Microwave-Assisted Solution Combustion Synthesis of WO3 Nanoparticles: Optical and Colorimetric Characteristics

Document Type : Original Research Article


1 Physics Department, Shahrood University of Technology, 3619995161, Shahrood, Iran

2 Department of Inorganic Pigments and Glazes, Institute for Color Science and Technology (ICST), Tehran, Iran


Tungsten oxide (WO3) and tungsten oxide hydrate (WO3.H2O) nanoparticles were synthesized via microwave-assisted solution combustion in comparison with the acidic precipitation method. Oxalic acid was used as a surfactant and forming agent in the acidic precipitation method. In addition to oxalic acid, glycine and citric acid were also used as fuels in the microwave-assisted combustion method. The synthesis process was investigated by thermogravimetric (TG) and Differential Thermal Analysis (DTA) analysis. The obtained nanoparticles were analyzed using the scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The sample synthesized via the acidic precipitation method showed an orthorhombic crystal structure. One of the samples synthesized via the microwave-assisted solution combustion method was monoclinic and the two others were amorphous. The acidic precipitation method resulted in uniform plate-like structures while the combusted samples indicated irregular spherical morphology. Fourier-transform infrared (FTIR) analysis revealed stretching-vibrating bands relating to W-O bonds in the synthesized tungsten oxide nanoparticles. The bandgap energy of the nanoparticles calculated using UV-Vis spectra and Tauc plot extrapolation increased with decreasing the particle size. The data of reflectance and colorimetry had good agreement with the maximum peak position in the absorption spectra. The results indicated that the acidic precipitation method controls the particle's morphology as well as the size distribution. Although the combustion of fuels releases a lot of heat, the synthesis by solution combustion can control the size and shape of the nanoparticles, which can be an appropriate method for mass production of nanoparticles.


Main Subjects


    1. Zheng, H., Ou, J.Z., Strano, M.S., Kaner, R.B., Mitchell, A., Kalantar‐zadeh, K., "Nanostructured tungsten oxide – properties , synthesis , and applications", Advanced Functional Materials, Vol. 21, No. 12, (2011), 2175–2196.
    2. Cong, S., Geng, F., Zhao, Z., "Tungsten oxide materials for optoelectronic applications", Advanced Materials, Vol. 28, No. 47, (2016), 10518-10528.
    3. Chang, X., Sun, S., Dong, L., Dong, Y., Yin Y., "Large-scale production of tungsten trioxide nanoparticles for electrochromic application", RSC Advances, Vol. 4, No. 18, (2014), 8994–9002.
    4. Kumar, V.B., Mohanta, D., "Formation of nanoscale tungsten oxide structures", Bulletin of Materials Science, Vol. 34, No. 3, (2011), 435–442.
    5. Rezaee, O., Mahmoudi Chenari, H., Ghodsi, F. E, "Precipitation synthesis of tungsten oxide nanoparticles: X-ray line broadening analysis and photocatalytic efficiency study", Journal of Sol-Gel Science and Technology, Vol. 80, No. 1, (2016), 109-118.
    6. Liu, Z., Miyauchi, M., Yamazaki, T., Shen, Y., "Facile synthesis and NO2 gas sensing of tungsten oxide nanorods assembled microspheres", Sensors and Actuators B: Chemical, Vol. 140, No.2, (2009), 514–519.
    7. Thummavichai, K., Wang, N., Xu, F., Rance, G., Xia, Y., Zhu, Y., "In situ investigations of the phase change behaviour of tungsten oxide nanostructures", Royal Society Open Science, Vol. 5, No. 4, (2018), 171932.
    8. Zhao, B., Zhang, X., Dong, G., Wang, H., Yan, H., "Efficient electrochromic device based on sol – gel prepared WO3 films", Ionics, Vol. 21, No.10 (2015), 2879-2887.
    9. Patil, V.B., Adhyapak, P. V., Suryavanshi, S.S., Mulla, I.S., "Oxalic acid induced hydrothermal synthesis of single crystalline tungsten oxide nanorods", Journal of Alloys and Compounds, Vol. 590, (2014), 283-288.
    10. Ahmadi, M., Younesi, R., Guinel, M.J., "Synthesis of Tungsten Oxide Nanoparticles using a Hydrothermal Method at Ambient Pressure", Journal of Materials Research, Vol. 29, No. 13, (2014), 1424-1430.
    11. Park, Y., Hong, Y., Lee, K., "Characterization of electrochromic WO3 thin films fabricated by an RF sputtering method", Journal of Ceramic Processing Research,Vol.14, No. 3, (2013), 337-341.
    12. Migas, D.B., Shaposhnikov, V.L., Rodin, V.N., Borisenko, V.E., "Tungsten oxides . I . Effects of oxygen vacancies and doping on electronic and optical properties of different phases of WO3", Journal of Applied Physics, Vol. 108, No. 9 , (2010), 093714.
    13. Jiayin, L., Jianfeng, H., Jianpeng, W., Liyun, C., Yanagisawa, K., "Morphology-controlled synthesis of tungsten oxide hydrates crystallites via a facile, additive-free hydrothermal process", Ceramics International, Vol. 38, No. 6, (2012), 4495–4500.
    14. Sharma, P., Lotey, G.S., Singh, S., Verma, N.K., "Solution-combustion: the versatile route to synthesize silver nanoparticles", Journal of Nanoparticle Research, Vol. 13, No. 6, (2011), 2553–2561.
    15. Patil, K.C., "Advanced ceramics: Combustion synthesis and properties", Bulletin of Materials Science, Vol. 16, No. 6, (1993), 533–541.
    16. Li, L., Zhao, J., Wang, Y., Li, Y., Ma, D., Zhao, Y., Hou, S., Hao, X., "Oxalic acid mediated synthesis of WO3.H2O nanoplates and self-assembled nanoflowers under mild conditions", Journal of Solid State Chemistry,Vol.184, No. 7, (2011), 1661–1665.
    17. Ali Asghari, H., Aarabi, A. M., Haratizadeh, H., "Synthesis of Nanostructured Tungsten Oxide Thin Film", The 7th International Color & Coating Congress (ICCC2017), Amirkabir University of Technology, Tehran, (2017).
    18. Aliasghari, H., Arabi, A.M., Haratizadeh, H., "A novel approach for solution combustion synthesis of tungsten oxide nanoparticles for photocatalytic and electrochromic applications", Ceramics International,Vol. 46, No. 1, (2020), 403-414.
    19. Nayak, A.K., Sohn, Y., Pradhan, D., "Facile green synthesis of WO3·H2O nanoplates and WO3 nanowires with enhanced photoelectrochemical performance", Crystal Growth & Design, Vol. 17, No. 9, (2017), 4949–4957.
    20. Breedon, M., Spizzirri, P., Taylor, M., du Plessis, J., McCulloch, D., Zhu, J., Yu, L., Hu, Z., Rix, C., Wlodarski, W., Kalantar-zadeh, K., "Synthesis of nanostructured tungsten oxide thin films: a simple , controllable , inexpensive , aqueous sol - gel method", Crystal Growth & Design, Vol. 10, No. 1, (2010), 430-439.
    21. Khodadadi, M.R., Olya, M.E., Naeimi, A., "Highly efficient Al-doped ZnO:Ag catalyst for RB19 photocatalytic degradation: Microwave-assisted synthesis and characterization", Korean Journal of Chemical Engineering, Vol. 33, No. 7., (2016), 2018-2026.
    22. Ahmadian, H., Al. Hessari, F., Arabi, A.M., "Preparation and characterization of Luminescent nanostructured Gd2O3-Y2O3:Eu synthesized by the solution combustion process", Ceramics International, Vol. 45, No. 15., (2019), 18778-18787.
    23. Chen, P., Qin, M., Chen, Z., Jia, B., Qu, X., "Solution combustion synthesis of nanosized WOx: Characterization, mechanism and excellent photocatalytic properties", RSC Advances, Vol. 6, No. 86, (2016), 83101–83109.
    24. Hossain, M.K., Kecsenovity, E., Varga, A., Molnár, M., Janáky, C., Rajeshwar, K., "Solution combustion synthesis of complex oxide semiconductors", International Journal of Self-Propagating High-Temperature Synthesis, Vol. 27, No. 3, (2018), 129–140.
    25. Higgins, J., Zhou, X., Liu, R., Huang, T.T.S., "Theoretical study of thermal decomposition mechanism of oxalic acid", The Journal of Physical Chemistry A, Vol. 101, No. 14, (1997), 2702–2708.
    26. Kakumoto, T., Saito, K., Imamura, A., "Unimolecular decomposition of oxalic acid", Journal of Physical Chemistry, Vol. 91, No. 9, (1987), 2366–2371.
    27. Raudoniene, J., Laurikenas, A., Kaba, M.M., Sahin, G., Morkan, A.U., Brazinskiene, D., Asadauskas, S., Seidu, R., Kareiva, A., Garskaite, E., "Textured WO3 and WO3: Mo films deposited from chemical solution on stainless steel", Thin Solid Films, Vol. 653, (2018), 179–187.
    28. Liu, Y., Li, B., Wei, X., Pan,W., "Citric-nitrate combustion synthesis and electrical conductivity of the Sm3+ and Nd3+ co-doped ceria electrolyte", Journal of the American Ceramic Society, Vol. 91, No. 12, (2008), 3926–3930.
    29. Miao, B., Zeng, W., Lin, L., Xu, S., Ding, X., "Syntheses and mechanism of WO3·H2O nanoflowers assembled of square nanoplates with the assistance of oxalic acid", Nanoscience and Nanotechnology Letters, Vol. 5 , No.7 (2013), 765–769.
    30. Rajeshwar, K., De Tacconi, N.R., "Solution combustion synthesis of oxide semiconductors for solar energy conversion and environmental remediation", Chemal Society Review, Vol. 38, No. 7, (2009), 1984–1998.
    31. Sharma, N., Deepa, M., Varshney, P., Agnihotry, S.A., "FTIR investigations of tungsten oxide electrochromic films derived from organically modified peroxotungstic acid precursors", Thin Solid Films, Vol. 401, No. 1-2, (2001), 45–51.
    32. Yin, J., Cao, H., Zhang, J., Qu, M., Zhou, Z., "Synthesis and applications of γ‑tungsten oxide hierarchical nanostructures", Crystal Growth & Design, Vol. 13, No.2, (2013), 759-769.
    33. Djaoued, Y., Ashrit, P.V., Badilescu, S., Brüning, R., "Synthesis and characterization of macroporous tungsten oxide films for electrochromic application", Journal of Sol-Gel Science and Technology, Vol. 28, (2003), 235–244.
    34. Solis, J.L., Hoel, A., Lantto, V., Granqvist, C.G., "Infrared spectroscopy study of electrochromic nanocrystalline tungsten oxide films made by reactive advanced gas deposition Infrared spectroscopy study of electrochromic nanocrystalline tungsten oxide films made by reactive advanced gas deposition", Journal of Applied Physics, Vol. 89, No. 5, (2001), 2727-2732.
    35. Pang, H.F., Xiang, X., Li, Z.J., Fu, Y.Q. Zu, X.T., "Hydrothermal synthesis and optical applications and
      materials science properties of hexagonal tungsten oxide nanocrystals assisted by ammonium tartrate", Physica Status Solidi (a), Vol. 209, No. 3, (2012), 537–544.
    36. Murphy, A.B, "Band-gap determination from diffuse reflectance measurements of semiconductor films, and application to photoelectrochemical water-splitting", Solar Energy Materials and Solar Cells, Vol. 91, No. 14, (2007), 1326–1337
    37. Madhavi, V. Kondaiah, P. Hussain, O.M., Uthanna, S., "Structural, optical and electrochromic properties of RF magnetron sputtered WO3 thin films", Physica B: Condensed Matter, Vol. 454, (2014), 141–147.