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

Larder, Ryan R; Bennett, Thomas M; Blankenship, Leo S; Alves Fernandes, Jesum; Husband, Bethany K; Atkinson, Rachel L; Derry, Matthew J; Thomas William Toolan, Daniel; Centurion, Higor A.; Topham, Paul D.; Vitalino Goncalves, Renato; Taresco, Vincenzo; Howdle, Steven M

Abstract

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.

Citation

Larder, R. R., Bennett, T. M., Blankenship, L. S., Alves Fernandes, J., Husband, B. K., Atkinson, R. L., Derry, M. J., Thomas William Toolan, D., Centurion, H. A., Topham, P. D., Vitalino Goncalves, R., Taresco, V., & Howdle, S. M. (2021). Porous hollow TiO2 microparticles for photocatalysis: exploiting novel ABC triblock terpolymer templates synthesised in supercritical CO2. Polymer Chemistry, 12(19), 2904-2913. https://doi.org/10.1039/d1py00334h

• Journal Article Type: Article
• Acceptance Date: Apr 21, 2021
• Online Publication Date: Apr 22, 2021
• Publication Date: May 21, 2021
• Deposit Date: Apr 22, 2021
• Publicly Available Date: Apr 22, 2021
• Journal: Polymer Chemistry
• Print ISSN: 1759-9954
• Electronic ISSN: 1759-9962
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 12
• Issue: 19
• Pages: 2904-2913
• DOI: https://doi.org/10.1039/d1py00334h
• Keywords: Organic Chemistry; Biochemistry; Bioengineering; Polymers and Plastics
• Public URL: https://nottingham-repository.worktribe.com/output/5487786
• Publisher URL: https://pubs.rsc.org/en/Content/ArticleLanding/2021/PY/D1PY00334H#!divAbstract