏安法（CV）和电化学阻抗谱（EIS）分析，对模拟类囊体膜基本组织的共组装结构进行了表征。我们的结果表明，叶绿素成功插入膜中，并证实了 TiO 纳米壳在脂质双层/水界面处的原位形成。我们进一步表明，混合脂质体在可见光捕获和氧气释放中表现出明确的光活性，这可能是由于 TiO 壳的更大比表面积和叶绿素分子与薄 TiO 层之间的有效界面共轭。密度泛函理论（DFT）计算与电子注入过程一致。我们期望本工作将为光捕获颜料与其敏化光催化之间的界面复合提供新的见解，并开发出一种新型的人工光合作用材料，具有零环境降解成本和高效的光催化 O 生产。
