Reconstruction of D‐Π‐A Polymer Accelerating Photocatalytic Degradation of BPA and Production of H₂O₂

Abstract

Advanced oxidation processes (AOPs) using hydroxyl radicals (•OH) as oxidizing agents are a promising technology. Herein, a feasible strategy is developed to initially construct carbazole‐based D‐π‐A type conjugated polymer (PBNCZ) via the oxidative coupling. Additionally, introducing ─COO− through Cyano hydrolysis extends its conjugated structure and improves the energy band structure, which greatly facilitates the generation of •OH as well as the enrichment of pollutants. Detailed experiments and theoretical calculations have proved that the introduction of ─COO− enhances the adsorption of O2 and bisphenol A (BPA), optimizing the reaction path of •OH. Thus, it completely decomposes 10 ppm of BPA within just 10 min, exceeding all previously organic photocatalysts. Meanwhile, the efficiency of photocatalytic H2O2 production by PBNCZ‐COO− reaches 1719.03 µmol h−1 g−1 under visible light. This multifunctional material with high adsorption capacity, photodegradation efficiency, and photocatalytic H2O2 production activity provides a solid foundation for the preparation of organic photocatalysts.

Leveraging phenazine and dihydrophenazine redox dynamics in conjugated microporous polymers for high-efficiency overall photosynthesis of hydrogen peroxide

“…2d). 5,11,21–34 Meanwhile, TPE-PNZ achieved an impressive SCC efficiency of 0.58%, surpassing most CMP-based photocatalysts reported to date (Table S1†). In contrast, TPE-AC, designed as a comparative benchmark by replacing phenothiazine with anthracene in TPE-PNZ, only exhibited a much lower H 2 O 2 production rate of 2183 μmol g −1 h −1 .…”

Donor–Acceptor-Conjugated Porous Polymer for Photopromoted N–H Formylation of Secondary Amines: Efficient In Situ N-Heterocyclic Carbene Catalysis in Radical Manner

“…Conjugated porous polymers (CPPs), − including covalent organic frameworks (COFs), − crystalline covalent triazine frameworks, − or conjugated microporous polymers, − have emerged as promising heterogeneous photocatalysts due to large conjugated system, tailor-made functions, adjustable energy level, and remarkable stability. − The predesign strategy by selecting well-arranged electron donor–acceptor (D–A) building blocks is an ideal way for precisely adjusting the photocatalytic performance of CPPs at the molecular level. ,,,, The push–pull effect of D–A pairs can effectively enhance the light absorption range and improve the transport and separation efficiency of photogenerated carriers (e – –h + ). ,,,, Facts proved that the photogenerated electrons or holes showed effectively reductive or oxidative activities in organic conversion reactions through a radical mechanism, such as oxidative amine coupling, reductive dehalogenation reaction, trifluoromethylated ketones, and radical polymerization. − Wang and co-workers introduced pyrene and benzothiadiazole cores into conjugated D–A Py-BSZ-COF COFs, which showed good photocatalytic activity for oxidative amine coupling because of its improved charge separation. Under visible light irradiation, photogenerated h + oxidized amine to give amine radical anion and ROS O 2 · – to oxidize amine radical anion to form the key imine intermediate .…”

Advancements in controlling COFs structure for enhanced crystallization properties and self-generated photocatalytic hydrogen peroxide

“…, TiO 2 , ZnO), 4,5 carbon-based materials ( e.g. , graphene, polymerized carbon nitride), 6–8 conjugated polymers 9 and metal–organic frameworks (MOFs). 10,11 In contrast to inorganic semiconductors, organic polymers consist of elements ( e.g.…”