Binary Hybridization Strategy toward Stable Porphyrinic Zr‐MOF Encapsulated Perovskites as High‐Performance Heterogeneous Photocatalysts for Red to NIR Light‐Induced PET‐RAFT Polymerization

Abstract

Stable binary nanohybrids based on all-inorganic halide perovskite encapsulated in porphyrinic Zr-MOF (PCN-222) are constructed for photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. The synergistic effect of perovskite and PCN-222 endows the photocatalyst with high-efficiency photogenic charge carrier separation and light absorption property. CsPbI 3 @PCN-222 (20%) is finally screened out as the oxygen and solvent-resistant photocatalyst for highly efficient photocontrolled polymerization of conjugated and unconjugated monomers under red to near infrared (NIR) light with high monomer conversion and narrow molecular weight distribution well-defined polymers (Đ < 1.20). Controllable polymers and ultrahigh molecular weight polymers (up to 1730000 g mol −1 ) are successfully obtained by chain extension and block copolymerization of various monomers. The constructed photocatalysts easily achieve excellent light and temporal control, and even show high MMA conversion with NIR light under a thick barrier.

Construction of membrane reactors coupled with conjugated network hollow microspheres for cascade production of block copolymers

“…While homogeneous catalysts are undoubtedly useful for the majority of photopolymerizations, heterogeneous catalysts are still favorable on an industrial scale as they offer distinct advantages including straightforward separation and effective recovery. [29][30][31][32][33][34][35] Based on the input mode of heterogeneous catalysts, membrane reactors can be categorized into suspended-catalysts-based membrane reactors (SCBMR) and catalytic active membrane reactors (CAMR). In the CAMR system, the membrane performs as a lter, while simultaneously serving as a support for active catalyst immobilization.…”

Heterogeneous Photocatalysts for Light‐Mediated Reversible Deactivation Radical Polymerization

“…demonstrated the utility of Zr‐based (PCN‐222) MOFs to house CsPbI 3 perovskite photocatalysts. This PC was successfully used for PET‐RAFT polymerization of methyl methacrylate under sunlight (wavelengths of light ranging from 460–850 nm) [286] . In addition, the PCs were able to polymerize styrene under red light up to ~85 % conversion in 4 hours.…”

Structure and Morphology Engineering of Hollow Conjugated Microporous Photocatalysts to Boost Photo-Controlled Polymerization at Near-Infrared Wavelengths

“…Since Ciamician put forward the concept of photochemistry, harnessing the inexhaustible solar energy as an efficient and low-energy consumption strategy has revolutionized organic synthesis. − Over the past decade, photoinduced electron/energy transfer–reversible addition–fragmentation chain transfer (PET–RAFT) polymerization has significantly altered the thermodynamic equilibrium of the polymerization and enabled the polymerization to proceed under a wide variety of light wavelengths, which can effectively suppress unfavorable side reactions. − A visible spectrum between 400 and 700 nm accounts for only 44% of the total solar energy, while long wavelengths above 700 nm (near infrared, NIR) account for more than 50%. − In addition, the strong absorption of light at the wavelength greater than 950 nm by water and lipids constricts the transmission of optical information, and therefore the NIR light between 650 and 900 nm, the so-called “therapeutic window”, has aroused widespread interest in photopolymerization. − Due to its high penetration ability, the development of a NIR-light-driven aqueous PET–RAFT system will not only contribute to the sustainability of energy supply but will also have a significant environmental and biological benefit. Some aqueous NIR light-mediated RAFT polymerizations have been trialed with great successes, but sluggish polymerization kinetics and catalyst contamination place restrictions on their broader applications. − …”