Sodyum Borohidrürün Metanoliziyle Hidrojen Üretimi için Co/AlSi Katalizör Sentezi

Öz

Bu çalışmada NaBH₄ metanolizi için silika bazlı bir Co/AlSi katalizörü geliştirilmiştir. Sentezlenen Co/AlSi katalizörünün yapı ve bileşimini analiz etmek amacıyla Fourier dönüşümlü kızılötesi spektroskopisi (FTIR), X-ışını kırınımı (XRD), taramalı elektron mikroskobu (SEM) ve enerji dağılımlı X-ışını spektroskopisi (EDS) kullanılmıştır. Bu çalışmadaki deneyler genel olarak 30 °C’de, 0,05 g NaBH₄ içeren 5 mL metanol çözeltisi ve 40 mg katalizör kullanılarak gerçekleştirilmiştir. Deneyler sırasında üretilen hidrojen hacmini belirlemek için gaz ölçüm sistemi kullanılmıştır. Sıcaklık, katalizör miktarı ve NaBH₄ derişimindeki değişikliklerin etkileri incelenmiştir. Bu katalizör, NaBH₄’ün metanolizi yoluyla maksimum 6250 mL dk⁻¹ gmetal⁻¹ hidrojen üretim hızına ulaşmıştır. Co/AlSi katalizörü, 20,90 kJ/mol aktivasyon enerjisiyle NaBH₄ metanolizini katalizlemiştir. Katalizör kullanım sonrasında aktivitesini kısmen kaybetmiş olsa da seyreltilmiş bir çözeltiyle yıkanarak rejenere edilebilmiş ve üçüncü döngüden sonra aktivitesinin %89’unu korumuştur.

Anahtar Kelimeler

• Katalizör sentezi
• Hidrojen
• Metanoliz
• Silika
• CoB.

Co/AlSi Catalyst Synthesis for Hydrogen Production by Methanolysis of Sodium Borohydride

Öz

In this work, a silica-based Co/AlSi catalyst for NaBH4 methanolysis was developed. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS) were used to analyze the structure and composition of the synthesized Co/AlSi catalyst. The experiments in this study were typically conducted using 5 mL of methanol solution containing 0.05 g NaBH4 and 40 mg catalyst at 30 °C. The gas measurement system was used to determine the volume of hydrogen produced during the experiments. The effects of varying temperature, catalyst amount, and NaBH4 concentration were examined. This catalyst achieved a maximum hydrogen production rate of 6250 mL min⁻¹ gmet⁻¹ through the methanolysis of NaBH4. The Co/AlSi catalyst catalyzed the methanolysis of NaBH4 with an activation energy of 20.90 kJ/mol. Although the catalyst partially lost activity after use, regeneration by washing with a diluted solution was possible, and after the third cycle, the activity remained at 89%.

Anahtar Kelimeler

• Catalyst synthesis
• Hydrogen
• Methanolysis
• Silica
• CoB.

Kaynakça

1. Aslam, N., Yang, W., & Saeed, R. (2026). Analyzing environmental resilience through energy rebalancing and transitions in global perspectives. Environment, Development and Sustainability. https://doi.org/10.1007/s10668-025-07280-3
2. Ecer, U., Yilmaz, S., Ulas, B., & Kaya, S. (2024). Constructing HNT-AC Supported CoNi Nanoparticles for Hydrogen Generation toward NaBH4 Hydrolysis: Optimization with RSM-CCD. Catalysis Letters, 154(10), 5472–5486. https://doi.org/10.1007/s10562-024-04727-6
3. Gurdal, S. (2024). High-Efficiency and Fast Hydrogen Production from Sodium Borohydride: The Role of Adipic Acid in Hydrolysis, Methanolysis and Ethanolysis Reactions. Molecules, 29(20), 4893. https://doi.org/10.3390/molecules29204893
4. Işik, U., Namli, M., Kantar, C., & Elma Karakaş, D. (2025). Zinc phthalocyanine as a heterogeneous catalyst for efficient H2 generation from NaBH4 methanolysis. International Journal of Hydrogen Energy, 176, 151497. https://doi.org/10.1016/j.ijhydene.2025.151497
5. Dudu, T. E., Alpaslan, D., & Aktas, N. (2022). Hydrogen Production from Methanolysis of Sodium Borohydride by Non-metal p(CO) Organo-particles Synthesized from Castor Oil. Journal of Polymers and the Environment, 30(11), 4562–4570. https://doi.org/10.1007/s10924-022-02521-2
6. Li, X., Yang, N., Cen, X., Li, S., Zhang, L., & Lu, Z.-H. (2023). Exceptional activity of hollow porphyrin frameworks-confined Ni nanoparticles for hydrogen production from NaBH4 methanolysis. Fuel, 354, 129332. https://doi.org/10.1016/j.fuel.2023.129332
7. Koşar, C. (2021). Hidrojen Depolama Yöntemleri. Open Journal of Nano, 6(1), 1–10.
8. Akbar, S., Qureshi, M. N., & Khan, S. A. (2025). Fabrication of chitosan supported copper nano catalyst for the hydrogen gas production through methanolysis and hydrolysis of NaBH4. International Journal of Hydrogen Energy, 101, 313–322. https://doi.org/10.1016/j.ijhydene.2024.12.462

9. Chen, Y., Cai, X., Yang, C., Zhou, H., Tan, J., & Cheng, M. (2025). Preparation of Ni/activated carbon-catalyzed Mg-based solid-state hydrogen storage materials with enhanced hydrogen storage properties. Journal of Materials Research, 40(5), 819–832. https://doi.org/10.1557/s43578-025-01535-5
10. Gokkus, K., Ozbal, A., Gür, M., Akalin, S. A., & Bütün, V. (2025). Hyperbranched novel functional polymeric catalysts offering new approaches in hydrogen production via NaBH4 methanolysis. International Journal of Hydrogen Energy, 98, 106–126. https://doi.org/10.1016/j.ijhydene.2024.12.059
11. Dang, T. H., Nguyen, M. D., Tuan, D. D., & Nguyen, T. M. P. (2025). Robust hydrogen production from NaBH4 hydrolysis using 2D/3D hierarchical hollow-architected cobalt oxide: The relationship between structural properties and catalytic activities. International Journal of Hydrogen Energy, 129, 1–9. https://doi.org/10.1016/j.ijhydene.2025.04.278
12. Elma Karakaş, D. (2022). A novel cost-effective catalyst from orange peel waste protonated with phosphoric acid for hydrogen generation from methanolysis of NaBH4. International Journal of Hydrogen Energy, International Conference on Energy, Environment and Storage of Energy, 15. International Combustion Symposium, 47(24), 12231–12239. https://doi.org/10.1016/j.ijhydene.2021.09.102
13. Guye, M. E., Egualle, F. K., Dabaro, M. D., & Kim, H. (2024). Rapid hydrogen generation via NaBH4 methanolysis: The synergetic effect of Zn(OH)₂/ZnO@sp2-C heterostructure tuned via biomass-derived carbon nanodots. International Journal of Hydrogen Energy, 93, 207–220. https://doi.org/10.1016/j.ijhydene.2024.10.429
14. Yildiz, D. (2024). Hydrogen Generation from NaBH4 Methanolysis with Ru/AC Catalyst Synthesized by Microwave Reduction Method. Waste and Biomass Valorization, 15(7), 4061–4070. https://doi.org/10.1007/s12649-024-02435-1
15. Gokkus, K., Kaya, S., Gür, M., Yildiz, D., Yıldırım, E., Kivrak, H., & Bütün, V. (2025). Catalytic Application of a Zwitterionic Polymeric Network for Hydrogen Generation via Sodium Borohydride Methanolysis. Catalysis Letters, 155(12), 378. https://doi.org/10.1007/s10562-025-05207-1
16. Canpolat, G., & Kaya, M. (2023). Metal-Free Coal Catalyst for Hydrogen Production: Synthesis and Performance Assessment. Journal of the Turkish Chemical Society Section B: Chemical Engineering, 6(2), 63–72. https://doi.org/10.58692/jotcsb.1291544
17. Bekirogullari, M. (2024). Synthesis of waste eggshell-derived Au/Co/Zn/eggshell nanocomposites for efficient hydrogen production from NaBH4 methanolysis. International Journal of Hydrogen Energy, 52, 1380–1389. https://doi.org/10.1016/j.ijhydene.2023.06.270
18. Bilgiç, C., Hoşgün, S., & Çiftci, A. (2025). Hydrothermal synthesis and characterization of zeolite A and zeolite X from kaolinite, fly ash, slag and their application in hydrogen generation systems on NaBH4 hydrolysis. International Journal of Hydrogen Energy, 109, 742–752. https://doi.org/10.1016/j.ijhydene.2025.02.171
19. Akti, F. (2021). Hydrogen generation from hydrolysis of sodium borohydride by silica xerogel supported cobalt catalysts: Positive roles of amine modification and calcination treatment. Fuel, 303, 121326. https://doi.org/10.1016/j.fuel.2021.121326
20. Sahiner, N., & Yasar, A. O. (2016). A New Application for Colloidal Silica Particles: Natural, Environmentally Friendly, Low-Cost, and Reusable Catalyst Material for H2 Production from NaBH4 Methanolysis. Industrial & Engineering Chemistry Research, 55(43), 11245–11252. https://doi.org/10.1021/acs.iecr.6b03089
21. Salt, S., Celep, K., Figen, H. E., & Karaismailoğlu Elibol, M. (2026). Al2O3 pellet supported transition metal oxide catalysts for H2 generation from alkaline NaBH4 solution. International Journal of Hydrogen Energy, 209, 153581. https://doi.org/10.1016/j.ijhydene.2026.153581
22. Elibol, M. K. (2025). Development of High-Surface-Area Alumina-Supported Catalysts for the Generation of Hydrogen from NaBH4. Afyon Kocatepe Üniversitesi Fen Ve Mühendislik Bilimleri Dergisi, 25(1), 53–58. https://doi.org/10.35414/akufemubid.1515815
23. Arınan, E., Dogan, M., Uysal, D., & Doğan, Ö. M. (2025). Use of Alumina Supported Co-P and Ni-P Catalysts Synthesized By Electroless Plating Method in NaBH4 Hydrolysis. Gazi University Journal of Science, 38(3), 1159–1176. https://doi.org/10.35378/gujs.1602928
24. Gülen, J., Zorbay, F., & Arslan, S. (2012). Zeolitler ve Kullanım Alanları. Karaelmas Fen ve Mühendislik Dergisi, 2(1), 63–68.
25. Jansoda, I., Patdhanagul, N., Poo-arporn, Y., & Chanapattharapol, K. C. (2024). Zeolite-supported cobalt catalysts derived from natural diatomite with high catalytic activity for catalyzing NaBH4 hydrolysis. Journal of Materials Research, 39(24), 3370–3384. https://doi.org/10.1557/s43578-024-01475-6
26. Cardenas-Flechas, L. J., Freire, P. T. C., Paris, E. C., Moreno, L. C., & Joya, M. R. (2021). Temperature-induced structural phase transformation in samples of Co3O4 and Co3-xNixO4 for CoO. Materialia, 18, 101155. https://doi.org/10.1016/j.mtla.2021.101155
27. Zhang, J., Li, X., Chen, H., Qi, M., Zhang, G., Hu, H., & Ma, X. (2017). Hydrogen production by catalytic methane decomposition: Carbon materials as catalysts or catalyst supports. International Journal of Hydrogen Energy, 42(31), 19755–19775. https://doi.org/10.1016/j.ijhydene.2017.06.197
28. Lu, Y.-C., Chen, M.-S., & Chen, Y.-W. (2012). Hydrogen generation by sodium borohydride hydrolysis on nanosized CoB catalysts supported on TiO2, Al2O3 and CeO2. International Journal of Hydrogen Energy, Portable Fuel Cells – Fundamental and Applications (ISPFC2010), 37(5), 4254–4258. https://doi.org/10.1016/j.ijhydene.2011.11.105
29. Kaya, M., & Bekirogullari, M. (2019). Investigation of Hydrogen Production from Sodium Borohydride Methanolysis in the Presence of Al2O3/Spirulina Platensis Supported Co Catalyst. Avrupa Bilim ve Teknoloji Dergisi, (16), 69–76. https://doi.org/10.31590/ejosat.549911
30. Sahiner, N., & Sengel, S. B. (2017). Environmentally benign halloysite clay nanotubes as alternative catalyst to metal nanoparticles in H2 production from methanolysis of sodium borohydride. Fuel Processing Technology, 158, 1–8. https://doi.org/10.1016/j.fuproc.2016.12.009
31. Wang, F., Zhang, Y., Wang, Y., Luo, Y., Chen, Y., & Zhu, H. (2018). Co-P nanoparticles supported on dandelion-like CNTs-Ni foam composite carrier as a novel catalyst for hydrogen generation from NaBH4 methanolysis. International Journal of Hydrogen Energy, 43(18), 8805–8814. https://doi.org/10.1016/j.ijhydene.2018.03.140
32. Saka, C. (2023). Highly active hydrogen generation from sodium borohydride methanolysis and ethylene glycolysis reactions using protonated chitosan-zeolite hybrid metal-free particles. Applied Catalysis B: Environmental, 325, 122335. https://doi.org/10.1016/j.apcatb.2022.122335
33. Saka, C. (2022). Efficient and durable H2 production from NaBH4 methanolysis using N doped hybrid g-C3N4-SiO2 composites with ammonia as a nitrogen source. Fuel, 324, 124594. https://doi.org/10.1016/j.fuel.2022.124594
34. Kaya, M., Bekiroğullari, M., & Saka, C. (2019). Highly efficient CoB catalyst using a support material based on Spirulina microalgal strain treated with ZnCl2 for hydrogen generation via sodium borohydride methanolysis. International Journal of Energy Research, 43(9), 4243–4252. https://doi.org/10.1002/er.4548
35. Caglar, A., Kaya, S., Saka, C., Yildiz, D., & Kivrak, H. (2024). Investigation of electrooxidation and methanolysis of sodium borohydride on activated carbon supported Co catalysts from poplar sawdust. International Journal of Hydrogen Energy, 75, 171–178. https://doi.org/10.1016/j.ijhydene.2024.01.083
36. Selvitepe, N., Balbay, A., & Saka, C. (2019). Optimisation of sepiolite clay with phosphoric acid treatment as support material for CoB catalyst and application to produce hydrogen from the NaBH4 hydrolysis. International Journal of Hydrogen Energy, 44(31), 16387–16399. https://doi.org/10.1016/j.ijhydene.2019.04.254
37. Saka, C., Eygi̇, M. S., & Balbay, A. (2021). Cobalt loaded organic acid modified kaolin clay for the enhanced catalytic activity of hydrogen release via hydrolysis of sodium borohydride. International Journal of Hydrogen Energy, 46(5), 3876–3886. https://doi.org/10.1016/j.ijhydene.2020.10.201