A THEORETICAL STUDY FROM FIRST PRINCIPLES OF THE MODIFICATION OF BARIUM TITANATE BY CARBON

Structures based on atomic thin carbon and created by combining two or more graphene-like materials with alternating oxide perovskites change the properties of the source materials and a material with new hybrid properties is formed, which in turn will be a prerequisite for the design of Functional Materials and nanostructures. Strong covalent bonds provide the surface stability of 2D crystals, and the connection between the different layers is mediated by Van der Waalst interaction.

Heterostructures based on carbon materials and nanostructured ferroelectric perovskites, including barium titanate, ferromagnetic (La_2/3Sr_1/3MnO₃, SrRuO₃), alternating metal oxides are promising for the development of new multifunctional materials for memory cells, quantum computer elements, Li-ion battery anodes, photocatalysts, supercapacitors, transistors, sensor materials, solar cells, fuel cells, electrochromic devices.

The paper examines the influence of the density functional theory method on the structural and energy properties of the carbon mixture on the surface of BaTiO₃, which is theoretically important for catalytic purposes, in combination with the pseudopotential method of plane-waves in basis. Based on the theory of density functionality, the process of adsorption of barium titanate as a result of modification with carbon atoms with a gradual increase in concentration on a TiO₂ – terminating (001) surface, pure and doped with carbon atoms, was studied. The most effective locations on the TiO₂ – terminating (001) surface were the “top Ti” locations, and the state density was determined when the concentration of carbon was increased in the order of the graphene structure from 0.125 to 0.75 in the distribution of each TiO₂, and the width of the Forbidden Zone was reduced by 0.27−2 eV compared to the pure surface for the considered structures. The adsorption energy was −0.5 eV for atomic oxygen adsorbed near the energy efficient location defined for carbon on a clean surface, and −2.12 eV for Molecular. For atomic oxygen adsorbed on a carbon −doped surface, the adsorption energy was reduced by −0.2 eV, and for Molecular − by −0.4 eV.

1. S. Kappadan, S. Thomas and N. Kalarikkal Enhanced photocatalytic performance of BaTiO3/g −C3N4 heterojunction for the degradation of organic pollutants // Chemical Physics Letters. –2021. – V. 771. – art. id. 138513. https://doi.org/10.1016/j.cplett.2021.138513

2. S. Alex Pandian, M. Sivakumar, M. Kandasamy, S. Suresh, G. Madhavi Latha, S. Srinivasan, K. Prem Ananth Barium titanate nanorods/nanoparticles embedded reduced graphene oxide nanocomposite photoanode for dye −sensitized solar cell // Chemical Physics Letters. – 16 September 2024. – V. 851. – art. id. 141491.

3. Monisha Rastogi, Chris Bowen, H.S. Kushwaha and Rahul Vaish First principles insights into improved catalytic performance of BaTiO3 − graphene nanocomposites in conjugation with experimental investigations // Materials Science in Semiconductor Processing. – 2016. – V. 51. – P. 33. https://doi.org/10.1016/j.mssp.2016.04.008

4. Kaptagai G.A., Satanova B.M., Abuova F.U., Koilyk N.O., Abuova A.U., Nurkenov S.A., Zharkymbekova A.P. Optical properties of low-dimensional systems: methods of theoretical study of 2D materials // NNC RK Bulletin. – 2022. – No. 4. – P. 35–40. https://doi.org/10.52676/1729-7885-2022-4-35-40

5. Satanova B.M., Kaptagay G.A., Zharkymbekova A.P., Abuova F.U., Abuova A.U., Assylbayev R.N., Koylyk N.O., Tugelbayeva K.T. Ab-initio calculations of rhombohedral BaTiO3 (111) surface combined with graphene films // NNC RK Bulletin. – 2023 – No. 4 – P. 91–97. https://doi.org/10.52676/1729-7885-2023-4-91-97

6. Kaptagay, G.A.; Satanova, B.M.; Abuova, A.U.; Konuhova, M.; Zakiyeva, Z.Y.; Tolegen, U.Z.; Koilyk, N.O.; Abuova, F.U. Effect of rhodium doping for photocatalytic activity of barium titanate // Opt. Mater. X. – 2025. – V. 25. – art. id. 100382.

7. Hadeer k. El Emam, S. I. El −Dek and Waleed M. A. El Rouby aerosol spray assisted synthesis of ni doped batio3 hollow porous spheres/graphene as photoanode for water splitting // J. Electrochem. Soc. – 2021. – V. 168. – art. id. 050540. https://doi.org/10.1149/1945-7111/ac001e

8. Yongjie Zhao, Xiaowei Zhang, Jialin Liu, Chengzhi Wang, Jingbo Li and Haibo Jin Graphene oxide modified nano-sized BaTiO3 as photocatalyst // Ceramics International. – 2018. – V. 44. – art. id. 15929. https://doi.org/10.1016/j.ceramint.2018.06.013

9. Horacio Edgardo Garrafa-Gálvez, Clemente Guadalupe Alvarado-Beltrán, Jorge Luis Almaral-Sánchez, Abel Hurtado-Macías, Angélica María Garzon-Fontecha, Priscy Alfredo Luque and Andrés Castro-Beltrán Graphene role in improved solar photocatalytic performance of TiO2 −RGO nanocomposite // Chemical Physics. – 2019. – V. 521. – art. id. 35. https://doi.org/10.1016/j.chemphys.2019.01.013

10. B. Murali, K. Gireesh Baiju, R. Krishna Prasad and Duraisamy Kumaresan Fabrication of Barium Titanate Nanowires −GNP Composite Bilayer Photoanodes for the High-Performance Dye-Sensitized Solar Cells // Applied Surface Science. – 2023. – V. 610. – art. id. 155316. https://doi.org/10.1016/j.apsusc.2022.155316

11. Z. Mengting, T. Agustiono Kurniawan, S. Fei, T. Ouyang, M. Hafiz Dzarfan Othman, M. Rezakazemi and S. Shirazian Applicability of BaTiO3/graphene oxide (GO) composite for enhanced photodegradation of methylene blue (MB) in synthetic wastewater under UV-vis irradiation // Environmental Pollution. – 2019. – V. 255. – art. id. 113182. https://doi.org/10.1016/j.envpol.2019.113182

12. Y. Li, W. Yang, S. Ding, X.-Z. Fu, R. Sun, W.-H. Liao and C.-P. Wong Tuning dielectric properties and energy density of poly(vinylidene fluoride) nanocomposites by quasi core–shell structured BaTiO3@graphene oxide hybrids // J Mater Sci: Mater Electron. – 2018. – V. 29. – art. id. 1082. https://doi.org/10.1007/s10854-017-8009-9

13. D. Krishna Bhat, H. Bantawal, Uma P.I. and U. Sandhya Shenoy Enhanced photoresponse and efficient charge transfer in porous graphene − BaTiO3 nanocomposite for high performance photocatalysis // Diamond and Related Materials. – 2023. – V. 139. – art. id. 110312. https://doi.org/10.1016/j.diamond.2023.110312

14. Y.-H. Li, Z.-R. Tang and Y.-J. Xu Multifunctional graphene-based composite photocatalysts oriented by multifaced roles of graphene in photocatalysis / Chinese Journal of Catalysis. – 2022. – V. 43. – art. id. 708. https://doi.org/10.1016/S1872-2067(21)63871-8

15. P. Blyweert, A. Zharov, D. Meisak, A. Plyushch, J. Macutkevic Electromagnetic properties of 3D-printed carbon-BaTiO3 composites // Appl. Phys. Lett. – 2023. – V. 123. – art. Id. 012903. https://doi.org/10.1063/5.0145532

16. Q. Tang, J. Wu, D. Kim, C. Franco, A. Terzopoulou, A. Veciana, J. Puigmartí‐Luis, X.‐Z. Chen, Bradley J. Nelson and S. Pané Enhanced piezocatalytic performance of BaTiO3 nanosheets with highly exposed {001} facets // Adv. Funct. Materials. – 2022. – V. 32. https://doi.org/10.1002/adfm.202202180

17. S. Alex Pandian and M. Sivakumar Barium titanate perovskite nanoparticles integrated reduced graphene oxide nanocomposite photoanode for high performance dye −sensitized solar cell // Results in Chemistry. – 2023. – V. 6. – art. id. 101091. https://doi.org/10.1016/j.rechem.2023.101091

18. S. Alex Pandian and M. Sivakumar Ab-initio simulation package for quantum modeling // Phys. Rev. B. – 1999. – V. 59. – P. 558–561.

19. G. Kresse, J. Furthmüller Vasp-code // Phys. Rev. B. – 1996. – V. 54. – P. 11169–11186.

20. P.E. Bloch // Phys. Rev. B. – 1994. – V. 50. – P. 17953– 17959.

21. J.P. Perdew, K. Burke, M. Ernzerhof Functional for the generalized-gradient approximation // Phys. Rev. Lett. – 1996. – V. 77. – P. 3865–3868.

22. H.J. Monkhorst, J.D. Pack Special points for Brillouinzone integrations // Phys. Rev. B. – 1976. – V. 13. –P. 5188–5192.

23. Satanova, B. Study of carbon admixture to oxygen adsorption on the surface of ВаТіО3 (001) from the first principles // Bulletin of the L.N. Gumilyov Eurasian National University. Physics. Astronomy series. – 2025. – V. 150(1). – P. 204–218 (In Kaz.) https://doi.org/10.32523/2616-6836-2025-150-1-204-218