Mechanism of the Hydrazine Monohydrate Decomposition by Means of IR Spectroscopy  In Situ

V. A. Matyshak; Матышак В. А.; O. N. Silchenkova; Сильченкова О. Н.; A. N. Ilichev; Ильичев А. Н.; M. Ya. Bykhovsky; Быховский М. Я.; R. А. Mnatsakanyan; Мнацаканян Р. А.

doi:10.31857/S0453881123060114

Mechanism of the Hydrazine Monohydrate Decomposition by Means of IR Spectroscopy In Situ

Authors: Matyshak V.A.¹, Silchenkova O.N.¹, Ilichev A.N.¹, Bykhovsky M.Y.¹, Mnatsakanyan R.А.²
Affiliations:
1. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences
2. Nalbandyan Institute of Chemical Physics National Academy of Sciences
Issue: Vol 64, No 6 (2023)
Pages: 773-784
Section: ARTICLES
URL: https://kazanmedjournal.ru/0453-8811/article/view/660328
DOI: https://doi.org/10.31857/S0453881123060114
EDN: https://elibrary.ru/KVCILK
ID: 660328

Cite item

Full Text

Open Access
Restricted Access

Access granted
Restricted Access

Subscription or Fee Access

Abstract

Pd-containing catalysts (1%Pd/Al₂O₃ and 5%Pd/Al₂O₃) deposited on aluminum oxide were studied in the decomposition reaction of hydrazine monohydrate. According to in situ IR spectroscopy, it was found that hydrazine monohydrate is adsorbed on the coordination unsaturated centers of the catalyst surface in a linear form. When the temperature rises, the adsorbed hydrazine monohydrate loses a water molecule, which is accompanied by a change in the geometry of the molecular complex. Adsorption of hydrazine on a support and its diffusion onto palladium clusters is a more advantageous process than direct adsorption on active centers. This circumstance shows that the hydrazine adsorbed on the support can be an intermediate of its decomposition process. The studied catalysts have a maximum activity in the temperature range of 100–120°C, while the ratio of hydrogen and nitrogen concentrations in the reaction products was equal to 2, which corresponds to 100% selectivity for hydrogen. As the reaction temperature increases, the selectivity decreases significantly. The explanation of the high selectivity for hydrogen at low temperatures is due to the fact that the adsorption of N₂H₄ is carried out through the formation of hydrogen–metal bonds. The hydrogen–metal bond strength in such a complex is higher than the nitrogen–metal bond strength, hence the barrier for breaking the N–H bond is lower than the barrier for breaking N–N bond, which leads to breaking N–H bond and preserving the N–N bond. At elevated temperatures, some of the hydrogen atoms formed recombine, the other reacts with the surface complexes of hydrazine to form the intermediate NH₃–NH₃, the breaking of the bond in which leads to the formation of ammonia molecules in the gas phase.

Keywords

hydrogen, hydrazine, hydrazine monohydrate, intermediates, IR spectroscopy in situ, fuel cell

References

Hydrogen and other Alternative Fuels for Air and Ground Transportation. Ed. Pohl H.W. UK: Wiley, 1995. 206 p.
Deng Z.-Y., Ferreira J.M.F., Sakka Y. Hydrogen generation materials for portable applications // J. Am. Ceram. Soc. 2008. V. 91. № 12. P. 3825.
Nikolaidis P., Poullikkas A. // Renew. Sustain. Energy Rev. 2017. V. 67. P. 597.
Khan Z. // Int. J. Hydrogen energy. 2019. V. 44. P. 1150.
Lang C., Jia Y., Yao X. // Energy Storage Mater. 2020. V. 26. P. 290.
Martin C., Quintanilla A., Vega G., Casas J.A. // Appl. Catal. B: Environ. 2022. V. 317. P. 121802.
Al-Thabaiti S.A., Khan Z., Malik M.A. // Int. J. Hydrogen Energy. 2019. V. 44. P. 16452.
Ekinci A. // Кинетика и катализ. 2020. Т. 61. № 4. С. 540.
Jiang H.L., Singh S.K., Yan J.M., Zhang X.B., Xu Q. // ChemSusChem. 2010. V. 3. P. 541.
Lan R., Irvine J.T.S., Tao S. // Int. J. Hydrogen Energy. 2012. V. 37. P. 1482.
Singh S.K., Xu Q. // Catal. Sci. Technol. 2013. V. 3. P. 1889.
Song J., Ran R., Shao Z. // Int. J. Hydrogen Energy. 2010. V. 35. P. 7919.
Zheng M., Cheng R., Chen X., Li N., Li L., Wang X., Zhang T. // Int. J. Hydrogen Energy. 2005. V. 30. P. 1081.
Al-Thubaiti K.S., Khan Z. // Int. J. Hydrogen energy. 2020. V. 45. P. 13960.
Motta D., Barlocco I., Bellomi S., Villa A., Dimitratos N. // Nanomaterials. 2021. V. 11. P. 1340.
Schmidt E.W. Hydrazine and its Derivatives, 2nd edition. New York: Wiley Interscience, 2001. 2232 p.
Manukyan K.V., Cross A., Rouvimov S., Miller J., Mukasyan A.S., Wolf E.E. // Appl. Catal. A: Gen. 2014. V. 476. P. 47.
Singh S.K., Zhang X.-B., Xu Q. // J. Am. Chem. Soc. 2009. V. 131. P. 9894.
Singh S.K., Zhang X.-B., Xu Q. // Eur. J. Inorg. Chem. 2011. V. 14. P. 2232.
Jain P., Anila K.A., Vinod C.P. // Chem. Select. 2019. V. 4. № 9. P. 2734.
Tong D.G. // J. Mater. Chem. A. 2019. V. 7. P. 20442.
Матышак В.А., Сильченкова О.Н. // Кинетика и катализ. 2022. Т. 63. № 4. С. 405. (Matyshak V.A., Silchenkova O.N. // Kinet. Catal. 2022. V. 63. № 4.).
Block J., Schulz-Ekloff G. // J. Catal. 1973. V. 30. P. 327.
Gosser R.C., Tompkins F.C. // Trans. Faraday Soc. 1971. V. 67. P. 545
Aika K.I., Ohhata T., Ozaki A. // J. Catal. 1970. V. 19. P. 140.
Wood B.J., Wise H. // J. Catal. 1975. V. 39. P. 471.
Maurel R., Menezo J.C. // J. Catal. 1978. V. 51. P. 293.
Swarc M. // Proc. Roy. Soc. A. 1949. V. 198. P. 267.
Contour J.P., Pannetier G. // J. Catal. 1972. V. 24. P. 434.
Amores J.M.G., Escribano V.S., Ramis G., Busca G. // Appl.Catal. B: Environ. 1997. V. 13 P. 45.
Ramis G., Li Y., Busca G. // Catal. Today. 1996. V. 28. P. 373.
Chuang C.-C., Shiu J.-S., Lin J.L. // Phys. Chem. Chem. Phys. 2000.V. 2. P. 2629.
Sathyanarayana D.N., Nicholls D. // Spectrochim. Acta, Part A. 1978. V. 34. P. 263.
Firdous N., Janjua N.K., Qazi I., Wattoo M.H.S. // Int. J. Hydrogen Energy. 2016. V. 41. P. 984.
Matyshak V.A., Krylov O.V. // Catal. Today. 1995. V. 25. P. 1.
Valden M., Keiski R.L., Xiang N., Pere J., Aaltonen J., Pessa M., Maunula T., Savimaki A., Lahti A., Harkonen M. // J. Catal. 1996. V. 161. P. 614.
Choi K.I., Vannice M.A. // J. Catal. 1991. V. 127. P. 465.
Матышак В.А., Крылов О.В. // Кинетика и катализ. 2002. Т. 43. С. 422. (Matyshak V.A., Krylov O.V. // Kinet. Catal. 2002. V. 43. № 3. P. 391.)
Contour J.P., Pannetier G. // Bull. Soc. Chim. France. 1970. P. 4260.
Sacconi L., Sabatini A. // J. Inorg. Nucl. Chem. 1963. V. 25. P. 1389.
Durig J.R., Bush S.F., Mercer E.E. // J. Chem. Phys. V. 1965. V. 44. P. 4238.
Sathyanarayana D.N., Nicholls D. // Spectrochim. Acta. Part A. 1978. V. 34. P. 263.
Amores J.M.G., Escribano V.S., Ramis G., Busca G. //Appl.Catal. B: Environ. 1997. V. 13. P. 45.
Ramis G., Li Y., Busca G. // Catal. Today. 1996. V. 28. P. 373.
Lieske H., Lietz G., Sprindler H., Volter J. // J. Catal. 1983. V. 81. P. 8.
Zhanga P.X., Wanga Y.G., Huang Y.Q., Zhang T., Wua G.S., Li J. // Catal. Today. 2011. V. 165. P. 80.
Alberas D.J., Kiss J., Liu Z.-M., White J.M. // Surf. Sci. 1992. V. 278. P. 51.