Photocatalytic polymer nanomaterials for the production of high value compounds

Abstract

Nanotechnology has provided a platform for producing new photocatalytic materials, where the reduction in length scales has been used to amplify the efficiency of these light active materials. The progression...

Tunable Photocatalytic Selectivity by Altering the Active Center Microenvironment of an Organic Polymer Photocatalyst

“…Over the past decade, photocatalysis has proven to be a reliable and valuable synthetic tool, with numerous reported examples of photocatalytic variants for classical catalytic reactions. − Through harnessing of visible light, photocatalysis facilitates a large array of different chemical reactions . Additionally, changes within the photocatalysts’ molecular structure allow enhanced control over the desired reaction through adjustable physicochemical properties, such as redox potential and lifetime. − Embedding photocatalysts into macro- or supramolecular structures offers additional opportunities for tunability through morphological control, therefore enabling photocatalyst compartmentalization and enhanced substrate accessability. − Homogeneous, nanoscale distributions of photocatalysts within polymersomes, micelles, nanoparticles, and on surfaces were reported, but the desired implementation of selectivity concepts into these structures is still a subject of on-going research. ,, …”

“…23−26 Homogeneous, nanoscale distributions of photocatalysts within polymersomes, 25 micelles, 26 nanoparticles, 27 and on surfaces 28 were reported, but the desired implementation of selectivity concepts into these structures is still a subject of on-going research. 23,24,29 Its versatility has already been demonstrated in a variety of chemical reactions such as water splitting, 30,31 CO 2 reduction, 32,33 organic pollutant degradation, 34 C−C coupling reactions, 35−37 C�C bond cleavage, 38−40 metal reduction, 41 oxidative coupling of amines, 42 trifluoromethylation of arenes, 43 oxidation of sulfides, 42 free radical polymerizations, 44−46 dehalogenation of halo ketones, 47 photodynamic therapy, 48−50 heterocycle formation, 51 bacterial treatment, 52 and enantioselective alpha-alkylation. 53 However, the scope in selectivity has been limited to date with restricted control given by the structural properties of the photocatalyst.…”

“… 23 − 26 Homogeneous, nanoscale distributions of photocatalysts within polymersomes, 25 micelles, 26 nanoparticles, 27 and on surfaces 28 were reported, but the desired implementation of selectivity concepts into these structures is still a subject of on-going research. 23 , 24 , 29 …”

Rational design of a graphitic carbon nitride catalytic–biocatalytic system as a photocatalytic platform for solar fine chemical production from CO2

“…[16][17][18][19] Various light-harvesting materials, including organic dye-based polymeric materials, 20,21 nitrogen-containing polymeric materials, and polymer-based nanomaterials, have been investigated for catalytic reactions. 4,[22][23][24][25] Nitrogen-containing polymeric materials have garnered considerable attention due to their excellent solar light-harvesting photocatalytic ability compared with other, more expensive materials, and chemical stability and extraordinary biocompatibility. [26][27][28][29][30] Few promising instances of in situ polymerization of g-C 3 N 4 with dyes (e.g., eosin) have been reported.…”

Hairy Conjugated Microporous Polymer Nanoparticles Facilitate Heterogeneous Photoredox Catalysis with Solvent-Specific Dispersibility

“…Moreover, the formation of CMP nanoparticles (NPs) by miniemulsion polymerization − can greatly increase photoactive surface area-to-volume ratios. This large surface area can potentially improve substrate accessibility to the active sites on the photocatalysts , as demonstrated by linear conjugated polymer nanoparticles with hydrophilic oligomer or polymer chains achieving good water dispersibility and considerable improvement in hydrogen evolution rates. − However, this underexplored potentiality of the CMP NPs as efficient and broadly applicable photocatalysts has not been accessed owing to their limited dispersibility and colloidal stability in many solvents, particularly in water.…”