PROCEEDINGS OF THE SHEVCHENKO SCIENTIFIC SOCIETY

Chemical Sciences

Archive / Volume LXXV 2024

Liliya BAZYLYAK1, Yaroslav PILYUK1, Ihor HALATYN1, Andriy KYTSYA1, 2, Ihor ZAVALIY2

1Department of Physical Chemistry of Fossil Fuels of the Institute of Physical Organic Chemistry and Coal Chemistry named after L. М. Lytvynenko of the National academy of Ukraine, Naukova Str. 3а, 79060, Lviv, Ukraine
e-mail: bazylyak.liliya@gmail.com

2Physico-Mechanical Institute named after G. V. Karpenko National Academy of Sciences of Ukraine 5 Naukova Str., Lviv, 79060, Ukraine

DOI: https://doi.org/10.37827/ntsh.chem.2024.75.136

CATALYTIC ACTIVITY OF NICKEL NANOPARTICLES IN THE PROCESS OF HYDROGEN GENETAYION BY THE DECOMPOSITION OF HYDRAZINE

Catalytic systems based on nickel nanoparticles (NiNPs) can be used to reduce the nitroaromatic compounds with sodium borohydride, to obtain synthesis gas from reducing raw materials, etc. The mechanism of catalytic action of nickel in such processes is similar to the mechanism of action of Raney nickel, however, the nanosize of nickel particles makes it possible to create a much wider range of catalytic systems due to the use of various carriers. Research into the use of NiNPs in hydrogen generation processes deserves the special attention. In particular, it is known that the NiNPs are an effective catalyst for the decomposition of alkaline NaBH4 solutions. Another promising source of hydrogen is hydrazine hydrate, which has a high hydrogen capacity, solid reaction products are not formed during its decomposition, and it is also economically more profitable compared to NaBH4. Recently it was shown that in alkaline solutions of ethylene glycol in the presence of NiNPs, hydrazine is decomposed according to the reaction N2H4 ➔ N2↑ + 2H2↑, i. e., only nitrogen and hydrogen are reaction products. Therefore, the purpose of this work is to investigate the catalytic activity of NiNPs in the process of generating hydrogen by the decomposition of hydrazine. NiNPs were synthesized by the reduction of nickel acetate with hydrazine in an alkaline solution of ethylene glycol in the absence of surfactants. Using the SEM, EDX and XRD it was shown that the obtained NiNPs are spherical in shape with a size of 150-200 nm and do not contain nickel hydroxide residues. The catalytic activity of NiNPs in the process of hydrogen generation by decomposition of an alkaline solution of hydrazine in ethylene glycol was investigated using the volumetric method. It was shown that the rate of hydrogen evolution is 130 ml/min per 1 gram of catalyst, and the activation energy of the catalytic decomposition of hydrazine is 65 ± 2 kJ/mol.

Keywords: nickel nanoparticles, hydrogen generation, hydrazine, catalysis.

References:

    1. Raney M. Method of producing finely-divided nickel. USA Patent No 1628190A. Publ. 10. 05. 1927.
    2. Lu S., Wu J., Peng H., Chen Y. Carbon-supported Raney nickel catalyst for acetone hyd-rogenation with high selectivity. Molecules. 2020. Vol. 25(4). P. 803. (https://doi.org/10.3390/molecules25040803).
    3. García B., Moreno J., Iglesias J., Melero J. A., Morales G. Transformation of glucose into sorbitol on Raney nickel catalysts in the absence of molecular hydrogen: Sugar disproportionation vs catalytic hydrogen transfer. Top. Catal. 2019. Vol. 62(5–6). P. 570–578. (https://doi.org/10.1007/s11244-019-01156-3).
    4. Zhang K., Suh J. M., Choi J. W., Jang H. W., Shokouhimehr M., Varma R. S. Recent advances in the nanocatalyst-assisted NaBH4 reduction of nitroaromatics in water. ACS Omega. 2019. Vol. 4(1). P. 483–495. (https://doi.org/10.1021/acsomega.8b03051).
    5. Gai C., Zhu N., Hoekman S.K., Liu Z., Jiao W., Peng N. Highly dispersed nickel nano-particles supported on hydrochar for hydrogen-rich syngas production from catalytic reforming of biomass. Energ. Convers. Manag. 2019. Vol. 183. P. 474–484. (https://doi.org/10.1016/j.enconman.2018.12.121).
    6. Huang J., Zhu C., Lian X., Feng H., Sun J., Wang L., Jin H. Catalytic supercritical water gasification of glucose with in-situ generated nickel nanoparticles for hydrogen production. Int. J. Hydrogen. Energ. 2019. Vol. 44(38). P. 21020–21029. (https://doi.org/10.1016/j.ijhydene.2019.04.184).
    7. Lee J., Shin H., Choi K. S., Lee J., Choi J. Y., Yu H. K. Carbon layer supported nickel catalyst for sodium borohydride (NaBH4) dehydrogenation. Int. J. Hydrogen. Energ. 2019. Vol. 44(5). P. 2943–2950. (https://doi.org/10.1016/j.ijhydene.2018.11.218).
    8. Kytsya A., Berezovets V., Verbovytskyy Y., Bazylyak L., Kordan V., Zavaliy I., Yartys V. Bimetallic Ni-Co nanoparticles as an efficient catalyst of hydrogen generation via hydrolysis of NaBH4. J. Alloys Compd. 2022. Vol. 908. Article ID 164484. (https://doi.org/10.1016/j.jallcom.2022.164484).
    9. Yang P., Yang L., Gao Q., Luo Q., Zhao X., Mai X., Guo Z. Anchoring carbon nanotubes and post-hydroxylation treatment enhanced Ni nanofiber catalysts towards efficient hydrous hydrazine decomposition for effective hydrogen generation. Chem. Commun. 2019. Vol. 55(61). P. 9011–9014. (https://doi.org/10.1039/C9CC04559G).
    10. Qiu Y. P., Shi Q., Zhou L. L., Chen M. H., Chen C., Tang P. P., Wang P. NiPt nanoparticles anchored onto hierarchical nanoporous N-doped carbon as an efficient catalyst for hydrogen generation from hydrazine monohydrate. ACS Appl. Mater. Interf. 2020. Vol. 12. P. 18617–18624. (https://doi.org/10.1021/acsami.0c03096).
    11. Qin S. H., Qiu Y. P., Chen M. H., Wang P. Noble-metal-free Ni 10 MoCox/Mo–Ni–O as an active and durable catalyst for hydrogen generation from hydrazine monohydrate. J. Mater. Chem. A. 2023. Vol. 11(39). P. 21411–21419. (https://doi.org/10.1039/D3TA04602H).
    12. Kytsya A. R., Verbovytskyy Y. V., Vlad H. I., Bazylyak L. I., Kordan V. M., Berezovets V. V., Zavaliy I. Y. Synthesis and hydrogenation properties of Ni–Co bimetallic nanoparticles. Appl. Nanosci. 2023. Vol. 13(7). P. 5265–5276. (https://doi.org/10.1007/s13204-022-02752-8).
    13. Kytsya A., Pobigun-Halaiska O., Bazylyak L., Berezovets V., Verbovytskyy Y. Synthesis of nickel nanopowders in water/ethylene glycol solutions. The influence of the solution composition on the particles’ size. Visnyk Lviv Univ., Ser. Chem. 2018. Vol. 59(2). P. 460–466. (in Ukrainian). (https://doi.org/10.30970/vch.5902.460).
    14. Kytsya A., Pobigun-Halaiska O., Bazylyak L., Zasadnyy T., Verbovytskyy Y., Lutyy P. Synthesis of nickel nanopowders in water/ethylene glycol solutions. The influence of precursor concentration and temperature on the particles’ size. Visnyk Lviv Univ., Ser. Chem. 2019. Vol. 60(2). P. 421–427 (in Ukrainian). (https://doi.org/10.30970/vch.6002.421).
    15. Kytsya A. R., Bazylyak L. I., Zavaliy I. Y., Verbovytskyy Y. V., Zavalij P. Synthesis, structure and hydrogenation properties of Ni–Cu bimetallic nanoparticles. Appl. Nanosci. 2022. Vol. 12(4). P. 1183–1190. (https://doi.org/10.1007/s13204-021-01742-6).
    16. Rodriguez-Carvajal J. Recent advances in magnetic structure determination by neutron powder diffraction. Phys. B: Condens. 1993. Vol. 192. P. 55–69. (https://doi.org/10.1016/0921-4526(93)90108-I).
    17. Wu S. H., Chen D. H. Synthesis and characterization of nickel nanoparticles by hydrazine reduction in ethylene glycol. J. Colloid Interface Sci. 2003. Vol. 259. P. 282–286. (https://doi.org/10.1016/S0021-9797(02)00135-2).
    18. Monshi A., Foroughi M. R., Monshi M. R. Modified Scherrer equation to estimate more accurately nano-crystallite size using XRD. WJNSE. 2012. Vol. 2(3). P. 154–160. (https://doi.org/10.4236/wjnse.2012.23020).


How to Cite

BAZYLYAK L., PILYUK Ya., HALATYN I., KYTSYA A., ZAVALIY I. CATALYTIC ACTIVITY OF NICKEL NANOPARTICLES IN THE PROCESS OF HYDROGEN GENETAYION BY THE DECOMPOSITION OF HYDRAZINE. Proc. Shevchenko Sci. Soc. Chem. Sci. 2024. Vol. LXXV. P. 136-143.

Download the pdf