In situ XRD study of the crystallization process of MnOx–ZrO2 oxide
https://doi.org/10.17586/2220-8054-2026-17-1-69-80
Abstract
The crystallization process of MnOx–ZrO2 mixed oxide in different gas environments was studied by in situ X-ray diffraction and thermogravimetric analysis. The non-modified ZrO2 was used as a reference. The process of crystallization in Mn-containing sample dependents on the environment: the crystallization temperature in reducing and inert environment was 450 – 455 ◦C and in oxidizing it was 560 ◦C. Thus, the addition of manganese led to the shift of crystallization temperature to the higher values compared to reference sample ZrO2 (425 ◦C). The resulting crystalline phase was Zr1−yMnyO2 solid solution rather than pure zirconia. Mn cations seemed to stabilize the tetragonal zirconia instead of monoclinic.
Supporting agencies: The work was supported by the Ministry of Science and Higher Education of the Russian Federation within the governmental order for Boreskov Institute of Catalysis (project FWUR-2024-0032).
About the Authors
V. P. Konovalova
Boreskov Institute of Catalysis SB RAS
Russian Federation
Russian Federation
Valeria P. Konovalova
Lavrentiev Ave, 5, Novosibirsk, 630090
E. Yu. Gerasimov
Boreskov Institute of Catalysis SB RAS
Russian Federation
Russian Federation
Evgeny Yu. Gerasimov
Lavrentiev Ave, 5, Novosibirsk, 630090
Z. S. Vinokurov
Synchrotron Radiation Facility SKIF
Russian Federation
Russian Federation
Zahar S. Vinokurov
Nikol’sky Prospekt,1, Kol’tsovo, 630559
A. A. Pochtar
Boreskov Institute of Catalysis SB RAS
Russian Federation
Russian Federation
Alena A. Pochtar
Lavrentiev Ave, 5, Novosibirsk, 630090
O. A. Bulavchenko
Boreskov Institute of Catalysis SB RAS; Synchrotron Radiation Facility SKIF
Russian Federation
Russian Federation
Olga A. Bulavchenko
Lavrentiev Ave, 5, Novosibirsk, 630090
References
1. Scotti N., Bossola F., Zaccheria F., Ravasio N. Copper–zirconia catalysts: Powerful multifunctional catalytic tools to approach sustainable processes. Catalysts, 2020, 10 (2), 168.
2. Goscianska J., Ziolek M., Gibson E., Daturi M. Novel mesoporous zirconia-based catalysts for WGS reaction. Appl. Catal. B Environ., 2010, 97, P. 49–56.
3. Liu J., Zhao Z., Xu C., Liu J. Structure, synthesis, and catalytic properties of nanosize cerium-zirconium-based solid solutions in environmental catalysis. Chinese J. Catal., 2019, 40, P. 1438–1487.
4. Khurshid M., Al-Daous M. A., Hattori H., Al-Khattaf S.S. Effects of hydrogen on heptane isomerization over zirconium oxide modified with tungsten oxide and platinum. Appl. Catal. A Gen., 2009, 362, P. 75–81.
5. Kumar A., Badoni R.P., Singhal S., Agarwal S., Tripathi A.R. Synthesis and characterization of zirconia-based catalyst for the isomerization of n-hexane. Chem. Eng. Commun., 2017, 205 (1), P. 92–101.
6. Howard C.J., Hill R.J., Reichert B.E. Structures of ZrO2 polymorphs at room temperature by high-resolution neutron powder diffraction. Acta Crystallogr., 1988, B44, P. 116–120.
7. Yanwei Z., Fagherazzi G., Polizzi S. The local structure characterization and resulting phase-transition mechanism of amorphous ZrO2. J. Mater. Sci., 1995, 30, P. 2153–2158.
8. Tiseanu C., Parvulescu V.I., Cojocaru B., Pemartin K., Sanchez-Dominguez M., Boutonnet M. In situ Raman and time-resolved luminescence investigation of the local structure of ZrO2 in the amorphous to crystalline phase transition. J. Phys. Chem. C, 2012, 116 (31), P. 16776–16783.
9. Svoboda R., Bul´anek R., Galusek D., Hadidimasouleh R., Ganjkhanlou Y. Crystal formation in vanadium-doped zirconia ceramics. Cryst. Eng. Comm., 2018, 20, P. 3105–3116.
10. Sohn J.R., Cho S.G., Pae Y.Il., Hayashi S. Characterization of vanadium oxide-zirconia catalyst. J. Catal., 1996, 159 (1), P. 170–177.
11. Ushakov S.V., Brown C.E., Navrotsky A. Effect of La and Y on crystallization temperatures of hafnia and zirconia. J. Mater. Res., 2004, 19, P. 693–696.
12. Afonasenko T.N., Bulavchenko O.A., Gulyaeva T.I., Tsybulya S.V., Tsyrul’nikov P.G. Effect of the Calcination Temperature and Composition of the MnOx–ZrO2 System on Its Structure and Catalytic Properties in a Reaction of Carbon Monoxide Oxidation. Kinet. Catal., 2018, 59, P. 104–111.
13. Grabchenko M.V., Mamontov G.V., Chernykh M.V., Vodyankina O.V., Salaev M.A. Synergistic effect in ternary CeO2-ZrO2-MnOx catalysts for CO oxidation and soot combustion. Chem. Eng. Sci., 2024, 285, 119593.
14. Liberman E.Y., Kleusov B.S., Naumkin A.V. Thermal Stability and Catalytic Activity of the MnOx–CeO2 and the MnOx–ZrO2–CeO2 Highly Dispersed Materials in the Carbon Monoxide Oxidation Reaction. Inorg. Mater. Appl. Res., 2021, 12, P. 468–476.
15. L´opez E.F., Escribano V.S., Resini C., Gasllardo-Amores J.M., Busca G. A study of coprecipitated Mn-Zr oxides and their behaviour as oxidation catalysts. Appl. Catal. B Environ., 2001, 29, P. 251–261.
16. Qu Y., Zhu S., Zhang L. Low-temperature catalytic combustion of benzene over Zr–Mn mixed oxides synthesized by redox-precipitation method. J. Mater. Sci., 2021, 56, P. 13540–13555.
17. Xu H., Yan N., Qu Z., Liu W., Mei J., Huang W., Zhao S. Gaseous Heterogeneous Catalytic Reactions over Mn-Based Oxides for Environmental Applications: A Critical Review. Environ. Sci. Techno., 2017, 51 (16), P. 8879–8892.
18. Koh D.J., Chung J.S., Kim Y.G., Lee J.S., Nam I., Moon S.H. Structure of MnZr mixed oxide catalysts and their catalytic properties in the CO hydrogenation reaction. Journal of Catalysis., 1992, 138, P. 630–639.
19. Choudhary V.R., Uphade B.S., Pataskar S.G. Low temperature complete combustion of dilute methane over Mn-doped ZrO2 catalysts: Factors influencing the reactivity of lattice oxygen and methane combustion activity of the catalyst. Appl. Catal. A Gen., 2002, 227 (1–2), P. 29–41.
20. Bulavchenko O.A., Konovalova V.P., Saraev A.A., Kremneva A.M., Rogov V.A., Gerasimov E.Y., Afonasenko T.N. The Catalytic Performance of CO Oxidation over MnOx–ZrO2 Catalysts: The Role of Synthetic Routes. Catalysts., 2023, 13, 57.
21. Aulchenko V.M., Evdokov O.V., Kutovenko V.D., Pirogov B.Ya., Sharafutdinov M.R. One-coordinate X-ray detector OD-3M. Nucl. Instruments Methods Phys. Res. Sect. A Accel. Spectrometers, Detect. Assoc. Equip., 2009, 603, P. 76–79.
22. Kabekkodu S.N., Dosen A., Blanton T.N. PDF–5+: A comprehensive powder diffraction file™ for materials characterization. Powder Diffr., 2024, 39, P. 47–59.
23. Degen T., Sadki M., Bron E., K¨onig U., N´enert G. The high score suite. Powder Diffraction., 2014, 29, S13–S18.
24. Patterson A.L. The Scherrer Formula for X-ray Particle Size Determination. Phys. Rev., 1939, 56, 978.
25. Qiu X., Thompson J.W., Billinge S.J.L. PDFgetX2: A GUI-driven program to obtain the Pair Distribution Function from X-ray Powder Diffraction Data. J. Appl. Cryst., 2004, 37, 678.
26. Farrow C.L., Juhas P., liu J.W., Bryndin D., Boˇzin E.S. PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals. J. Phys. Condens. Matter., 2007, 19, 33.
27. Bulavchenko O.A., Vinokurov Z.S., Afonasenko T.N., Tsyrul P.G. Reduction of mixed Mn–Zr oxides: in situ XPS and XRD studies. Dalt. Trans., 2015, 44, P. 15499–15507.
28. Shannon R.D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr., 1976, A32, P. 751–767.
29. Vanderbilt D., Zhao X., Ceresoli D. Structural and dielectric properties of crystalline and amorphous ZrO2. Thin Solid Films., 2005, 486, P. 125– 128.
30. Aguilar D.H., Torres-Gonzalez L.C., Torres-Martinez L.M., Lopez T., Quintana P. A study of the crystallization of ZrO2 in the sol-gel system: ZrO2-SiO2. J. Solid State Chem., 2001, 158, P. 349–357.
31. Prasad K., Pinjari D.V., Pandit A.B., Mhaske S.T. Synthesis of zirconium dioxide by ultrasound assisted precipitation: Effect of calcination temperature. Ultrason. Sonochem., 2011, 18, P. 1128–1137.
32. Afonasenko T.N., Glyzdova D.V., Yurpalov V.L., Konovalova V.P., Rogov V.A., Gerasimov E.Y., Bulavchenko O.A. The Study of Thermal Stability of Mn–Zr–Ce, Mn–Ce and Mn-Zr Oxide Catalysts for CO Oxidation. Materials., 2022, 15 (21), 7553.
Review
For citations:
Konovalova V.P., Gerasimov E.Yu., Vinokurov Z.S., Pochtar A.A., Bulavchenko O.A. In situ XRD study of the crystallization process of MnOx–ZrO2 oxide. Nanosystems: Physics, Chemistry, Mathematics. 2026;17(1):69-80. https://doi.org/10.17586/2220-8054-2026-17-1-69-80
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