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Influence of substituted acetic acids on “bridge” synthesis of highly photocatalytic active heterophase TiO2 in hydrogen production

  • Original Paper: Sol-gel and hybrid materials for catalytic, photoelectrochemical and sensor applications
  • Published:
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Abstract

Anatase/brookite nanoparticles were prepared by low-temperature hydrolysis and polycondensation of titanium isopropoxide in the presence of low concentrations of acetic acid substituted in the α−position with Cl, F, NH2 or OH groups. A bridging mechanism described the formation of TiO2 with heterophase junctions between anatase and brookite. Substituted acetic acids formed short Ti---X-CH2-COO---Ti bridges that held neighboring Ti species close together and facilitated their condensation and the formation of Ti-O-Ti bonds. The structure of the anatase-brookite heterophase junctions was located and fully characterized by HR-TEM. The most acidic acetic acids substituted with groups with a strongly negative inductive effect, monochloroacetic, dichloroacetic, trichloroacetic, trifluoroacetic and amino acetic acids, supported the formation of TiO2, which in cooperation with the Pt cocatalyst had photocatalytic activity, 144.6–165.6 μmol H2/min. g, in the production of hydrogen. All photocatalysts had a pronounced mesoporous structure and a large specific surface area (212.6 to 247.2 m2/g), which contributed to the high photocatalytic activity.

Graphical Abstract

Heterophase anatase-brookite photocatalysts were prepared by hydrolysis and polycondensation of titanium isoproproxide in a solution of substituted acetic acids. Bridges between substituted acetic acids and Ti atoms supported the formation of heterophase anatase-brookite junctions, which formed highly active photocatalysts in hydrogen production.

Highlights

  • Heterophase anatase-brookite nanoparticles were prepared by hydrolysis and polycondensation of titanium isopropoxide in a solution of substituted acetic acids.

  • The bridges between substituted acetic acids and Ti atoms facilitate the formation of heterophase anatase-brookite junctions.

  • Anatase-brookite heterophase junctions deposited by Pt nanoparticles formed photocatalytically active centers.

  • acetic acids substituted with Cl-, F- and NH2- groups produced highly active photocatysts in hydrogen production.

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Acknowledgements

The work was carried out in the frame of the COST Action CA18125 “Advanced Engineering and Research of aeroGels for Environment and Life Sciences” (AERoGELS) and funded by the European Commission. The authors acknowledge the support of the Ministry of Education, Youth and Sports of the Czech Republic under grant no. LTC20019. We also acknowledge CzechNanoLab Research Infrastructure supported by MEYS CR (project LM2018110).

Funding

This work was supported by Ministry of Education, Youth and Sports of the Czech Republic under Grant numbers LTC20019.

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Authors and Affiliations

  1. CEITEC-Central European Institute of Technology, Brno University of Technology, Purkynova 656/123, 612 00, Brno, Czech Republic

    Jaroslav Cihlar, Lizeth Katherine Tinoco Navarro, Jaroslav Cihlar, Vit Kasparek, Jan Michalicka, Klara Castkova, Jaroslav Kastyl & Ladislav Celko

  2. Institute of Materials Science and Engineering, Brno University of Technology, Technicka 2, 616 69, Brno, Czech Republic

    Jaroslav Cihlar & Klara Castkova

  3. The Czech Academy of Sciences, Institute of Rock Structure and Mechanics, V Holesovickach 94/41, 182 09, Prague 8, Czech Republic

    Jaroslav Cihlar

  4. University of Debrecen, AerogelLab, Department of Inorganic and Analytical Chemistry, H-4032, Debrecen, Hungary

    Istvan Lazar

  5. Faculty of Chemistry, Brno University of Technology, Purkynova 118, 612 00, Brno, Czech Republic

    Michal Vesely & Petr Dzik

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  1. Jaroslav Cihlar
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Contributions

(CRediT author statement) All authors contributed to the study conception and design. JC: conceptualization, supervision, methodology, investigation, writing - original draft. KTN: investigation, visualization. JC: visualization, investigation, formal analysis. VK: investigation. JM: formal analysis, writing - original draft. KC: project administration, validation, writing - review & editing. IL: writing - original draft, writing - review & editing. JK: formal analysis, writing - original draft. LC: resources, validation. MV: resources, funding acquisition. PD: resources, funding acquisition. The first draft of the manuscript was written by JC and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Jaroslav Cihlar.

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Cihlar, J., Navarro, L.K.T., Cihlar, J. et al. Influence of substituted acetic acids on “bridge” synthesis of highly photocatalytic active heterophase TiO2 in hydrogen production. J Sol-Gel Sci Technol 105, 471–488 (2023). https://doi.org/10.1007/s10971-022-06011-8

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