Caffeine Coated Iron Oxide Crustacean for Ammonia Borane Dehydrogenation Development of Magnetic Nickel Nanoparticles

Year 2025, Volume: 14 Issue: 1, 633 - 646, 26.03.2025

Erhan Onat

https://doi.org/10.17798/bitlisfen.1628206

Abstract

The aim of this study was to develop nickel (Ni) nanoclusters with caffeine-coated magnetic iron oxide (Fe3O4) center shells for the catalytic hydrolysis of ammonia borane (AB). In the study, magnetic iron oxide (MIO) clusters were obtained by hydrothermal treatment. These clusters were first coated with caffeine according to the reflux method at 150 oC for 12 hours, and then Ni was decorated on these clusters by impregnation method. Magnetic Ni catalyst (Ni@C/Fe3O4) was synthesized by dropping 10 M 20 mL sodium borohydride (NaBH4-SBH) into the Ni-C/ Fe3O4 magnetic nanoclusters in solution as a result of the loading processes carried out at room conditions. After filtration, washing and drying in nitrogen atmosphere, the crumbled catalyst was identified by advanced identification techniques (FT-IR, BET, SEM, EDX, XPS) and used in AB hydrolysis.
The solvate medium, catalyst amount, AB concentration, temperature and repeated use parameters were investigated for AB catalytic hydrolysis. As a result of the optimization at 303 K, the best hydrogen production was determined as 7873 mL/g.min using 2.5 % NaOH, 30 mg catalyst and 300 mM AB. The catalyst cycle frequency (TOF) was measured as 1447 s-1. As a result of reaction kinetics investigations, it was determined that the reaction was 1st order and the reaction activation energy was 35.07 kJ/mol.

Keywords

Ammonia borane, Dehydrogenation, Fe3O4, Hydrolysis, Catalyst, Ni@C/Fe3O4

Ethical Statement

The study is complied with research and publication ethics.

References

• P. J. Megía, A. J. Vizcaíno, J. A. Calles, and A. Carrero, “Hydrogen production technologies: From fossil fuels toward renewable sources. A mini review,” Energy Fuels, vol. 35, no. 20, pp. 16403–16415, 2021.
• A. Pareek, R. Dom, J. Gupta, J. Chandran, V. Adepu, and P. H. Borse, “Insights into renewable hydrogen energy: Recent advances and prospects,” Mater. Sci. Energy Technol., vol. 3, pp. 319–327, 2020.
• E. Onat, F. A. Celik, E. Karabulut, and M. S. Izgi, “High availability and outstanding catalytic activity in sodium borohydride hydrolytic dehydrogenation of CQD/GO@Co catalyst by green synthesis: Experimental and computational perspective,” Int. J. Hydrogen Energy, vol. 83, pp. 903–915, 2024.
• A. Midilli and I. Dincer, “Hydrogen as a renewable and sustainable solution in reducing global fossil fuel consumption,” Int. J. Hydrogen Energy, vol. 33, no. 16, pp. 4209–4222, 2008.
• M. A. Rosen and S. Koohi-Fayegh, “The prospects for hydrogen as an energy carrier: an overview of hydrogen energy and hydrogen energy systems,” Energy Ecol. Environ., vol. 1, no. 1, pp. 10–29, 2016.
• E. L. V. Eriksson and E. M. Gray, “Optimization and integration of hybrid renewable energy hydrogen fuel cell energy systems—A critical review,” Appl. Energy, vol. 202, pp. 348–364, 2017.
• W. Jiao et al., “Magnetic Ni and Ni/Pt hollow nanospheres and their catalytic activities for hydrolysis of ammonia borane,” J. Mater. Chem. A Mater. Energy Sustain., vol. 2, no. 43, pp. 18171–18176, 2014.
• E. Onat, F. A. Çelik, Ö. Şahin, E. Karabulut, and M. S. İzgi, “H2 production from ammonia borane hydrolysis with catalyst effect of titriplex® III carbon quantum dots supported by ruthenium under different reactant conditions: Experimental study and predictions with molecular modelling,” Int. J. Hydrogen Energy, 2024.
• U. B. Demirci, “Ammonia borane, a material with exceptional properties for chemical hydrogen storage,” Int. J. Hydrogen Energy, vol. 42, no. 15, pp. 9978–10013, 2017.
• W.-W. Zhan, Q.-L. Zhu, and Q. Xu, “Dehydrogenation of ammonia borane by metal nanoparticle catalysts,” ACS Catal., vol. 6, no. 10, pp. 6892–6905, 2016.
• R. P. Shrestha, H. V. K. Diyabalanage, T. A. Semelsberger, K. C. Ott, and A. K. Burrell, “Catalytic dehydrogenation of ammonia borane in non-aqueous medium,” Int. J. Hydrogen Energy, vol. 34, no. 6, pp. 2616–2621, 2009.
• A. K. Figen, “Dehydrogenation characteristics of ammonia borane via boron-based catalysts (Co–B, Ni–B, Cu–B) under different hydrolysis conditions,” Int. J. Hydrogen Energy, vol. 38, no. 22, pp. 9186–9197, 2013.
• M. S. İzgi, Ö. Şahin, E. Onat, and S. Horoz, “Metanolde sentezlenen Co-B katalizörün sodyum hidrolizi üzerine etkisi,” J. Inst. Sci. Technol., vol. 7, no. 4, pp. 151–160, 2017.
• N. C. Smythe and J. C. Gordon, “Ammonia borane as a hydrogen carrier: Dehydrogenation and regeneration,” Eur. J. Inorg. Chem., vol. 2010, no. 4, pp. 509–521, 2010.
• H. Cui, Y. Liu, and W. Ren, “Structure switch between α-Fe₂O₃, γ-Fe₂O₃ and Fe₃O₄ during the large scale and low temperature sol–gel synthesis of nearly monodispersed iron oxide nanoparticles,” Adv. Powder Technol., vol. 24, no. 1, pp. 93–97, 2013.
• M. Seehra, Magnetic Spinels: Synthesis, Properties and Applications, Bod–Books on Demand, 2017.
• M. S. İzgi, M. Ş. Ece, H. Ç. Kazici, Ö. Şahin, and E. Onat, “Hydrogen production by using Ru nanoparticle decorated with Fe₃O₄@SiO₂-NH₂ core-shell microspheres,” Int. J. Hydrogen Energy, vol. 45, no. 55, pp. 30415–30430, 2020.
• Y. Hao and A. S. Teja, “Continuous hydrothermal crystallization of α–Fe₂O₃ and Co₃O₄ nanoparticles,” J. Mater. Res., vol. 18, no. 2, pp. 415–422, 2003.
• S. Gil, C. R. Correia, and J. F. Mano, “Magnetically labeled cells with surface-modified Fe₃O₄ spherical and rod-shaped magnetic nanoparticles for tissue engineering applications,” Adv. Healthcare Mater., vol. 4, no. 6, pp. 883–891, 2015.
• S. Shabestari Khiabani, M. Farshbaf, A. Akbarzadeh, and S. Davaran, “Magnetic nanoparticles: preparation methods, applications in cancer diagnosis and cancer therapy,” Artif. Cells Nanomed. Biotechnol., vol. 45, no. 1, pp. 6–17, 2017.
• D. V. Voronin et al., “In vitro and in vivo visualization and trapping of fluorescent magnetic microcapsules in a bloodstream,” ACS Appl. Mater. Interfaces, vol. 9, no. 8, pp. 6885–6893, 2017.
• L. Xu, M.-J. Kim, K.-D. Kim, Y.-H. Choa, and H.-T. Kim, “Surface modified Fe₃O₄ nanoparticles as a protein delivery vehicle,” Colloids Surf. A Physicochem. Eng. Asp., vol. 350, no. 1–3, pp. 8–12, 2009.
• S. Liu, H. Chen, X. Lu, C. Deng, X. Zhang, and P. Yang, “Facile synthesis of copper (II) immobilized on magnetic mesoporous silica microspheres for selective enrichment of peptides for mass spectrometry analysis,” Angew. Chem. Int. Ed., vol. 41, no. 49, pp. 7557–7561, 2010.
• E. Onat, “Synthesis of a cobalt catalyst supported by graphene oxide modified perlite and its application on the hydrolysis of sodium borohydride,” Synth. Met., vol. 306, 2024.
• E. Onat and S. Ekinci, “A new material fabricated by the combination of natural mineral perlite and graphene oxide: Synthesis, characterization, and methylene blue removal,” Diam. Relat. Mater., vol. 143, 110848, 2024.
• Ö. Şahin, S. Ekinci, M. S. İzgi, and E. Onat, “Effect of different solvents on hydrogen production from hydrolysis of potassium borohydride with a new and active Ni-based catalyst synthesized by green synthesis,” Int. J. Hydrogen Energy, 2024.
• P. Panneerselvam, N. Morad, and K. A. Tan, “Magnetic nanoparticle (Fe₃O₄) impregnated onto tea waste for the removal of nickel (II) from aqueous solution,” J. Hazard. Mater., vol. 186, no. 1, pp. 160–168, 2011.
• A. Mulyasuryani, R. Tjahjanto, and R. Andawiyah, “Simultaneous voltammetric detection of acetaminophen and caffeine base on cassava starch–Fe₃O₄ nanoparticles modified glassy carbon electrode,” Chemosensors, vol. 7, no. 4, p. 49, 2019.
• H. İ. Ulusoy, E. Yılmaz, and M. Soylak, “Magnetic solid phase extraction of trace paracetamol and caffeine in synthetic urine and wastewater samples by a using core-shell hybrid material consisting of graphene oxide/multiwalled carbon nanotube/Fe₃O₄/SiO₂,” Microchem. J., vol. 145, pp. 843–851, 2019.
• H. W. Di, Y. L. Luo, F. Xu, Y. S. Chen, and Y. F. Nan, “Fabrication and caffeine release from Fe₃O₄/P(MAA-co-NVP) magnetic microspheres with controllable core-shell architecture,” J. Biomater. Sci., vol. 22, no. 4–6, pp. 557–576, 2011.
• E. Onat, M. S. İzgi, Ö. Şahin, and C. Saka, “Nickel/nickel oxide nanocomposite particles dispersed on carbon quantum dot from caffeine for hydrogen release by sodium borohydride hydrolysis: Performance and mechanism,” Diam. Relat. Mater., 2024.
• E. Onat and S. Ekinci, “Study of the sodium borohydride hydrolysis reaction’s performance via a kaolin-supported Co–Cr bimetallic catalyst,” Afyon Kocatepe Univ. J. Sci. Eng., vol. 24, pp. 1061–1070, 2024.
• S. Ekinci and E. Onat, “Activated carbon assisted cobalt catalyst for hydrogen production: Synthesis and characterization,” Balıkesir Univ. J. Inst. Sci., vol. 26, no. 2, pp. 455–471, 2024.
• E. Onat, S. Ekinci, Ö. Şahin, and M. S. İzgi, “Effective and environmentally friendly Co nanocatalyst on sodium borohydride hydrolysis in different solvents,” Int. J. Hydrogen Energy, 2025.
• L. Zhou, T. Zhang, Z. Tao, and J. Chen, “Ni nanoparticles supported on carbon as efficient catalysts for the hydrolysis of ammonia borane,” Nano Res., vol. 7, no. 5, pp. 774–781, 2014.
• X. Yang, F. Cheng, J. Liang, Z. Tao, and J. Chen, “PtxNi₁₋ₓ nanoparticles as catalysts for hydrogen generation from hydrolysis of ammonia borane,” Int. J. Hydrogen Energy, vol. 34, no. 21, pp. 8785–8791, 2009.
• J. Zhang, X. Zheng, W. Yu, X. Feng, and Y. Qin, “Unravelling the synergy in platinum-nickel bimetal catalysts designed by atomic layer deposition for efficient hydrolytic dehydrogenation of ammonia borane,” Appl. Catal. B, vol. 306, 121116, 2022.
• X. Yang, F. Cheng, J. Liang, Z. Tao, and J. Chen, “Carbon-supported Ni₁₋ₓ@Ptx (x = 0.32, 0.43, 0.60, 0.67, and 0.80) core-shell nanoparticles as catalysts for hydrogen generation from hydrolysis of ammonia borane,” Int. J. Hydrogen Energy, vol. 36, no. 3, pp. 1984–1990, 2011.
• Ö. Metin, S. Özkar, and S. Sun, “Monodisperse nickel nanoparticles supported on SiO₂ as an effective catalyst for the hydrolysis of ammonia–borane,” Nano Res., vol. 3, no. 9, pp. 676–684, 2010.