本文要点：
虽然光催化氧化是广泛化学合成中的一类重要反应，但是制备用于广泛氧化反应的有效光催化剂仍然是一个巨大的挑战。
本文通过合理整合卟啉和三苯胺两种光致变色物质，成功构建了用于光催化氧化的三维光活性共价有机框架(COF)。
表征研究不仅显示了晶体和三维多孔框架的形成，而且揭示了其源于卟啉和三苯胺部分的有效光化学半导体性质。
电子顺磁共振测量表明，COF是产生单线态氧(1O2)和超氧自由基阴离子(O2)的有效光催化剂。
实验和理论研究都证实了烷基苯和硅烷以及硫代苯甲醚的光催化有氧氧化以及N-苯基四氢异喹啉和吲哚的交叉脱氢偶联反应在所有光催化反应中协同增强的效率，展示了其在广泛的光催化氧化反应中的有希望的潜力。
Figure 1.Schematic illustration of integrating two photoactive functionalities into one COF for triggering the generation of two types of ROS for multiple photocatalytic oxidation reactions.
Figure 2. a) Schematic illustration for the synthesis of TFPA-TAPP-COF. b) FT-IR spectra of TFPA, TAPP, and TFPA-TAPP-COF. c) 13C NMR spectrum of TFPA-TAPP-COF. d) PXRD patterns of the TFPA-TAPP-COF: experimental (black), Pawley refined (red), Bragg positions (green) and the difference between the Pawley refined and experimental patterns (blue). e) Simulated structure of TFPA-TAPP-COF in pto topological model. f) N2 sorption isotherm at 77 K and g) poresize distribution of TFPA-TAPP-COF.
Figure 3. a) UV-Vis DRS spectra of TFPA, TAPP, and TFPA-TAPP-COF. b) Kubelka-Munk-transformed reflectance spectrum, c) Mott−Schottky curves, d) calculated electronic band structure, e) transient photocurrent curve and f) time-resolved photoluminescent decay plots of TFPA-TAPP-COF.
Figure 4.Reactions of a) 5,5-dimethyl-1-pyrrole-N-oxide (DMPO) with •O2 − and b) 2,2,6,6-tetramethylpiperidine (TEMP) with of 1O2. ESR spectra after irradiation by the Xe lamp of TFPA in MeCN with c) DMPO and d) TEMP as trapping agents, TAPP in MeCN with e) DMPO and f) TEMP as trapping agents and TFPATAPP-COFin MeCN with g) DMPO and h) TEMP as trapping agents. i) Schematic illustration of radical generation.
Figure 5. Comparison of the oxidation scenarios including a) ethylbenzene oxidation, b) silane oxidation, c) thioether oxidation, and d) CDC reactions catalyzed by TFPA, TAPP and TFPA-TAPP-COF.
Figure 6. Absorption of the samples under lamp with 420 nm: a) ABDA solution, b) ABDA solution containing TFPA, c) ABDA solution containing TAPP, d) ABDA solution containing TFPA-TAPP-COF, and e) ABDA solution containing the mixture of TFPA and TAPP. f) Absorption quenching percentage of ABDA solutions in the presences of COF and its monomers along with the exposure time. The HOMO and LUMO distributions of the reactants of g) TFPA and h) TAPP, and i) constructed TFPA-TAPP-COF.
Figure 7. Proposed mechanism for the photocatalytic aerobic oxidations of alkylbenzene, silanes, and thioanisoles, as well as CDC reaction based on TFPATAPP-COF.
https://doi.org/10.1002/anie.202425668
