Structural, spectroscopic and improved photoelectrochemical properties of TiO2/C composites with anatase/brookite matrix, prepared by air-thermolysis of microspherical titanium glycolate

• Published in: Materials chemistry and physics 2024-09, Vol.323, p.129638, Article 129638
• Main Authors: Ulyanova, E.S., Shalaeva, E.V., Krasil'nikov, V.N., Gyrdasova, O.I., Selyanin, I.O., Zykov, F.M., Koshkina, A.A., Melentsova, A.A., Buldakova, L. Yu, Samigulina, R.F.
• Format: Article
• Language: English
• Subjects: Carbon/anatase/brookite composites; Nanostructure; Photoelectrochemical properties; Raman spectroscopy; Thermolysis synthesis
• ISSN: 0254-0584; 1879-3312
• DOI: 10.1016/j.matchemphys.2024.129638

X-ray powder diffraction, Raman spectroscopy, HRTEM, electron diffraction and differential thermal analysis methods were used to study structural and spectroscopic properties and thermal stability of the products obtained by air-thermolysis of Ti-glycolate in the temperature range 300–450°С. TiO2/C composites were obtained, which have anatase/brookite matrix with a variable degree of crystallinity and contain different contents of brookite and free polymeric-like carbon with COO− groups. It was found that the residual content of carbonaceous component and the intensity of exothermal decomposition of Ti-glycolate have an effect on the formation of brookite-rich TiO2 matrix. Correlations between the phase composition and the free carbon content suggest that during crystallization brookite/carbon nanoparticles are more stable than anatase/carbon nanoparticles. PEC tests demonstrated that the composite photoanode, which has the greatest degree of crystallinity, the optimal carbon content and is most enriched with brookite, exhibits the greatest incident photon-to-current conversion efficiency (IPCE), and its IPCE peak value is twice as great as the IPCE peak value for Degussa P25. The increased IPCE value is associated with the preferable formation of carbon/brookite/anatase heterostructures. The carbon component has an optical gap of approx. 1.1 eV, and at the optimal contents it ensures efficient photogeneration and transfer of electrons into the conduction band of brookite and then into the conduction band of anatase. HRTEM study demonstrated the formation of such heterostructure with anatase/brookite heterojunction. [Display omitted] •TiO2/C composites were synthesized by air thermolysis of Ti-glycolate microspheres.•Composites contain anatase/brookite/amorphous TiO2 and polymeric-like carbon (C).•Influence of thermolysis rate and C-content on the brookite formation is discussed.•Nanocrystalline brookite-rich composite with optimal C-content shows the higher IPCE.•The (1.1eV-optical gap-C)/brookite/anatase heterojunction is assumed to enhance IPCE.