Sodyum Borhidrürün Aktif Karbon Destekli Mangan(II) Bromür Katalizörü ile Katalitik Dehidrojenasyonu

Öz

Alkali koşullar altında sodyum borohidrürün (NaBH₄) kontrollü dehidrojenasyonu için, aktif karbon destekli mangan(II) bromür (MnBr₂/AC) temelli, maliyet etkin ve yeniden kullanılabilir bir katalizör geliştirilmiştir. Sistem, 1 M NaOH çözeltisinde 22 °C’de kararlı hidrojen salınımı göstermiş, %98,3 hidrojen verimine ulaşmış ve sıfırıncı mertebeden kinetik davranış sergileyerek 14 çevrim boyunca etkinliğini korumuştur. MnBr₂/AC katalizörü, uzun süreli hidrojen üretimi için basit, dayanıklı ve ölçeklenebilir bir yaklaşım sunmaktadır.

Anahtar Kelimeler

• Sodyum borhidrür
• hidrojen üretimi
• MnBr2
• Aktif karbon
• Sıfırıncı derece kinetik; Döngüsel kararlılık.

Catalytic Dehydrogenation of Sodium Borohydride with Activated Carbon-Supported Manganese(II) Bromide Catalyst

Öz

A cost-effective and reusable catalyst, manganese(II) bromide supported on activated carbon (MnBr₂/AC), was developed for the controlled dehydrogenation of sodium borohydride (NaBH₄) under alkaline conditions. The system exhibited stable hydrogen release at 22 °C in 1 M NaOH solution, achieving 98.3 % hydrogen yield and maintaining activity over 14 cycles with zero-order kinetics. The MnBr₂/AC catalyst provides a simple, durable, and scalable approach for long-term hydrogen generation.

Anahtar Kelimeler

• Sodium borohydride
• Hydrogen generation
• MnBr₂
• Activated carbon
• Zero-order kinetics
• Reusability

Kaynakça

1. [1] Büyük, Y., and F. Eryaşar, “Controlled hydrogen release in alkaline media using transition-metal catalysts”, Journal of Polytechnic, 28(2): 102–115. (2025).
2. [2] Kaya, C., ve V. Başhan, “Navigating Türkiye’s Energy Horizon: A Bibliometric Exploration of Academic Contributions to Energy, Fuels, and Hydrogen Subjects”, Politeknik Dergisi, 28(1): 197–214., (2025).
3. [3] Rusman, N., and M. Dahari, “A review on the current progress of metal hydrides material for solid-state hydrogen storage applications”, International Journal of Hydrogen Energy, 41(28): 12108–12126., (2016).
4. [4] Bilen, M., and et al., “Conversion of KCl into KBH4 by mechano-chemical reaction and its catalytic decomposition”, Journal of Electronic Materials, 46(7): 4126–4132., (2017).
5. [5] Gündüz Meriç, G.; A.Ş. Yargıç, ve E. Yaman Çamlı, “Metal içerikli Katalizörler Varlığında Sodyum Bor Hidrürün Hidroliziyle Hidrojen Üretiminin İncelenmesi”, Politeknik Dergisi, 1–1., (2025).
6. [6] Paksoy, A., and et al., “Nanocrystalline cobalt–nickel–boron (metal boride) catalysts for efficient hydrogen production from the hydrolysis of sodium borohydride”, International Journal of Hydrogen Energy, 46(11): 7974–7988., (2021).
7. [7] Dou, S., and et al., “Shaggy-like Ru-clusters decorated core-shell metal-organic framework-derived CoOx@NPC as high-efficiency catalyst for NaBH₄ hydrolysis”, International Journal of Hydrogen Energy, 46(11): 7772–7781., (2021).
8. [8] Wang, F., and et al., “Preparation of dandelion-like Co–Mo–P/CNTs-Ni foam catalyst and its performance in hydrogen production by alcoholysis of sodium borohydride”, International Journal of Hydrogen Energy, 45(55): 30443–30454., (2020).

9. [9] Narasimharao, K.; B.M. Abu-Zied, and S.Y. Alfaifi, “Cobalt oxide supported multi wall carbon nanotube catalysts for hydrogen production via sodium borohydride hydrolysis”, International Journal of Hydrogen Energy, 46(9): 6404–6418., (2021).
10. [10] Zhang, H., and et al., “Carbon nanospheres supported bimetallic Pt-Co as an efficient catalyst for NaBH₄ hydrolysis”, Applied Surface Science, 540: 148296., (2021).
11. [11] Çakanyıldırım, Ç., and M. Gürü, “The Processing of NaBH₄ from Na₂B₄O₇ by Mechano-chemical Synthesis and Its Catalytic Dehydrogenation”, Energy Sources, Part A, 34(12): 1104–1113., (2012).
12. [12] Çakanyıldırım, Ç., and M. Gürü, “Decomposition of NaBH₄ with self-regeneration of carbon-supported CoCl₂ catalyst”, International Journal of Green Energy, 14(12): 1005–1010., (2017).
13. [13] Çakanyıldırım, Ç., and M. Gürü, “Production of NaBH₄ and hydrogen release with catalyst”, Renewable Energy, 34(11): 2362–2365., (2009).
14. [14] Çakanyıldırım, Ç., and M. Gürü, “Supported CoCl₂ catalyst for NaBH₄ dehydrogenation”, Renewable Energy, 35(4): 839–844., (2010).
15. [15] Ar, İ.; Ö.U. Güler, and M. Gürü, “Synthesis and characterization of sodium borohydride and a novel catalyst for its dehydrogenation”, International Journal of Hydrogen Energy, 43(44): 20214–20233., (2018).
16. [16] Bilen, M.; O. Yılmaz, and M. Gürü, “Synthesis of LiBH4 from LiBO2 as hydrogen carrier and its catalytic dehydrogenation”, International Journal of Hydrogen Energy, 40(44): 15213–15217., (2015).
17. [17] Onat, E., and et al., “Synthesis of a cobalt catalyst supported by graphene oxide modified perlite and its application on the hydrolysis of sodium borohydride”, Synthetic Metals, 306: 117621., (2024).
18. [18] İzgi, M.S., and ve diğerleri, “Hydrogen production through the cooperation of a catalyst synthesized in ethanol medium and the effect of the plasma”, Energy Sources, Part A, 1–14., (2019).
19. [19] İzgi, M.S., and et al., “Epoxy-activated acrylic particulate polymer-supported Co–Fe–Ru–B catalyst to produce H₂ from hydrolysis of NH₃BH₃”, International Journal of Hydrogen Energy, 45(43): 22638–22648., (2020).
20. [20] Li, K.T., and S.W. Li, “CoBr2-MnBr2 containing catalysts for catalytic oxidation of p-xylene to terephthalic acid”, Applied Catalysis A: General, 340(2): 271–277., (2008).
21. [21] Chandra, P., and et al., “Recent advancement in oxidation or acceptorless dehydrogenation of alcohols to valorised products using manganese based catalysts”, Coordination Chemistry Reviews, 411: 213241., (2020).
22. [22] Bruneau-Voisine, A., and et al., “Hydrogenation of ketones with a manganese PN3P pincer pre-catalyst”, Catalysis Communications, 92: 1–4., (2017).
23. [23] Pérez, E., and et al., “Selective aerobic oxidation of para-xylene in sub- and supercritical water. Part 1. Comparison with ortho-xylene and the role of the catalyst”, Green Chemistry, 13(9): 2389–2396., (2011).
24. [24] Karabulut, A.F., “Susuz bor oksit ve susuz kolemanitten kalsiyum borhidrür sentezi ve borhidrürlerin katalitik dehidrojenasyonu”, (2015).
25. [25] Demirci, U.B., “Mechanistic and kinetic aspects of sodium borohydride hydrolysis”, Comptes Rendus Chimie, 17(5): 707–716., (2014).
26. [26] Zhou, H., and et al., “Effect of alkaline stabilizers on the hydrolysis of sodium borohydride”, Journal of Power Sources, 490: 229553., (2021).
27. [27] Wu, H., and et al., “Kinetics of hydrogen generation from NaBH₄ hydrolysis catalyzed by transition metal nanoparticles”, Renewable Energy, 147: 2149–2158., (2020).
28. [28] Wang, F., and et al., “Preparation of dandelion-like Co–Mo–P/CNTs-Ni foam catalyst and its performance in hydrogen production by alcoholysis of sodium borohydride”, International Journal of Hydrogen Energy, 45(55): 30443–30454., (2020).
29. [29] Karabulut, A., and et al., “Optimizing hydrogen production from alkali hydrides using supported metal catalysts”, Ionics, 29: 1975–1982., (2023).
30. [30] Wang, L., and et al., “Structural transformation and catalytic performance of Mn-based catalysts supported on porous carbon in hydrogen generation reactions”, International Journal of Hydrogen Energy, 47(15): 10521–10530., (2022).
31. [31] Shang, Y., and et al., “Kinetic study of NaBH₄ hydrolysis over carbon supported ruthenium”, International Journal of Hydrogen Energy, 40(20): 6723–6730., (2015).
32. [32] Bilen, M.; M. Gürü, and Ç. Çakanyıldırım, “Role of NaCl in NaBH₄ production and its hydrolysis”, Energy Conversion and Management, 72: 134–140., (2013).
33. [33] Al-Mamoori, S.K., and M.M. Yusoff, “Synthesis and catalytic activity of transition metal complexes in hydrogen generation from sodium borohydride”, International Journal of Hydrogen Energy, 44(7): 3560–3570., (2019).
34. [34] Narayanan, T.N., and et al., “Catalytic hydrogen generation using transition-metal-doped boron-based materials”, Journal of Physical Chemistry C, 114(40): 17009–17015., (2010).
35. [35] Kulkova, S.E., and A.N. Titov, “Structural and electronic properties of manganese borides: A DFT study”, Journal of Alloys and Compounds, 628: 218–225., (2015).