STRUCTURAL AND ELECTROCHEMICAL PROPERTIES OF SYNTHESIZED NANOSTRUCTURED Ca0.9Er0.1MnO3 BY HYDRAZINE NITRITE PROCEDURE
Abstract
Synthesis, structural, and electrochemical properties of nanostructured powders Ca0.9Er0.1MnO3 with perovskite-type crystal were studied. Nanopowders were prepared by the combustion method using the hydrazine nitrite procedure (HNP), which involves mixing metal nitrate salts (Ca, Mn, Er) in a stoichiometric ratio and varying the quantity of added hydrazine. In this synthetic procedure, the aim is to adjust the amount of hydrazine in order to control the combustion of the reactions, obtain the required amount of fuel energy, but also the amount that will complex the reactants in the mixture. The powders obtained by hydrazine nitrate synthesis were then calcined for 15 minutes at temperatures of 800, 900, and 1000 °C. Characterization of the synthesized and calcined samples was performed using advanced techniques such as X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and electrochemical measurements. The results clearly indicate that the amount of hydrazine added is crucial in preparing the Ca0.9Er0.1MnO3 sample. This highlights the importance of precise hydrazine dosage in optimizing the synthesis process to enhance the material's properties. Further, the electrochemical properties of the obtained perovskite nanopowders were investigated by cyclic voltammetry (CV) and electrochemical spectroscopic impedance (EIS) on perovskite-modified carbon paste electrodes. Electrochemical measurements showed improved electrochemical properties of perovskite-modified carbon paste electrodes compared to bare carbon paste electrode (CPE). The electrode modified with the material synthesized with the smallest amount of hydrazine presented the best results.
References
Ansari, A. A., Adil, S. F., Alam, M., Ahmad, N., Assal, M. E., Labis, J. P. & Alwarthan, A. 2020. Catalytic performance of the Ce-doped LaCoO3 perovskite nanoparticles. Scientific Reports, 10, 15012. https://doi.org/10.1038/s41598-020-71869-z
Bayode, A. A., Ore, O. T., Nnamani, E. A., Sotunde, B., Koko, D. T., Unuabonah, E. I., Helmreich, B. & Omorogie, M. O. 2024. Perovskite Oxides: Syntheses and Perspectives on Their Application for Nitrate Reduction. ACS Omega, 9, pp. 19770-19785. https://pubs.acs.org/doi/10.1021/acsomega.4c01487
Bispo-Jr, A. G., de Morais, A. J., Calado, C. M. S., Mazali, I. O. & Sigoli, F. A. 2022. Lanthanide-doped luminescent perovskites: A review of synthesis, properties, and applications. Journal of Luminescence, 252, 119406. https://doi.org/10.1016/j.jlumin.2022.119406
Du, J., Zhang, T., Cheng, F., Chu, W., Wu, Z. & Chen, J. 2014. Nonstoichiometric Perovskite CaMnO3−δ for Oxygen Electrocatalysis with High Activity. Inorganic Chemistry, 53, 9106-9114. https://pubs.acs.org/doi/10.1021/ic501631h
Dukić, J., Bošković, S. & Matović, B. 2009. Crystal structure of Ce-doped CaMnO3 perovskite. Ceramics International, 35, pp. 787-790. https://doi.org/10.1016/j.ceramint.2008.02.023
Durai, L. & Badhulika, S. 2022. Current Challenges and Developments in Perovskite-Based Electrochemical Biosensors for Effective Theragnostics of Neurological Disorders. ACS Omega, 7, pp. 39491-39497. https://pubs.acs.org/doi/10.1021/acsomega.2c05591
Giguère, P. A. & Liu, I. D. 1952. On the Infrared Spectrum of Hydrazine. The Journal of Chemical Physics, 20, pp. 136-140. https://doi.org/10.1063/1.1700155
Julien, C. M. & Massot, M. 2003. Lattice vibrations of materials for lithium rechargeable batteries I. Lithium manganese oxide spinel. Materials Science and Engineering: B, 97, pp. 217-230. https://doi.org/10.1016/S0921-5107(02)00582-2
Kanas, N., Williamson, B. A. D., Steinbach, F., Hinterding, R., Einarsrud, M.-A., Selbach, S. M., Feldhoff, A. & Wiik, K. 2022. Tuning the Thermoelectric Performance of CaMnO3-Based Ceramics by Controlled Exsolution and Microstructuring. ACS Applied Energy Materials, 5, pp. 12396-12407. https://pubs.acs.org/doi/10.1021/acsaem.2c02012
Katz, E. A. 2020. Perovskite: Name Puzzle and German-Russian Odyssey of Discovery. Helvetica Chimica Acta, 103, e2000061. https://doi.org/10.1002/hlca.202000061
Kraus, W. & Nolze, G. 1996. POWDER CELL - a program for the representation and manipulation of crystal structures and calculation of the resulting X-ray powder patterns. Journal of Applied Crystallography, 29, pp. 301-303. https://doi.org/10.1107/S0021889895014920
Kuganathan, N. & Chroneos, A. 2021. Defect and dopant properties in CaMnO3. AIP Advances, 11, 055106. https://doi.org/10.1063/5.0048401
Macan, J., Brleković, F., Kralj, S., Supina, A., Gracin, D., Šantić, A. & Gajović, A. 2020. Soft chemistry synthesis of CaMnO3 powders and films. Ceramics International, 46, pp. 18200-18207. https://doi.org/10.1016/j.ceramint.2020.04.142
Mary, S. B., Mohan, K. S. & Krishnan, M. M. 2024. Effect of A-site and B-site ion substitution on the electrical and thermoelectric properties of nanostructured perovskite CaMnO3. Journal of Materials Science: Materials in Electronics, 35, 600. https://doi.org/10.1007/s10854-024-12351-8
Mihaylov, M. Y., Zdravkova, V. R., Ivanova, E. Z., Aleksandrov, H. A., Petkov, P. S., Vayssilov, G. N. & Hadjiivanov, K. I. 2021. Infrared spectra of surface nitrates: Revision of the current opinions based on the case study of ceria. Journal of Catalysis, 394, pp. 245-258. https://doi.org/10.1016/j.jcat.2020.06.015
Patil, K. C. H., M. S.; Rattan, T.; Aruna, S. T. 2008. Solution Combustion Synthesis of Oxide Materials. Chemistry of Nanocrystalline Oxide Materials. Singapore: World Scientific Publishing Co. Pte. Ltd. https://doi.org/10.1142/6754
Rezaei, B. & Damiri, S. 2008. Voltammetric behavior of multi-walled carbon nanotubes modified electrode-hexacyanoferrate(II) electrocatalyst system as a sensor for determination of captopril. Sensors and Actuators B: Chemical, 134, pp. 324-331. https://doi.org/10.1016/j.snb.2008.05.004
Rigaku 2011. PDXL Integrated X-Ray Powder Diffraction Software. In: RIGAKU (ed.). Tokyo, Japan.
Rosić, M., Kljaljević, L., Jordanov, D., Stoiljković, M., Kusigerski, V., Spasojević, V. & Matović, B. 2015. Effects of sintering on the structural, microstructural and magnetic properties of nanoparticle manganite Ca1−xGdxMnO3 (x=0.05, 0.1, 0.15, 0.2). Ceramics International, 41, pp. 14964-14972. https://doi.org/10.1016/j.ceramint.2015.08.041
Rosić, M., Logar, M., Devečerski, A., Prekajski, M., Radosavljević-Mihajlović, A., Kusigerski, V., Spasojević, V. & Matović, B. 2011. Synthesis, structural and magnetic properties of nanostructured Ca0.9Gd0.1MnO3 obtained by modified glycine nitrate procedure (MGNP). Ceramics International, 37, pp. 1313-1319. https://doi.org/10.1016/j.ceramint.2010.12.015
Shannon, R. D. 1976. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica Section A, 32, pp. 751-767. https://doi.org/10.1107/S0567739476001551
Shimizu, Y., Komatsu, H., Michishita, S., Miura, N. & Yamazo, N. 1996. Sensing characteristics of hydrogen peroxide sensor using carbon-based electrode loaded with perovskite-type oxide. Sensors and Actuators B: Chemical, 34, pp. 493-498. https://doi.org/10.1016/S0925-4005(97)80021-4
Srivastava, D., Azough, F., Freer, R., Combe, E., Funahashi, R., Kepaptsoglou, D. M., Ramasse, Q. M., Molinari, M., Yeandel, S. R., Baran, J. D. & Parker, S. C. 2015. Crystal structure and thermoelectric properties of Sr–Mo substituted CaMnO3: a combined experimental and computational study. Journal of Materials Chemistry C, 3, pp. 12245-12259. https://doi.org/10.1039/C5TC02318A
Tadić, M., Marković, D., Panjan, M. & Spasojević, V. 2016. Solution combustion synthesis method and magnetic properties of synthesized polycrystalline calcium manganite CaMnO3−δ powder. Ceramics International, 42, pp. 19365-19371. https://doi.org/10.1016/j.ceramint.2016.09.109
Xia, Z.-R., Li, R.-Q., Liu, F.-F., Tong, Y., Zheng, Q.-H., Ping, Z.-Y., Zhao, W., Zhou, W.-W. & Song, M.-J. 2025. Upconversion and Downconversion Luminescence of CaLaLiTeO6:Mn4+/Er3+ Phosphors for Dual-Mode Optical Thermometry and Anti-Counterfeiting Application. Inorganics, 13, 308. https://doi.org/10.3390/inorganics13090308
Yadav, R. S., Kumar, D., Kanwal, M., Singh, A. K. & Rai, S. B. 2020. Synthesis Techniques and Applications of Perovskite Materials. In: TIAN, H. (ed.) Perovskite Materials, Devices and Integration. Rijeka: Intech Open. DOI: 10.5772/intechopen.86794
Yang, P., Tai, B., Wu, W., Zhang, J.-M., Wang, F., Guan, S., Guo, W., Lu, Y. & Yang, S. A. 2017. Tailoring lanthanide doping in perovskite CaTiO3 for luminescence applications. Physical Chemistry Chemical Physics, 19, pp. 16189-16197. https://doi.org/10.1039/C7CP01953J
International Crystallographical Database (ICDD); PDF-2, Release 2023; ICDD: Newtown Square, PA, USA, 2012.
https://icsd.products.fiz-karlsruhe.de/ (accessed on 10 September 2025).
http://powdercell-for-windows.software.informer.com/2.4/ (accessed on 10 September 2025).
Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution License that allows others to share the work with an acknowledgement of the work's authorship and initial publication in this journal.
