Enhanced Charge Transfer via S‐Scheme Heterojunction Interface Engineering of Supramolecular SubPc–Br/UiO‐66 Arrays for Efficient Photocatalytic Oxidation

Abstract Constructing heterojunction of supramolecular arrays self‐assembled on metal–organic frameworks (MOFs) with elaborate charge transfer mechanisms is a promising strategy for the photocatalytic oxidation of organic pollutants. Herein, H₁₂SubPcB–Br (SubPc–Br) and UiO‐66 are used to obtain the step‐scheme (S‐scheme) heterojunction SubPc–Br/UiO‐66 for the first time, which is then applied in the photocatalytic oxidation of minocycline. Atomic‐level B–O–Zr charge‐transfer channels and van der Waals force connections synergistically accelerated the charge transfer at the interface of the SubPc–Br/UiO‐66 heterojunction, while the establishment of the B–O–Zr bonds also led to the directional transfer of charge from SubPc–Br to UiO‐66. The synergy is the key to improving the photocatalytic activity and stability of SubPc–Br/UiO‐66, which is also verified by various characterization methods and theoretical calculations. The minocycline degradation efficiency of supramolecular SubPc–Br/UiO‐66 arrays reach 90.9% within 30 min under visible light irradiation. The molecular dynamics simulations indicate that B–O–Zr bonds and van der Waals force contribute significantly to the stability of the SubPc–Br/UiO‐66 heterojunction. This work reveals an approach for the rational design of semiconducting MOF‐based heterojunctions with improved properties.