ТОНКИЕ ПЛЕНКИ WS2, НАНЕСЕННЫЕ НА ПОДЛОЖКИ Ti И Ti/УНС МЕТОДОМ RF МАГНЕТРОННОГО РАСПЫЛЕНИЯ: СТРУКТУРНАЯ ХАРАКТЕРИЗАЦИЯ И ЭФФЕКТИВНОСТЬ РЕАКЦИИ ВЫДЕЛЕНИЯ ВОДОРОДА

Электрокатализаторы реакции выделения водорода (РВВ) на основе распространенных в природе материалов являются перспективной альтернативой катализаторам из благородных металлов. В данной работе тонкие пленки WS₂ были нанесены на титановые подложки методом RF магнетронного распыления при временах осаждения от 30 до 120 мин. с целью исследования влияния толщины пленки на структурные и электрохимические свойства. Кроме того, были изготовлены композитные электроды Ti/УНС/WS2 путем сочетания вертикально ориентированных углеродных наностенок (УНС) с каталитическим слоем WS₂ . Рамановская спектроскопия подтвердила успешное формирование многослойных пленок WS₂ . Электрохимические измерения показали, что эффективность РВВ существенно зависит от времени осаждения WS₂ . Среди исследованных образцов электрод Ti/WS₂ , приготовленный при времени осаждения 90 мин., продемонстрировал наибольшую каталитическую активность: перенапряжение при плотности тока 10 мА·см^-2 составило 294 мВ, а сопротивление переносу заряда оказалось наименьшим в серии Ti/WS₂ (Rct = 15,9 Ом). После электрохимической активации перенапряжение дополнительно снизилось до 144 мВ. Электрохимическая импедансная спектроскопия (ЭИС) показала, что введение УНС значительно улучшает кинетику переноса заряда, снижая Rct до 3,7 Ом. Однако, несмотря на улучшенный электронный транспорт, электрод Ti/УНС/WS₂ не превзошел Ti/WS₂ по активности в РВВ, что свидетельствует о том, что каталитическая эффективность определяется не только свойствами переноса заряда, но и плотностью и доступностью активных центров. Полученные результаты подчеркивают важность оптимизации толщины пленки WS2 и архитектуры электрода для эффективного производства водорода.

1. Nelson, C., Gui, M.M., and Robertson, P.K.J. The Environmental Emission and Climate Change Impact of Hydrogen Fuel Derived from Photocatalysis Water‐Splitting Reaction. Advanced Energy and Sustainability Research, 6 (5) (2025). https://doi.org/10.1002/aesr.202400337.

2. Tiwari, A. Hydrogen Leading the Green Energy Future. Advanced Materials Letters, 13 (2), 2202– 1690 (2022). https://doi.org/10.5185/amlett.2022.021690.

3. Wang, X., Zhou, W., Wang, Y., Gong, L., Liu, X., and Zhou, X. MoO2/Mo heterostructures for hydrogen evolution reaction and ammonia sensing in self-powered mode. Nano Energy, 109, 108253 (2023). https://doi.org/10.1016/j.nanoen.2023.108253.

4. Boretti, A., and Pollet, B.G. Hydrogen economy: Paving the path to a sustainable, low-carbon future. International Journal of Hydrogen Energy, 93, 307–19 (2024). https://doi.org/10.1016/j.ijhydene.2024.10.350.

5. Shaterabadi, M., Sadeghi, S., and Jirdehi, M.A. The Role of Green Hydrogen in Achieving Low and Net-Zero Carbon Emissions: Climate Change and Global Warming. pp. 141–53 (2024). https://doi.org/10.1007/978-3-031-52429-5_6.

6. Kalkozova, Zh.K., Markhabayeva, A.A., Mukhametkarimov, Y.S., Yerlanuly, Y., Tulegenova, A.T., Abdullin, Kh.A., Nuraje, N., and Cao, C.D. PHOTOELECTROCHEMICAL PROPERTIES OF NANOSTRUCTURED SILICON FOR SOLAR WATER SPLITTING. Herald of the Kazakh-British technical university, 21 (4), 245–53 (2024). https://doi.org/10.55452/1998-6688-2024-21-4-245-253.

7. He, H., Mai, J., Hu, K., Yu, H., Zhang, Z., Zhan, F., and Liu, X. Recent advances in electrocatalysts for efficient hydrogen evolution reaction. Rare Metals, 44 (4), 2208–38 (2025). https://doi.org/10.1007/s12598-024-02649-1.

8. Kim, J., Jung, S., Lee, N., Kim, K., Kim, Y., and Kim, J.K. Efficient Alkaline Hydrogen Evolution Reaction Using Superaerophobic Ni Nanoarrays with Accelerated H 2 Bubble Release. Advanced Materials, 35 (52) (2023). https://doi.org/10.1002/adma.202305844.

9. Bozheyev, F., Nemkayeva, R., Yerlanuly, Y., Gabdullin, M., and Markhabayeva, A. Performance of Transition Metal Oxides for Solar Hydrogen Conversion. ACS Catalysis, 15 (18), 16449–62 (2025). https:// doi.org/10.1021/acscatal.5c03869.

10. Huang, T.-X., Cong, X., Wu, S.-S., Wu, J.-B., Bao, Y.-F., Cao, M.-F., Wu, L., Lin, M.-L., Wang, X., Tan, P.-H., and Ren, B. Visualizing the structural evolution of individual active sites in MoS2 during electrocatalytic hydrogen evolution reaction. Nature Catalysis, 7 (6), 646–54 (2024). https://doi.org/10.1038/s41929-024-01148-x.

11. Xu, Y., Ge, R., Yang, J., Li, J., Li, S., Li, Y., Zhang, J., Feng, J., Liu, B., and Li, W. Molybdenum disulfide (MoS2)-based electrocatalysts for hydrogen evolution reaction: From mechanism to manipulation. Journal of Energy Chemistry, 74, 45–71 (2022). https://doi.org/10.1016/j.jechem.2022.06.031.

12. Kong, L., Pan, L., Guo, H., Qiu, Y., Alshahrani, W.A., Amin, M.A., and Lin, J. Constructing WS2/WO3-x heterostructured electrocatalyst enriched with oxygen vacancies for accelerated hydrogen evolution reaction. Journal of Colloid and Interface Science, 664, 178–85 (2024). https://doi.org/10.1016/j.jcis.2024.03.002.

13. Yang, F., Pan, Y., and Zhu, J. Enhanced catalytic activity of noble metal@borophene/WS2 heterojunction for hydrogen evolution reaction. Applied Surface Science, 680, 161321 (2025). https://doi.org/10.1016/j.apsusc.2024.161321.

14. Tekalgne, M.A., Do, H.H., Nguyen, T. Van, Le, Q. Van, Hong, S.H., Ahn, S.H., and Kim, S.Y. MXene Hybrid Nanosheet of WS 2 /Ti 3 C 2 for Electrocatalytic Hydrogen Evolution Reaction. ACS Omega, 8 (44), 41802–8 (2023). https://doi.org/10.1021/acsomega.3c06403.

15. Sun, R., Wang, Z., and Zhao, J. Transition metal-anchored WS2 nanosheets as efficient electrocatalysts for hydrogen evolution reaction: A first-principles study. Molecular Catalysis, 588, 115519 (2026). https://doi.org/10.1016/j.mcat.2025.115519.

16. Rahmani, E., Reyhani, A., Khanlary, M.R., Mortazavi, S.Z., Mohammadi, M.R., Dau, H., Gholami, M.F., Mohammadi, A.B., Rabe, J.P., Soleimani, M., and Zarabadipoor, M. Phosphorus doped few layer WS2 flakes grown by chemical vapor deposition for hydrogen evolution reactions. Scientific Reports, 15 (1), 6350 (2025). https://doi.org/10.1038/s41598-025-90341-4.

17. Joseph, A., Chacko, L., Sanal, K.C., Pineda-Aguilar, N., Jasna, M., Antony, A., and Aneesh, P.M. Efficient hydrogen evolution reaction performance of Ni substituted WS2 nanoflakes. Applied Physics A, 130 (12), 875 (2024). https://doi.org/10.1007/s00339-024-08050-0.

18. Nguyen, T. Van, Huynh, K.A., Le, Q. Van, Ahn, S.H., and Kim, S.Y. Facile Synthesis of WS 2 /WO 3 Materials in a Batch Reactor for the Hydrogen Evolution Reaction. International Journal of Energy Research, 2024 (1) (2024). https://doi.org/10.1155/2024/4878549.

19. Singh, T., Deepak, D., Panghal, A., and Roy, S.S. Laser-induced graphene nano-anchored WS2/WO3 heterostructures for electrocatalytic oxygen evolution reaction. International Journal of Hydrogen Energy, 84, 939–50 (2024). https://doi.org/10.1016/j.ijhydene.2024.08.272.

20. Markhabayeva, A. Synthesis of hierarchical wo3 microspheres for photoelectrochemical water splitting application. Physical Sciences and Technology, 10 (2) (2023). https://doi.org/10.26577/phst.2023. v10.i2.04.

21. Liao, L., Zhao, Y., Zhou, H., Li, D., Qi, Y., Zhang, Y., Sun, Y., Zhou, Q., and Yu, F. Edge‐oriented N‐Doped WS 2 Nanoparticles on Porous Co 3 N Nanosheets for Efficient Alkaline Hydrogen Evolution and Nitrogenous Nucleophile Electrooxidation. Small, 18 (40) (2022). https://doi.org/10.1002/smll.202203171.

22. Huang, X., Jiang, H., Ge, B., Huang, C., and Tang, J. Nitrogen‐Doped NiS/WS 2 Heterostructures on Carbon Cloth: A Synergistic Route to High‐Performance Hydrogen Evolution Catalysts. ChemSusChem, 19 (11) (2026). https://doi.org/10.1002/cssc.70782.

23. Arumugam, D., Subramani, M., Subramani, D., and Ramasamy, S. Unraveling the potential of transition metals as single atom catalyst in Graphene/WS2 van der Waals heterostructure for enhanced HER performance – A first principles study. International Journal of Hydrogen Energy, 68, 545–58 (2024). https://doi.org/10.1016/j.ijhydene.2024.04.281.

24. Nasr, M., Benhamou, L., Kotbi, A., Rajput, N.S., Campos, A., Lahmar, A.-I., Hoummada, K., Kaja, K., El Marssi, M., and Jouiad, M. Photoelectrochemical Enhancement of Graphene@WS2 Nanosheets for Water Splitting Reaction. Nanomaterials, 12 (11), 1914 (2022). https://doi.org/10.3390/nano12111914.

25. Liu, F., Zeng, D., Tian, Y., Hu, Y., Shen, T., Gao, Y., and Guan, R. Ternary heterostructure Cu-ZnIn2S4/ WO3/WS2 flower-like microspheres for highly-efficient photocatalytic hydrogen evolution under visible-light irradiation. Applied Surface Science, 642, 158572 (2024). https://doi.org/10.1016/j.apsusc.2023.158572.

26. Rasool, F., Pirzada, B.M., Talib, S.H., Alkhidir, T., Anjum, D.H., Mohamed, S., and Qurashi, A. In Situ Growth of Interfacially Nanoengineered 2D–2D WS 2 /Ti 3 C 2 T x MXene for the Enhanced Performance of Hydrogen Evolution Reactions. ACS Applied Materials & Interfaces, 16 (11), 14229–42 (2024). https://doi.org/10.1021/acsami.3c11642.

27. Ladhane, S., Shah, S., Shinde, P., Punde, A., Waghmare, A., Hase, Y., Bade, B.R., Doiphode, V., Rahane, S.N., Kale, D., Rondiya, S.R., Prasad, M., Patole, S.P., and Jadkar, S.R. Enhanced Photoelectrochemical Activity Realized from WS 2 Thin Films Prepared by RF‐Magnetron Sputtering for Water Splitting. ChemElectroChem, 11 (7) (2024). https://doi.org/10.1002/celc.202400002.

28. Ladhane, S., Shah, S., Doiphode, V., Shinde, P., Kale, D., Rahane, S., Thombare, J., Ingole, M., Vairale, P., Hase, Y., Waghmare, A., Prasad, M., Patole, S.P., and Jadkar, S. Pressure-dependent growth of RF-sputtered WS2 nanostructures for enhanced hydrogen production via photoelectrochemical water splitting. Journal of Power Sources, 640, 236786 (2025). https://doi.org/10.1016/j.jpowsour.2025.236786.

29. Ladhane, S., Shah, S., Doiphode, V., Shinde, P., Kale, D., Rahane, S., Thombare, J., Ingole, M., Vairale, P., Hase, Y., Waghmare, A., Prasad, M., Patole, S.P., and Jadkar, S. Tailoring CdS/WS2 heterostructures for enhanced photoelectrochemical water splitting via RF magnetron sputtering. Journal of Power Sources, 656, 238056 (2025). https://doi.org/10.1016/j.jpowsour.2025.238056.

30. Van Toan, N., Sui, H., Li, J., Tuoi, T.T.K., and Ono, T. Nanoengineered micro-supercapacitors based on graphene nanowalls for self-powered wireless sensing system. Journal of Energy Storage, 81, 110446 (2024). https://doi.org/10.1016/j.est.2024.110446.

31. Farid, G., Amade, R., Chaitoglou, S., Alshaikh, I., Ospina, R., Ma, Y., and Bertran-Serra, E. Efficient flexible electrodes for lithium-ion batteries utilizing well-dispersed hybrid Mo2C nanoparticles on verticallyoriented graphene nanowalls. Journal of Alloys and Compounds, 968, 172109 (2023). https://doi.org/10.1016/j.jallcom.2023.172109.

32. Stoian, M.C., Romanitan, C., Simionescu, O.G., Djourelov, N., Brincoveanu, O., Dinescu, A., and Radoi, A. Growth of nanocrystalline graphite and vertically aligned graphite nanowalls thin films and their transfer on flexible substrates for applications as electrochemical sensors for anthracene detection. Microchemical Journal, 207, 111828 (2024). https://doi.org/10.1016/j.microc.2024.111828.

33. Chaitoglou, S., Ospina, R., Ma, Y., Amade, R., Vendrell, X., Rodriguez-Pereira, J., and Bertran-Serra, E. Deposition and in-situ formation of nanostructured Mo2C nanoparticles on graphene nanowalls support for efficient electrocatalytic hydrogen evolution. Journal of Alloys and Compounds, 972, 172891 (2024). https://doi.org/10.1016/j.jallcom.2023.172891.

34. Zhumadilov, B.Ye., Zhumadilov, R.Ye., Nemkayeva, R.R., Markhabayeva, A.A., Ramazanov, T.S., Yerlanuly, Y., and Gabdullin, M.T. WO3-modified carbon nanowall electrodes for efficient hydrogen evolution reaction. International Journal of Hydrogen Energy, 223, 154356 (2026). https://doi.org/10.1016/j.ijhydene.2026.154356.

35. Zhumadilov, B.Y., Zhumadilov, R.Y., Nemkayeva, R.R., Markhabayeva, A.A., Bozheyev, F., Ramazanov, T.S., Yerlanuly, Y., and Gabdullin, M.T. Influence of Substrate Type and Synthesis Time on Morphological and Structural Properties of Carbon Nanowalls. Advanced Physics Research, 4 (12) (2025). https://doi.org/10.1002/apxr.202500156.

36. Madadkhani, S., Nandy, S., Chae, K.H., Aleshkevych, P., and Najafpour, M.M. Advances in Understanding Tungsten Disulfide Dynamics during the Hydrogen-Evolution Reaction: An Initial Step in Elucidating the Mechanism. The Journal of Physical Chemistry Letters, 15 (19), 5112–9 (2024). https://doi.org/10.1021/acs.jpclett.4c00924.

37. Van Nguyen, T., Tekalgne, M., Nguyen, T.P., Van Le, Q., Ahn, S.H., and Kim, S.Y. Electrocatalysts based on MoS 2 and WS 2 for hydrogen evolution reaction: An overview. Battery Energy, 2 (3) (2023). https://doi.org/10.1002/bte2.20220057.

38. Wang, R., Zhang, D., Luo, S., Wang, Q., Jiang, L., Wei, G.-F., and Wang, X. Incorporation of tungsten nanoparticles on WS2 film for the enhanced hydrogen evolution. International Journal of Hydrogen Energy, 59, 645–53 (2024). https://doi.org/10.1016/j.ijhydene.2024.02.010.

39. Shin, Y., Kim, J., Jang, Y., Ko, E., Lee, N.-S., Yoon, S., and Kim, M.H. Vertically-Oriented WS2 Nanosheets with a Few Layers and Its Raman Enhancements. Nanomaterials, 10 (9), 1847 (2020). https://doi.org/10.3390/nano10091847.

40. Rajeswaran, B., Konar, R., Yitzhari, R., Nessim, G.D., and Tischler, Y.R. Enhancement of the E 1 2g and A 1g Raman modes and layer identification of 2H‐WS 2 nanosheets with metal coatings. Journal of Raman Spectroscopy, 54 (9), 1030–7 (2023). https://doi.org/10.1002/jrs.6585.

41. ZHUMADILOV, B., KENZHEGULOV, A., NEMKAYEVA, R., PARTIZAN, G., YERLANULY, Y., and GADBULLIN, M. Synthesis of carbon nanowalls by oxy-acetylene torch method. Journal of Metals, Materials and Minerals, 33 (4), 1806 (2023). https://doi.org/10.55713/jmmm.v33i4.1806.

42. Minh, N.Q., Van Nong, N., Dela Vega, M.S.D.C., Oda, O., and Hori, M. Synthesis of highly dense and multi-branched carbon nanowalls by two-step growth combining different plasma chemical vapor deposition methods. Vacuum, 213, 112118 (2023). https://doi.org/10.1016/j.vacuum.2023.112118.