Highly dispersed chromium(III) molybdate powders obtained by solid phase synthesis

Objectives. To obtain highly dispersed powders of chromium(III) molybdate Cr₂(MoO₄)₃ by solid phase synthesis and to study their porous structure.
Methods. After stirring in water, a mixture of Cr₂O₃ and MoO₃ oxide powders was dried in air and subjected to heat treatment in the temperature range of 600–800°C. After heat treatment, the products were identified by X-ray phase and sedimentation analysis. The specific surface area was measured using the Brunauer–Emmett–Teller static adsorption method. Porosity parameters were measured using the Barrett–Joyner–Halenda (BJH) method.
Results. The Gibbs free energy ΔG of the reaction between chromium and molybdenum oxides was calculated and it was shown that the process is characterized by a significant negative value of ΔG. Concurrently, the Gibbs energy exhibits a relatively weak dependence on temperature. The highly dispersed chromium(III) molybdate powders with specific surface area of 15.3–29.7 m²·g⁻¹ obtained in this way were pure according to X-ray diffraction analysis. A study of the volume, diameter, and pore size distribution was conducted through the utilization of nitrogen adsorption–desorption isotherms in accordance with the BJH model.
Conclusions. It was demonstrated that Cr₂(MoO₄)₃ powders possess a mesoporous structure and are distinguished by a bimodal pore system comprising small pores with a diameter of 2–3 nm and larger pores with a diameter ranging from 15 to 30 nm.

1. Tyagi A.K., Achary S.N., Mathews M.D. Phase Transition and Negative Thermal Expansion in A2(MoO4)3 System (A=Fe3+, Cr3+ and Al3+). J. Alloys Compd. 2002;339(1–2):1377–1383. https://doi.org/10.1016/S0925-8388(01)02003-5

2. Liu J., Sharma N. Thermal Evolution and Phase Transitions in Electrochemically Activated Sc2(MoO4) 3. Inorg. Chem. 2019;58(9):9964–9973. https://doi.org/10.1021/acs.inorgchem.9b01116

3. Pudge G.J.F., Hutchings G.J., Kondrat S.A., Morrison K., PerkinsE.F., RushbyaA.V., Bartley J.K. Iron molybdate catalysts synthesised via dicarboxylate decomposition for the partial oxidation of methanol to formaldehyde. Catal. Sci. Technol. 2022;12(14):4552–4560. http://doi.org/10.1039/D2CY00699E

4. Dias A.P.S., Rijo B., Kiennemann A., Portela M.F. Methanol oxidation over iron molybdate catalysts. Main and side reactions kinetics. Appl. Catal. A Gen. 2023;658(5):119118. https://doi.org/10.1016/j.apcata.2023.119118

5. Gurusamy L., Karuppasamy L., Anandan S., Liu C.-H., Wu J.J. Recent advances on metal molybdate-based electrode materials for supercapacitor application. J. Energy Storage. 2024;79(2):110122. https://doi.org/10.1016/j.est.2023.110122

6. El-Aryan Y.F., Melhi S. Adsorption Study of Eriochrome Black T Dye on Polyacrylonitrile Chromium molybdate Composite. Russ. J.Appl. Chem. 2024. https://doi.org/10.1134/S1070427224020125

7. Miller W., Smith C.W., Mackenzie D.S., Evans K.E. Negative thermal expansion: a review. J. Mater. Sci. 2009;44(20): 5441–5451. https://doi.org/10.1007/s10853-009-3692-4

8. Zhang Z., Sun W., Zheng Q., Liu H., Zhou M., Wang W., Chen X. Tuning the Phase Transition Temperature of Cr2(MoO4)3 by A-site Substitution of Scandium. Ceram. Int. 2018;44(18):22165–22171. https://doi.org/10.1016/j.ceramint.2018.08.329

9. Battle P.D., Cheetham A.K., Harrison W.T.A., Pollard N.J., FaberJ. The Structure and Magnetic Properties of Chromium(III) Molybdate. J. Solid State. Chem. 1985;58(2):221–225. https://doi.org/10.1016/0022-4596(85)90238-5

10. AnsariT.H., YadavaY.P. Electrical Conduction in Polycrystalline Chromium Molybdate. Mater. Lett. 1990;9(11):469–473. https://doi.org/10.1016/0167-577x(90)90120-b

11. Popov T.S., Popov B.I., Bibin V.N., Bliznakov G.M., Boreskov G.K. Catalytic Properties of ChromiumMolybdenum Oxide Catalysts in Methanol Oxidation. React. Kinet. Catal. Lett. 1975;3(2):169–175. https://doi.org/10.1007/bf02187510

12. Oudghiri-Hassani H. Synthesis, Characterization and Application of Chromium Molybdate for Oxidation of Methylene Blue Dye. J. Mater. Environ. Sci. 2018;9(2): 1051–1057. https://doi.org/10.26872/jmes.2018.9.3,117

13. Yadagiri M., Ramakrishna S., Ravi G., Suresh P., Sreenu K., Jaya-Prakash D., Vithal M. Preparation, Characterization and Photocatalytic Studies of Cr2(MoO4)3 and Nitrogen-Doped Cr2(MoO4)3. Chem. Chem. Technol. 2015;9(4):391–399. https://doi.org/10.23939/chcht09.04.391

14. Bandaru H., Mahomed A.S., Singh S., Friedrich H.B. The Effect of Varying the Metal Ratio in a Chromium Molybdate Catalysts for the Oxidative Dehydrogenation of n-octane. Mol. Catal. 2018;460(9):74–82. https://doi.org/10.1016/j.mcat.2018.09.017

15. Klissurski D., Mancheva M., IordanovaR., KunevB. Synthesis of Cr2(MoO4) 3 from Mechanically Activated Precursors. Khimiya v interesakh ustoichivogo razvitiya = Chemistry for Sustainable Development. 2005;13(2):229–232 (in Russ.).

16. Batanov A.A., Rumyantsev R.N., Goryanskaya V.A., Il’in A.A., Il’in A.P. Mechanochemical synthesis of chromium(III) molybdates on the basis of various precursors. Vestnik Tverskogo Gosudarstvennogo Universiteta. Seriya: Khimiya = Herald of Tver State University. Series: Chemistry. 2020;1(39):96–109 (in Russ.). https://doi.org/10.26456/vtchem2020.1.11

17. Shurdumov G.K., Tlikhuryaeva M.M., Kardanova Yu.L., Shurdumov B.K. Solid-phase synthesis of highly dispersed chromium(III) molybdate based on the Cr2SO4-Na2CO3-MoO3 system. Khimiya v interesakh ustoichivogo razvitiya = Chemistry for Sustainable Development. 2016;24:805–810 (in Russ.). https://doi.org/10.15372/KhUR20160611

18. Plyasova L.M., Kefeli L.M. X-ray study of chromium and aluminum molybdates. Izvestiya AN SSSR. Neorganicheskie Materialy. 1967;3(5):906–908 (in Russ.).

19. Butukhanov V.D., Get’man E.I., Mokhosoev M.V. Interaction of lithium molybdate with chromium molybdate. Zhurnal Neorganicheskoi Khimii. 1972;17(4):1169–1171 (in Russ.).

20. Binnewies M., Mike E. Thermochemical Data of Elements and Compounds. Wenham: Wiley-VCH Verlag GmbH; 2002. 936 p. https://doi.org/10.1002/9783527618347

21. Tamm M.E., Tretyakov Yu.D. Neorganicheskaya khimiya (Inorganic Chemistry): in 3 v. Moscow: Akademiya; 2004. V.1. 240 p. (in Russ.).

22. Sing K.S.W. Reporting Physisorption Data for Gas/Solid Systems with Special Reference to the Determination of Surface Area and Porosity (Recommendations 1984). Pure Appl. Chem. 1985;57(4):603–619. https://doi.org/10.1351/pac198557040603

23. Thommes M., Kaneko K., Neimark A.V., Olivier J.P., Rodriguez-Reinoso F., Rouquerol J., Sing K.S.W. Physisorption of Gases, with Special Reference to the Evaluation of Surface Area and Pore Size Distribution (IUPAC Technical Report). Pure Appl. Chem. 2015;87(9):1051–1069. https://doi.org/10.1515/pac-2014-1117

24. Yu J., Wang G., Cheng B., Zhou M. Effects of Hydrothermal Temperature and Time on the Photocatalytic Activity and Microstructures of Bimodal Mesoporous TiO2 Powders. Appl. Catal. B: Environmental. 2007;69(3–4):171–180. https://doi.org/10.1016/j.apcatb.2006.06.022

25. Yang L., Guo M., Zhang F., Jing Y., Wang Y., Luo G. Controllable Preparation of γ-Alumina Nanoparticles with Bimodal Pore Size Distribution in Membrane Dispersion Microreactor. Particuology. 2018;41(12):1–10. https://doi.org/10.1016/j.partic.2018.04.001

26. Fuentes-Quezada E., de la Llave E., Halac E., Jobbágy M., Viva F.A., Bruno M.M., Corti H.R. Bimodal Mesoporous Hard Carbons from Stabilized Resorcinol-Formaldehyde Resin and Silica Template with Enhanced Adsorption Capacity. Chem. Eng. J. 2019;360(3):631–644. https://doi.org/10.1016/j.cej.2018.11.235

27. Kumar K.-N.P., Kumar J., Keizer K. Effect of Peptization on Densification and Phase-Transformation Behavior of Sol–Gel-Derived Nanostructured Titania. J. Am. Ceram. Soc. 1994;77(5):1396–1400. https://doi.org/10.1111/j.1151-2916.1994.tb05426.x