CMPs as Scaffolds for Constructing Porous Catalytic Frameworks: A Built-in Heterogeneous Catalyst with High Activity and Selectivity Based on Nanoporous Metalloporphyrin Polymers

Abstract

This article describes the synthesis and functions of a porous catalytic framework based on conjugated micro- and mesoporous polymers with metalloporphyrin building blocks (FeP-CMP). FeP-CMP was newly synthesized via a Suzuki polycondensation reaction and was developed as a heterogeneous catalyst for the activation of molecular oxygen to convert sulfide to sulfoxide under ambient temperature and pressure. FeP-CMP is intriguing because the polymer skeleton itself is built from catalytic moieties and serves as built-in catalysts, bears inherent open nanometer-scale pores that are accessible for substrates, and possesses large surface areas (1270 m(2) g(-1)) that facilitate the transformation reaction. It is highly efficient with high conversion (up to 99%) and a large turnover number (TON = 97,320), is widely applicable to various sulfides covering from aromatic to alkyl and cyclic substrates, displays high selectivity (up to 99%) to form corresponding sulfoxides, and is highly chemoselective for the oxidation of a sulfide group even in the coexistence of other oxidative functionalities. Owing to the covalent linkages between catalytic sites in the frameworks, FeP-CMP can be recycled with good retention of its porous structure and allows for large-scale transformation. These unique characteristics clearly originate from the covalent porous catalytic framework structure and demonstrate the usefulness of CMPs in the exploration of built-in heterogeneous catalysts, a new potential of these materials that have thus far been reported to exhibit noteworthy gas adsorption functions.

Conjugated Microporous Polymers for Heterogeneous Catalysis

“…Asian J. 2018,13,[9][10][11][12][13][14][15][16][17][18][19] www.chemasianj.org 2018 Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim activity waso bservedw ith Ru/CMP-5d after three cycles,t he ee value decreased from 94 %t o9 0% (reaction time:2 4h). Additionally, CMP-5d supported Ir species displayedh ighera ctivity for asymmetrich ydrogenationo fq uinaldine than the homogeneousI r/BINAP system.…”

“…Asian J. 2018,13,[9][10][11][12][13][14][15][16][17][18][19] www.chemasianj.org Figure 10. Structureso fCMPs used as photocatalysts.…”

Heterogeneous catalytic properties of unprecedented μ-O-[FeTCPP]2dimers (H2TCPP = meso-tetra(4-carboxyphenyl)porphyrin): an unusual superhyperfine EPR structure

“…35,36 Thus, our proposal is using the catalyst as a structural unit. As concluded by several recent works, [37][38][39][40][41][42][43][44][45][46][47][48][49] this approach has been observed to be effective. However, the number of metalloporphyrinic compounds in which the network itself 60 plays as a catalyst is very low.…”

Conjugated Microporous Polymer‐Derived Porous Hard Carbon as High‐Rate Long‐Life Anode Materials for Lithium Ion Batteries

“…In particular, traditional synthesis methods involving the carbonization of low-vapor-pressure polymeric precursors 19,21] or natural sources [20] have their respective drawbacks, which are mostly associated with cross-linking reactions that proceed with concomitant char formation or uncontrolled vaporization during high-temperature pyrolysis. [22] Conjugated microporous polymers (CMP) have received considerable research interest because of their 3D interlinked porous structure, large Brunauer-Emmett-Teller (BET) specific surface areas, and good chemical stability [23][24][25][26][27][28][29][30][31][32][33] with regard to potential applications for the selected adsorption of organic solvents [24] and gas adsorption. [25][26][27][28][29][30][31][32][33] More interestingly, the surface areas and pore volumes of the CMP could be easily tuned by using different monomers with various molecule lengths, making them ideal candidates for preparation of porous carbon.…”

“…The pore volume, micropore area, and external surface area are 0. 29 , respectively (see the Supporting Information). Interestingly, CMP-1 and PHC-1 exhibited similar porous characters especially with regard to their pore size distribution.…”