Skip to main content

Research Repository

Advanced Search

Clean Block Copolymer Microparticles from Supercritical CO 2 : Universal Templates for the Facile and Scalable Fabrication of Hierarchical Mesostructured Metal Oxides

Bennett, Thomas M.; He, Guping; Larder, Ryan R.; Fischer, Michael G.; Rance, Graham A.; Fay, Michael W.; Pearce, Amanda K.; Parmenter, Christopher D. J.; Steiner, Ullrich; Howdle, Steven M.


Thomas M. Bennett

Guping He

Ryan R. Larder

Michael G. Fischer

Amanda K. Pearce

Ullrich Steiner


© 2018 American Chemical Society. Metal oxide microparticles with well-defined internal mesostructures are promising materials for a variety of different applications, but practical routes to such materials that allow the constituent structural length scales to be precisely tuned have thus far been difficult to realize. Herein, we describe a novel platform methodology that utilizes self-assembled block copolymer (BCP) microparticles synthesized by dispersion polymerization in supercritical CO 2 (scCO 2 ) as universal structure directing agents for both hydrolytic and nonhydrolytic sol-gel routes to metal oxides. Spherically structured poly(methyl methacrylate-block-4-vinylpyridine) (PMMA-b-P4VP) BCP microparticles are translated into a series of the corresponding organic/inorganic composites and pure inorganic derivatives with a high degree of fidelity for the metal oxides TiO 2 and LiFePO 4 . The final products are comprised of particles close to 1 μm in size with a highly ordered internal morphology of interconnected spheres between 20-40 nm in size. Furthermore, our approach is readily scalable, enabling grams of pure or carbon-coated TiO 2 and LiFePO 4 , respectively, to be fabricated in a facile two step route involving ambient temperature mixing and drying stages. Given that both length scales within these BCP microparticles can be controlled independently by minor variations in the reagent quantities used, the present general strategy could represent a milestone in the design and synthesis of hierarchical metal oxides with completely tunable dimensions.


Bennett, T. M., He, G., Larder, R. R., Fischer, M. G., Rance, G. A., Fay, M. W., …Howdle, S. M. (2018). Clean Block Copolymer Microparticles from Supercritical CO 2 : Universal Templates for the Facile and Scalable Fabrication of Hierarchical Mesostructured Metal Oxides. Nano Letters, 18(12), 7560-7569.

Journal Article Type Article
Acceptance Date Nov 8, 2018
Online Publication Date Nov 8, 2018
Publication Date Dec 12, 2018
Deposit Date Nov 22, 2018
Publicly Available Date Nov 9, 2019
Journal Nano Letters
Print ISSN 1530-6984
Electronic ISSN 1530-6992
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 18
Issue 12
Pages 7560-7569
Keywords Block copolymer; hierarchical; mesostructures; metal oxide; microparticle; sol-gel
Public URL
Publisher URL
Additional Information This document is the Accepted Manuscript version of a Published Work that appeared in final form in Nano Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [insert ACS Articles on Request author-directed link to Published Work, see


You might also like

Downloadable Citations