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Mesoporous TiO2 from poly(N,N-dimethylacrylamide)-b-polystyrene block copolymers for long-term acetaldehyde photodegradation

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Abstract

Although already some mesoporous (2–50 nm) sol–gel TiO2 synthesis strategies exist, no pore size control beyond the 12 nm range is possible without using specialized organic structure-directing agents synthetized via controlled anionic/radical polymerizations. Here, we present the use of reversible addition–fragmentation chain transfer (RAFT) polymerization as a straightforward and industrial applicable alternative to the existing controlled polymerization methods for structure-directing agent synthesis. Poly(N,N-dimethylacrylamide)-block-polystyrene (PDMA-b-PS) block copolymer, synthesized via RAFT, was chosen as structure-directing agent for the formation of the mesoporous TiO2. Crack-free thin layers TiO2 with tunable pores from 8 to 45 nm could be acquired. For the first time, in a detailed and systematic approach, the influence of the block size and dispersity of the block copolymer is experimentally screened for their influence on the final meso-TiO2 layers. As expected, the mesoporous TiO2 pore sizes showed a clear correlation to the polystyrene block size and the dispersity of the PDMA-b-PS block copolymer. Surprisingly, the dispersity of the polymer was shown not to be affecting the standard deviation of the pores. As a consequence, RAFT could be seen as a viable alternative to the aforementioned controlled polymerization reactions for the synthesis of structure-directing agents enabling the formation of mesoporous pore size-controlled TiO2. To examine the photocatalytic activity of the mesoporous TiO2 thin layers, the degradation of acetaldehyde, a known indoor pollutant, was studied. Even after 3 years of aging, the TiO2 thin layer retained most of its activity.

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Acknowledgements

Ghent University is acknowledged for funding the research presented in this paper. M. Meire and S. W. Verbruggen acknowledge the FWO-Flanders (Fund for Scientific Research-Flanders) for financial support. The authors thank Bernhard De Meyer for the SEC analysis, Hannes Rijckaert for the cross-sectional analysis, Tom Planckaert for BET analysis of the meso-TiO2 powders, Jeroen Kint for the porosi-ellipsometry tests and Frank Driessen for the MALDI-TOF analysis.

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  1. Department of Chemistry, Sol–Gel Centre for Research on Inorganic Powders and Thin Films Synthesis (SCRiPTS), Faculty of Sciences, Ghent University, Krijgslaan 281 (S3), 9000, Ghent, Belgium

    Jonas Billet, Mieke Meire, Petra Lommens, Klaartje De Buysser & Isabel Van Driessche

  2. Polymer Chemistry Research group, Centre of Macromolecular Chemistry (CMaC), Department of Organic and Macromolecular Chemistry, Faculty of Sciences, Ghent University, Krijgslaan, 281 (S4-bis), 9000, Ghent, Belgium

    Jonas Billet, Stef Vandewalle & Filip Du Prez

  3. Department of Bioscience Engineering, University of Antwerp, Groenenborgerlaan 171, 2020, Antwerp, Belgium

    Natan Blommaerts & Sammy W. Verbruggen

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Billet, J., Vandewalle, S., Meire, M. et al. Mesoporous TiO2 from poly(N,N-dimethylacrylamide)-b-polystyrene block copolymers for long-term acetaldehyde photodegradation. J Mater Sci 55, 1933–1945 (2020). https://doi.org/10.1007/s10853-019-04024-3

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