Lead Halide Perovskite Nanocrystals as Photocatalysts for PET-RAFT Polymerization under Visible and Near-Infrared Irradiation

Abstract

A key challenge of harvesting solar energy for chemical transformations is the scarcity of photocatalysts with broad activation wavelength and easily tunable band structures. Here, we introduce lead halide perovskite (CsPbBr 3 ) nanocrystals as band-edge-tunable photocatalysts for efficient photoinduced electron/energy transfer−reversible addition−fragmentation chain transfer (PET-RAFT) polymerization. PET-RAFT polymerization of various functional monomers is successfully conducted using a broad range of irradiation sources ranging from blue to red light (460 to 635 nm), resulting in polymer products with narrow dispersity (Đ = 1.02−1.13) and high degree of chain-end fidelity. Furthermore, the giant two-photon absorption cross-section of CsPbBr 3 enables activation with a light source in the near-infrared region (laser pulses centered at 800 nm) for the PET-RAFT process.

Porphyrinic Zirconium Metal–Organic Frameworks (MOFs) as Heterogeneous Photocatalysts for PET‐RAFT Polymerization and Stereolithography

“…Ar ange of induction periods ranging from 5min (MOF-525 (Zn)) to 50 min (PCN-224 (Zn)) were investigated (Figure 2g). Thereafter, the polymerization kinetics progressed linearly,w here K app conformed to the order established above (SI,Table S5,(9)(10)(11)(12). Polymerizations in the presence of oxygen maintained living characteristics with linear evolution of M n versus conversion in combination with ad ecrease in the dispersity with increasing conversion (Figure 2h,i and SI, Figure S8).…”

“…[5] Such environmental and economic benefits become more attractive at industrial scales.Akey strategy in implementing heterogeneous catalysis for visible light mediated photoRDRP has been the immobilization of existing molecular photocatalysts onto heterogeneous supports. [6] In addition to this approach, heterogenous catalysis has introduced an exciting diversity of modified inorganic species capable of mediating PET-RAFT, such as plasmonic Ag 3 PO 4 , [7] semiconducting g-C 3 N 4 [8] or Bi 2 O 3 , [9] perovskite CsPbBr 3 , [10] carbon dots, [11] quantum dots [12] and others. [13] Some semiconductor nanoparticles (ZnO,T iO 2 and a-F 2 O 3 )h ave also been reported for controlling photoATRP.…”

Porphyrinic Zirconium Metal–Organic Frameworks (MOFs) as Heterogeneous Photocatalysts for PET‐RAFT Polymerization and Stereolithography

“…[5] Such environmental and economic benefits become more attractive at industrial scales.Akey strategy in implementing heterogeneous catalysis for visible light mediated photoRDRP has been the immobilization of existing molecular photocatalysts onto heterogeneous supports. [6] In addition to this approach, heterogenous catalysis has introduced an exciting diversity of modified inorganic species capable of mediating PET-RAFT, such as plasmonic Ag 3 PO 4 , [7] semiconducting g-C 3 N 4 [8] or Bi 2 O 3 , [9] perovskite CsPbBr 3 , [10] carbon dots, [11] quantum dots [12] and others. [13] Some semiconductor nanoparticles (ZnO,T iO 2 and a-F 2 O 3 )h ave also been reported for controlling photoATRP.…”

New Light in Polymer Science: Photoinduced Reversible Addition-Fragmentation Chain Transfer Polymerization (PET-RAFT) as Innovative Strategy for the Synthesis of Advanced Materials

“…The photoredox catalysts herein described are just a part of the wide classes of PCs suitable for PET-RAFT polymerization. Less common photocatalysts that have been used for PET-RAFT purposes are Perovskite nanocrystals (CsPbBr 3 ) [ 40 ], CdSe quantum dots (QDs) [ 41 , 42 ], tertiary amines (tris(2-(dimethylamino) ethyl)amine, N , N , N ′, N ′′, N ′′-pentamethyldiethylenetriamine, and triethylamine) [ 43 ], and graphitic carbon nitride [ 44 ]. In Table 1 the main advantages and disadvantages of the most used catalysts are reported.…”