Proton-Mediated ROS Amplification in Hydrazone-Linked Pillararene Microspheres for Photocatalysis
Menghao Li, Zhiqiang Yang, Hui Hui, Yan Wang, Bing Yang, Zhiquan Zhang, Ying‐Wei Yang
Abstract
Smart materials that adapt to environmental stimuli have massive technological potential. Translating well-established molecular-level responsiveness to macroscopic systems, particularly complex systems for photocatalysis, remains a significant hurdle. Herein, we introduce a new approach using a hydrazone-linked pillararene microsphere (NP5-TF-HPM) as a smart stimuli-responsive photocatalyst. NP5-TF-HPM showcases unique proton responsiveness owing to electron-rich cavities, resulting in a proton-induced structural rearrangement from the enol-imine to keto-amine form. Experiments and density functional theory calculations reveal that pillararenes in the protonated framework function as activity amplifiers. These molecules donate π-electrons from their cavities to another building unit, not only shifting the framework's conduction band to a more negative potential, which enhances its electron-donating capability, but also inducing a nonuniform charge distribution in the donor-acceptor moiety, thereby resulting in an intramolecular built-in electric field. Consequently, protonated HPM exhibits amplified photo-oxidation activity, efficiently catalyzing sulfide photo-oxidation with high conversions (up to 99%).