In situ construction of phenanthroline-based cationic radical porous hybrid polymers for metal-free heterogeneous catalysis
- 17 February 2021
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of Materials Chemistry A
- Vol. 9 (12), 7556-7565
- https://doi.org/10.1039/d0ta12018a
Abstract
Rational design of multifunctional radical porous polymers with redox activity for targeted metal-free heterogeneous catalysis is an important research topic. In this work, we reported a new class of phenanthroline-based cationic radical porous hybrid polymers (Phen˙+-PHPs), which were constructed from the Heck reaction between a newly designed dibromo-substituted phenanthroline ionic monomer (iDBPhen) and a rigid building block, octavinylsilsesquioxane (VPOSS). For the first time, the stable phenanthroline-based radical cation was unexpectedly discovered in these polyhedral oligomeric silsesquioxane (POSS)-based porous hybrid polymers, probably undergoing in situ reduction of the dicationic monomer iDBPhen during the alkaline reagent K2CO3-involved Heck reaction. The radical characters of the typical porous polymers Phen˙+-PHP-2 and Phen˙+-PHP-2Br were confirmed from the electron paramagnetic resonance (EPR) spectra and X-ray photoelectron spectra (XPS). The chemical structures and porous geometry were fully characterized by a series of advanced technologies. Surprisingly, the metal-free cationic radical polymer Phen˙+-PHP-2 exhibited high heterogeneous catalytic efficiency in the H2O2-mediated selective oxidation of various sulfides to sulfoxides with high yields under mild conditions, owing to the electron-accepting and redox ability of Phen-based dications and radical cations. Moreover, the extended sample Phen˙+-PHP-2Br prepared by post-treatment of Phen˙+-PHP-2 with aqueous HBr was also employed as a metal-free efficient heterogeneous catalyst in the conversion of CO2 with epoxides into cyclic carbonates under atmospheric pressure and low temperatures. The remarkable catalytic performance in CO2 conversion should be assigned to the synergistic catalysis of POSS-derived Si–OH groups and nucleophilic Br− anions and N active atom-involved Phen cationic radical moieties within Phen˙+-PHP-2Br. These two catalysts can be facilely recovered and reused, also with stable recyclability in the above catalytic reaction systems, achieving the heterogeneous catalytic demands for multipurpose reactions.Funding Information
- National Natural Science Foundation of China (21603089, 21706106, 21503098)
- Natural Science Foundation of Jiangsu Province (BK20160209)
- Graduate Research and Innovation Projects of Jiangsu Province (KYCX20_2357, KYCX20_2354)
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