Porous hollow TiO2 microparticles for photocatalysis: exploiting novel ABC triblock terpolymer templates synthesised in supercritical CO2

Reversible addition–fragmentation chain transfer (RAFT) mediated dispersion polymerisation in supercritical carbon dioxide (scCO2) is an efficient and green method for synthesising block copolymer microparticles with internal nanostructures. Here we report for the first time the synthesis of phase s...

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Bibliographic Details
Published in:Polymer chemistry 2021-05, Vol.12 (19), p.2904-2913
Main Authors: Larder, Ryan R, Bennett, Thomas M, Blankenship, L Scott, Fernandes, Jesum A, Husband, Bethany K, Atkinson, Rachel L, Derry, Matthew J, Toolan, Daniel T W, Centurion, Higor A, Topham, Paul D, Gonçalves, Renato V, Taresco, Vincenzo, Howdle, Steven M
Format: Article
Language:English
Subjects:
Block copolymers
Carbon dioxide
Chain transfer
Microparticles
Morphology
Nanostructure
Photocatalysis
Polymer chemistry
Polymethyl methacrylate
Polystyrene resins
Sol-gel processes
Synthesis
Terpolymers
Titanium dioxide
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Summary:Reversible addition–fragmentation chain transfer (RAFT) mediated dispersion polymerisation in supercritical carbon dioxide (scCO2) is an efficient and green method for synthesising block copolymer microparticles with internal nanostructures. Here we report for the first time the synthesis of phase separated poly(methyl methacrylate-block-styrene-block-4-vinylpyridine) (PMMA-b-PS-b-P4VP) triblock terpolymer microparticles using a simple two-pot sequential synthesis procedure in scCO2, with high monomer conversions and no purification steps. The microparticles, produced directly and without further processing, show a complex internal nanostructure, appearing as a “lamellar with spheres” [L + S(II)] type morphology. The P4VP block is then exploited as a structure-directing agent for the fabrication of TiO2 microparticles. Through a simple and scalable sol–gel and calcination process we produce hollow TiO2 microparticles with a mesoporous outer shell. When directly compared to porous TiO2 particles fabricated using an equivalent PMMA-b-P4VP diblock copolymer, increased surface area and enhanced photocatalytic efficiencies are observed.
ISSN:1759-9954
1759-9962
DOI:10.1039/d1py00334h