EFFECT OF Rh DOPING ON THE ACTIVITY OF THE OXYGEN RELEASE REACTION ON BaTiO₃(001) SURFACES

Photoinduced splitting of water using photocatalysts in the form of nanoparticles is a promising and simple way to produce environmentally friendly hydrogen. In this paper, we investigate the potential of modified barium titanate (BaTiO₃), an inexpensive perovskite oxide obtained from precursors widely distributed on earth, to develop effective electrocatalysts for water oxidation using first-principles calculations.

It has been shown that the BaTiO₃(001) surface terminated with TiO₂ is more promising in terms of its use as a catalyst. After replacing Ti with Rh, the dopant ion can take over part of the electron density from neighboring oxygen ions. As a result, during the oxidation reaction of water, rhodium ions can be in an intermediate oxidation state between 3+ and 4+. This affects the adsorption energy of the reaction intermediates on the surface of the catalyst, reducing the excess potential.

1. Fujishima, A., & Honda, K. Electrochemical photolysis of water at a semiconductor electrode // Nature. – 1972. – Vol. 238(5358). – P. 37–38.

2. Chen, X., & Mao, S. S. Titanium dioxide nanomaterials: Synthesis, properties, modifications, and applications // Chemical Reviews. – 2007. – Vol. 107(7). – P. 2891– 2959.

3. Grätzel, M. Photoelectrochemical cells // Nature. – 2001. – Vol. 414(6861). – P. 338–344.

4. Kudo, A., & Miseki, Y. Heterogeneous photocatalyst materials for water splitting // Chemical Society Reviews. – 2009. – Vol. 38(1). – P. 253–278.

5. Singh, D. P., & Zhao, H. Ferroelectric photocatalysis: The influence of polarization on surface chemical reactions // Nano Energy. – 2018. – Vol. 53. – P. 550–561.

6. Chen, D., Cheng, Y. B., & Caruso, R. A. Surface modification of BaTiO₃ nanoparticles and their application in dye-sensitized solar cells // Advanced Functional Materials. – 2010. – Vol. 20(2). – P. 339–345.

7. Lin, X., & Wang, X. BaTiO₃ nanostructures: Controlled synthesis and applications in photocatalysis // Materials Chemistry and Physics. – 2017. – Vol. 198. – P. 168–176.

8. Zhang, Y., & Tang, Z. Advances in BaTiO₃-based photocatalysts for solar-driven water splitting // Journal of Materials Science. – 2019. – Vol. 54(12). – P. 9408–9424.

9. Liu, H., & Zhang, W. (2021). Interface engineering of BaTiO₃ nanoparticles for enhanced photocatalytic performance // Applied Catalysis B: Environmental. – 2021. – Vol. 298, 120580.

10. Kim, T. H., & Park, J. Enhanced charge separation in BaTiO₃ nanostructures through surface modification: A route to high-efficiency photocatalysis // Nano Energy. – 2020. – Vol. 77. – P. 105266.

11. Y.M. Rangel-Hernandez, J. C. Rendón Angeles, Z. Matamoros-Veloza, Kazumichi Yanagisawa. One-step synthesis of fine SrTiO3 particles using SrSO4 ore under alkaline hydrothermal conditions // Chemical Engineering Journal. – 2009. – Vol. 155(s 1–2). – P. 483–492. https://doi.org/10.1016/j.cej.2009.07.024

12. Vittorio Berbenni, Amedeo Marini, Giovanna Bruni. Effect of Mechanical Activation on the Preparation of SrTiO3 and Sr2TiO4 Ceramics from the Solid State Systems SrCO3–TiO2 // Journal of Alloys and Compounds. – 2001. – Vol. 329(s 1–2). – P. 230–238. https://doi.org/10.1016/S0925-8388(01)01574-2

13. Xiaohua Liu. Haixin Bai. Liquid–solid reaction synthesis of SrTiO3 submicron-sized particles // Materials Chemistry and Physics. – 2011. – Vol. 127(s 1–2). – P. 21–23. https://doi.org/10.1016/j.matchemphys.2011.01.056

14. Shuang Zhi Liu. Tian Xi Wang. Li Yun Yang. Low temperature preparation of nanocrystalline SrTiO3 and BaTiO3 from alkaline earth nitrates and TiO2 nanocrystals // Powder Technology. – 2011. – Vol. 212(2). – P. 378–381. https://doi.org/10.1016/j.powtec.2011.06.010

15. Tao Xian. Hwami Yang. J.-F. Dai. W.-J. Feng. Photocatalytic properties of SrTiO3 nanoparticles prepared by a polyacrylamide gel route // Materials Letters. – 2011. – Vol. 65(21). – P. 3254–3257. https://doi.org/10.1016/j.matlet.2011.07.019

16. Qi-An Zhu. Jun-Gu Xu. S. Xiang. Zhi-Gang Tan. Preparation of SrTiO 3 nanoparticles by the combination of solid phase grinding and low temperature calcining. March 2011. Materials Letters 65(5):873-875. https://doi.org/10.1016/j.matlet.2011.07.019

17. Thanawat Klaytae, Phiram Panthong. Preparation of nanocrystalline SrTiO3 powder by sol–gel combustion method // Ceramics International. – 2013. – Vol. 39. – P.405–408. https://doi.org/10.1016/j.ceramint.2012.10.103

18. Kuang Q, Yang S. Template synthesis of single-crystallike porous SrTiO3 nanocube assemblies and their enhanced photocatalytic hydrogen evolution // ACS Appl Mater Interfaces. – 2013. – Vol. 5. – P. 3683–3690.

19. Xu X, Lv M, Sun X, et al. Role of surface composition upon the photocatalytic hydrogen production of Cr-doped and La/Cr-codoped SrTiO3 // J Mater Sci. – 2016. – Vol. 51. – P. 6464–6473.

20. Ali S, Granbohm H, Ge Y, et al. Crystal structure and photocatalytic properties of titanate nanotubes prepared by chemical processing and subsequent annealing // J Mater Sci. – 2016. – Vol. 51. – P. 7322–7335.

21. Nageri, M.; Kumar, V. Manganese-doped BaTiO3 nanotube arrays for enhanced visible light photocatalytic applications // Mater. Chem. Phys. – 2018. – Vol. 213. – P. 400–405. https://doi.org/10.1016/j.matchemphys.2018.04.003

22. Demircivi, P.; Simsek, E.B. Visible-light-enhanced photoactivity of perovskite-type W-doped BaTiO3 photocatalyst for photodegradation of tetracycline // J. Alloys Compd. – 2019. – Vol. 774. – P. 795–802. https://doi.org/10.1016/j.jallcom.2018.09.354

23. Artrith, N.; Sailuam, W.; Limpijumnong, S.; Kolpak, A.M. Reduced overpotentials for electrocatalytic water splitting over Fe- and Ni-modified BaTiO3 // Phys. Chem. Chem. Phys. – 2016. – Vol. 18. – P. 29561– 29570. https://doi.org/10.1039/C6CP06031E; https://www.ncbi.nlm.nih.gov/pubmed/27748475

24. Xie, P.; Yang, F.; Li, R.; Ai, C.; Lin, C.; Lin, S. Improving hydrogen evolution activity of perovskite BaTiO3 with Mo doping: Experiments and firstprinciples analysis // Int. J. Hydrogen Energy. – 2019. – Vol. 44. – P. 11695–11704. https://doi.org/10.1016/j.ijhydene.2019.03.145

25. Tanwar, N.; Upadhyay, S.; Priya, R.; Pundir, S.; Sharma, P.; Pandey, O. Eu-doped BaTiO3 perovskite as an efficient electrocatalyst for oxygen evolution reaction // J. Solid State Chem. – 2023. – Vol. 317. – P. 123674. https://doi.org/10.1016/j.jssc.2022.123674

26. Maeda, K. Rhodium-doped barium titanate perovskite as a stable p-type semiconductor photocatalyst for hydrogen evolution under visible light // ACS Appl. Mater. Interfaces. – 2014. – Vol. 6. – P. 2167–2173. https://doi.org/10.1021/am405293e; https://www.ncbi.nlm.nih.gov/pubmed/24410048

27. Konta, R.; Ishii, T.; Kato, H.; Kudo, A. Photocatalytic activities of noble metal ion doped SrTiO3 under visible light irradiation // J. Phys. Chem. B. – 2004. – Vol. 108. – P. 8992–8995. https://doi.org/10.1021/jp049556p

28. Nishioka, S.; Maeda, K. Hydrothermal synthesis of rhodium-doped barium titanate nanocrystals for enhanced photocatalytic hydrogen evolution under visible light // RSC Adv. – 2015. – Vol. 5. – P. 100123– 100128. https://doi.org/10.1039/C5RA20044J

29. Zakiyeva Zh.Ye., Inerbaev T.M., Abuova A.U., Abuova F.U., Merali N.A., Tolegen U.Zh., Kaptagay G.A. Ab-Initio calculations of the rhodium-doped (001) surface of the rhombohedral phase BaTiO3 // NNC RK Bulletin. – 2024. – Vol. 2. – P.104–109. (In Russ.) https://doi.org/10.52676/1729-7885-2024-2-104-109]

30. Inerbaev T.M., Zakiyeva Zh.Ye., F.U., Abuova A.U., Nurkenov S.A., Kaptagay G.A. DFT studies of BaTiO3 // Вестник Карагандинского университета. – 2023. P. 72–78].

31. Zakiyeva Z.Ye., Inerbaev T.M., Abuova A.U., Abuova F.U., Nurkenov S.A., Kaptagay G.A., Kabdrakhimova G.D. Effect of Rh-doping on the optical absorption of the (001) BaTiO3 surface // NNC RK Bulletin. – 2024. – Vol. 2. – P. 185–191. (In Russ.) https://doi.org/10.52676/1729-78852024-2-185-191]

32. Kresse G., Joubert D. From ultrasoft pseudopotentials to the projector augmented-wave method // Physical Review B. ‒ 1999. ‒ Vol. 59. – No. 3. ‒ P. 1758. https://doi.org/10.1103/PhysRevB.59.1758

33. Kresse G., Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set // Physical Review B. ‒ 1996. ‒ Vol. 54. – No. 16. ‒ P. 11169. https://doi.org/10.1103/PhysRevB.54.11169

34. Blöchl P. E. Projector augmented-wave method // Physical Review B. ‒ 1994. ‒ Vol. 50. – No. 24. ‒ P. 17953. https://doi.org/10.1103/PhysRevB.50.17953

35. Perdew J. P., Burke K., Ernzerhof M. Generalized gradient approximation made simple // Physical Review Letters. ‒ 1996. ‒ Vol. 77. – No. 18. ‒ P. 3865. https://doi.org/10.1103/PhysRevLett.77.3865

36. Mathew, K.; Sundararaman, R.; Letchworth-Weaver, K.; Arias, T.A.; Hennig, R.G. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways // J. Chem. Phys. – 2014. – Vol. 140. – P. 084106. https://doi.org./10.1063/1.4865107

37. Bader, R.F.W. Atoms in Molecules. A Quantum Theory. – Oxford University Press, Oxford, UK. – 1990.

38. Mom, R.V.; Cheng, J.; Koper, M.T.M.; Sprik, M. Modeling the Oxygen Evolution Reaction on Metal Oxides: The Infuence of Unrestricted DFT Calculations // J. Phys. Chem. C. – 2014. – Vol. 118. – P. 4095–4102.

39. Haynes, W.M. CRCHandbook of Chemistry and Physics, 93rd ed. – CRC Press: Boca Raton, FL, USA. – 2012.

40. Man, I.C., et al., Universality in oxygen evolution electrocatalysis on oxide surfaces // ChemCatChem. – 2011. – Vol. 3(7). – P. 1159–1165.

41. García-Mota, M., et al., Importance of correlation in determining electrocatalytic oxygen evolution activity on cobalt oxides // The Journal of Physical Chemistry C. – 2012. –Vol. 116(39). – P. 21077–21082.

42. Shi, K.; Zhang, B.; Liu, K.; Zhang, J.; Ma, G. RhodiumDoped Barium Titanate Perovskite as a Stable p-Type Photocathode in Solar Water Splitting // ACS Appl. Mater. Interfaces. – 2023. – Vol. 15. – P. 47754–47763. https://doi.org/10.1021/acsami.3c09635; https://www.ncbi.nlm.nih.gov/pubmed/37769117

43. Ng, J.W.D.; García-Melchor, M.; Bajdich, M.; Chakthranont, P.; Kirk, C.; Vojvodic, A.; Jaramillo, T.F. Gold-supported cerium-doped NiOx catalysts for water oxidation // Nat. Energy. – 2016. – Vol. 1. – P. 16053. https://doi.org/10.1038/nenergy.2016.53