Синтез, структура та електрохімічні властивості ультрадисперсного аморфного ?-FeOOH

A. B. Hrubiak; V. O. Kotsyubynsky; L. V. Mokhnatska; V. V. Moklyak; P. I. Kolkovsky; G. I. Mudryk

doi:10.15407/hftp07.03.300

Authors

A. B. Hrubiak Vasyl Stefanyk Precarpathian National University
V. O. Kotsyubynsky Vasyl Stefanyk Precarpathian National University
L. V. Mokhnatska Vasyl Stefanyk Precarpathian National University
V. V. Moklyak Institute of Metal Physics of National Academy of Sciences of Ukraine
P. I. Kolkovsky Institute of Metal Physics of National Academy of Sciences of Ukraine
G. I. Mudryk Vasyl Stefanyk Precarpathian National University

DOI:

https://doi.org/10.15407/hftp07.03.300

Keywords:

amorphous ultrafine β-FeOOH, ion of iron, magnetic microstructure, phase transformation

Abstract

The aim of the article is to findrelationshipsbetween synthesis conditions and phase composition, magnetic microstructure and electrochemical properties of ultrafine amorphous iron hydroxide phases obtained by iron citrate sol hydrothermal treatment. The sol of iron citrate was formed by mixing of 0.3 M iron nitrate aqueous solutions with citric acid. Hydrothermal treatment of iron citrate was carried out at 120°C for 5 hours with the next annealing of precipitation at 150, 200, 250, 300 and 350°C in air for 2 hours. X-ray analysis and M?ssbauer spectroscopy were used for phase composition and magnetic microstructure control of the obtained iron hydroxides. All the synthesized materials were X-ray amorphous so the M?ssbauer spectroscopy was used for phases recognition. In has been determined that the hydrothermal treatment of iron citrate solution at 120°C for 5 hours leads to Fe(OH)₃formation.The annealing in the temperature range of 150–200 °C causes the reduction of iron Fe³⁺ ? Fe²⁺as aresult of material dehydration . Under this condition the composite Fe(OH)₃/ Fe(OH)₂ was formed with the pentahydrate iron citrate C₆H₅O₇Fe?5H₂O and iron oxalate FeC₂ O₄ ·2H₂ O presence . Amorphous ultrafine ? -FeOOH was obtained after Fe(OH)₃annealing at 250°C for 2 hours . It has been found that after annealing at 350°Cphase transformation of ?- FeOOH??-Fe₂ O₃has occurred. The sizes of coherent scattering regions for ?-Fe₂ O₃ phase are about 15.0±1.5 nm. The electrochemical properties of ultrafine amorphous ?-FeOOH and composite ?-FeOOH/carbon nanotubes in 3.5M KOH aqueous solution were studied. The efficiency of ?-FeOOH/carbon nanotube as potential electrode material for supercapacitor was shown.

References

1. Xiong W., Xiangying C., Lisheng G., Huagui Z., Mingrong J., Chenming T., Tao S., Zude Z. Synthesis of β-FeOOH and α-Fe₂O₃ nanorods and electrochemical properties of β-FeOOH. J. Mater. Chem. 2004. 14: 905. https://doi.org/10.1039/B310722A

2. Zhihui X., Jianru L., Lixiang Z. Template-Free Hydrothermal Synthesis of β-FeOOH Nanorods and Their Catalytic Activity in the Degradation of Methyl Orange by a Photo-Fenton-Like Process. Open Journal of Inorganic Non-Metallic Materials. 2013. 3(4): 58. https://doi.org/10.4236/ojinm.2013.34010

3. Frausto C.T., Garcia A.A. Zinc and Pyrrole-added Akaganeite (β-FeOOH) Films by Ultrasonic Spray Pyrolisis Assessed as Propane Sensors. Sensors and Transducers. 2012. 146(11): 170.

4. Garcia K. E., Barrero C.A., Morales A.L., Greneche J.-M. Magnetic structure of synthetic akaganeite: A review of Mössbauer data. Rev. Fac. Ing. Univ. Antioquia. 2009. (49): 185.

5. Amine K., Yasuda H., Yamachi M. β-FeOOH, a new positive electrode material for lithium secondary batteries. J. Power Sources. 1999. 81–82(1–2): 221. https://doi.org/10.1016/S0378-7753(99)00138-X

6. Mackay A.L. β-Ferric Oxyhydroxide–Akaganéite. Mineral Mag. 1962. 33(259): 270. https://doi.org/10.1180/minmag.1962.033.259.02

7. Post J. E., Buchwald V. F. Crystal structure refinement of akaganeite. Am. Mineral. 1991. 76(1–2): 272.

8. Post J.E., Heaney P.J., Von Dreele R.B., Hanson J.C. Neutron and temperature-resolved synchrotron X-ray powder diffraction study of akaganéite. Am. Mineral. 2003. 88(5): 782. https://doi.org/10.2138/am-2003-5-607

9. Chambaere D.G., De Grave E. On the influence of the dual iron co-ordination on the hyperfine field in βFeOOH. Journal of Magnetic and Magnetism Materials. 1984. 44: 349. https://doi.org/10.1016/0304-8853(84)90263-4

10. Pollard R.J., Cardile C.M., Lewis D.G., Brown L.J. Characterization of FeOOH Polymorphs and Ferrihydrite Using Low-Temperature, Applied-Field, Mössbauer Spectroscopy. Clay Miner. 1992. 27: 57. https://doi.org/10.1180/claymin.1992.027.1.06

11. Pankhurst Q.A., Pollard R.J. Mossbauer-spectra of antiferromagnetic powders in applied fields. J. Phys.: Condens. Matter. 1990. 2(35): 7329. https://doi.org/10.1088/0953-8984/2/35/008

12. Rezel D., Genin J.M.R. The substitution of chloride ions to OH−-Ions in the akaganeite beta ferric oxyhydroxide studied by Mössbauer effec. Hyperfine Interact. 1990. 57(1): 2067. https://doi.org/10.1007/BF02405765

13. Dezsi I., Keszthelyi L., Kutgawczuk D., Moln B. Eissa N.A. Mössbauer Study of β- and δ-FeOOH and their Disintegration Products. Phys. Stat. Sol. 1967. 22(2): 617. https://doi.org/10.1002/pssb.19670220234

14. Braun H., Gallagher K.J. β-Fe2O3, a New Structural Form of Iron (III) Oxide. Nature Phys. Sci. 1972. 240: 13. https://doi.org/10.1038/physci240013a0

15. Howe A.T., Gallagher K.J. Mössbauer studies in the colloid system β-FeOOH–β-Fe₂O₃: structures and dehydration mechanism. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases. 1975. 71: 22.

16. Gonzalez-Calbet J.M., Alario Franco M.A. A thermogravimetric and electron microscopy study of the decomposition of akaganeite. Thermochim. Acta. 1982. 58(1): 45. https://doi.org/10.1016/0040-6031(82)87138-4

17. Chambaere D.G., De Grave E. The β-FeOOH to α-Fe₂O₃ phase transformation: Structural and magnetic phenomena. Phys. Chem. Miner. 1985. 12(3): 176. https://doi.org/10.1007/BF00308211

18. Nagai N., Hosoito N., Kiyama M., Shinjo T., Takada T. The Thermal Decomposition Intermediate Product of P-FeO(OH). In: Ferrites. Proc. of the International Conference (Sept.-Oct., 1980, Japan). P. 247.

19. Revo S., Alekseev A., Ivanenko E., Labi T., Boubertakh A., Hamamda S. Structure, tributechnical, and thermophysical characterristics of the fluoroplastic carbonnanotubes material. Nanoscale Res. Lett. 2014. 9(1): 1. https://doi.org/10.1186/1556-276X-9-213

20. Gin'e A. X-ray crystal. Theory and practice. (Moscow: Science, 1961).

21. Sei J.O., Cook D.C., Townsend H.E. Characterization of Iron Oxides Commonly Formed as Corrosion Products on Steel. Hyperfine Interact. 1998. 112(1–4): 59.

22. Bassi P.S., Randhawa B.S., Jamwal H.S. Mossbauer study of the thermal decomposition of iron(III) citrate pentahydrate. J. Therm. Anal. 1984. 29: 439. https://doi.org/10.1007/BF01913454

23. Buchanan D.N.E. Mossbauer and spectroscopy of radiolytic photolytic effects on ferric citrate. J. Inorg. Nucl. Chem. 1970. 32(11): 3531. https://doi.org/10.1016/0022-1902(70)80161-0

24. Bernal J.D., Dasgupta D.R., Mackay A.L. The Oxides and Hydroxides of Iron and Their Structural Inter-Relationships. Clay Miner. 1959. 4(21): 15. https://doi.org/10.1180/claymin.1959.004.21.02

25. Chambaere D.G., De Grave E., Vanleerberghe R.L., Vandenberghe R.E. The electric field gradient at the iron sites in β-FeOOH. Hyperfine Interact. 1984. 20(4): 249. https://doi.org/10.1007/BF02069375

26. Chambaere D.G., De Grave E. A study of the non-stoichiometrical halogen and water content of β-FeOOH. Phys. Stat. Sol. 1984. 83: 93. https://doi.org/10.1002/pssa.2210830109

27. Stahl K., Nielsen K., Jiang J., Lebech B., Hanson J.C., Norby P., Lanschot J. On the akaganeite crystal structure, phase transformations and possible role in post-excavational corrosion of iron artifacts. Corros. Sci. 2003. 45(11): 2563. https://doi.org/10.1016/S0010-938X(03)00078-7

28. Barrero C.A., Garcia K.E., Morales A.L. Kodjikian S., Greneche J.M. New analysis of the Mössbauer spectra of akaganeite. J. Phys.: Condens. Matter. 2006. 18(29): 6827. https://doi.org/10.1088/0953-8984/18/29/020

29. Garcia K.E., Morales A.L., Barrero C.A., Greneche J.M. Characterization of akaganeite synthesized in the presence of Al3+, Cr3+, and Cu²⁺ ions and urea. Mater. Chem. Phys. 2008. 112(1): 120. https://doi.org/10.1016/j.matchemphys.2008.05.021

30. Garcia K.E., Morales A.L., Barrero C.A., Arroyave C.E., Greneche J.M. Magnetic and crystal structure refinement in akaganeite nanoparticle. Physica B. 2004. 354(1–4): 187. https://doi.org/10.1016/j.physb.2004.09.045

31. Kuzmann E., Nagy S., Vertes A. Critical Review Of Analytical Applications Of Mossbauer Spectroscopy Illustrated By Mineralogical And Geological Examples. Pure Appl. Chem. 2003. 75(6): 801. https://doi.org/10.1351/pac200375060801

32. Long C., Jiang L., Wei T. Yan J., Fan Z. High-performance asymmetric supercapacitors with lithium interca-lation reaction using metal oxide-based composites as electrode materials. J. Mater. Chem. A. 2014. 2(39): 16678. https://doi.org/10.1039/C4TA03241A