Molecular Engineering Spatially Separated Redox Centers Enable Efficient Piezo‐Photocatalytic H2O2 Production

Piezo‐photocatalytic production of hydrogen peroxide (H2O2) from water and air is promising but still challenging as insufficient reaction active sites and low reaction efficiency. We have ingeniously applied molecular engineering methods to design an anthraquinone molecularly grafted metal‐organic framework piezo‐photocatalyst (denoted as UiO‐66‐AQ) for H2O2 generation from water and air. The catalyst achieves a peak H2O2 yield of 7872.4 μM g‐1 h‐1, primarily owing to the presence of spatially separated redox sites that enable simultaneously two‐step single‐electron water oxidation and two‐electron oxygen reduction reactions. Notably, experimental and computational simulations confirm rapid carrier separation under the ligand‐to‐chain charge transfer mode. Electrons transfer to the AQ part and rapidly form internal peroxides for spontaneous oxygen reduction reaction while holes direct to the UiO‐66 ligand for the water oxidation reaction. Additionally, a continuous flow tubular reactor with catalytic membranes made of UiO‐66‐AQ affords 96% removal of organic dyes through the self‐Fenton process under visible light and vibrating water flow, confirming the significant potential of the catalyst for practical applications. This work deepens the understanding of directional carrier migration at piezo‐photocatalytic spatial separation sites, opening new pathways for environmentally friendly and efficient H2O2 synthesis.