Sensory properties of h-WO3 doped with Co2+ and Fe3+ cations in relation to toxic gases

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Abstract

The sensory properties of solid solutions of h-CoxWO3 (0 ≤ x ≤ 0.09) and h-W1–xFexO3 (0 ≤ x ≤ 0.06), as well as m-WO3, were studied in relation to various toxic gases at the maximum permissible concentrations in the air. Doping of h-WO3 with Co2+ or Fe3+ ions does not affect the sensitivity of the sensory response to CH3COCH3 and NH3, but leads to a decrease in the sensory signal relative to NO2. A comparative analysis of the sensory properties of tungsten trioxide of hexagonal and monoclinic crystallographic modification has been performed. When detecting CH3COCH3 and NH3, the sensitivity of h-WO3 is 1.5 and 1.3 times higher than that of m-WO3, respectively. The oxygen vacancy concentration and pore volume are key parameters that determine the higher sensitivity of m-WO3 to NO2 compared to h-WO3.

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About the authors

N. V. Podval'naya

Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences

Author for correspondence.
Email: podnat@inbox.ru
Russian Federation, Pervomaiskaya str., 91, Yekaterinburg, 620990

A. V. Marikutsa

Lomonosov Moscow State University

Email: podnat@inbox.ru

Faculty of Chemistry

Russian Federation, Leninskie Gory, 1–3, Moscow, 119234

G. S. Zakharova

Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences

Email: podnat@inbox.ru
Russian Federation, Pervomaiskaya str., 91, Yekaterinburg, 620990

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Supplementary files

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2. Fig. 1. Diffraction patterns of h-WO3 (1), h-Co0.09WO3 (2), h-W0.94Fe0.06O3 (3) (a) and m-WO3 (b) powders. The inset shows the position of the 002 peak. The vertical lines show the positions of the Bragg peaks for h-WO3 (ICDD 85-2460) and m-WO3 (ICDD 43-1035).

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3. Fig. 2. SEM images of h-WO3 (a), h-Co0.09WO3 (b), h-W0.94Fe0.06O3 (c) powders and energy-dispersive X-ray microanalysis spectra of h-Co0.09WO3 (1) and h-W0.94Fe0.06O3 (2) (d) powders. The additional peak from carbon is due to the substrate used to fix the sample.

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4. Fig. 3. SEM (a) and TEM images (b) of m-WO3 powder.

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5. Fig. 4. TG, DSC and MS curves for h-Co0.09WO3 (a) and h-W0.94Fe0.06O3 (b).

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6. Fig. 5. Sorption isotherms (a) and pore size distribution curves (b) of h-WO3 (1), h-Co0.09WO3 (2), h-W0.94Fe0.06O3 (3), m-WO3 (4) powders.Fig. 5. Sorption isotherms (a) and pore size distribution curves (b) of h-WO3 (1), h-Co0.09WO3 (2), h-W0.94Fe0.06O3 (3), m-WO3 (4) powders.

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7. Rice. 6. Temperature dependences of resistance m-WO3, h-WO3, h-Co0.01WO3, h-Co0.03WO3, h-Co0.09WO3, h-W0.99Fe0.01O3, h-W0.97Fe0.03O3, h-W0.94Fe0.06O3.

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8. Fig. 7. Dynamic response of sensors based on h-WO3, h-Co0.01WO3, h-Co0.03WO3, h-Co0.09WO3 in relation to different concentrations of acetone vapor at 250°C (a). Temperature dependence of the sensor response of m-WO3, h-WO3, h-Co0.01WO3, h-Co0.03WO3, h-Co0.09WO3, h-W0.99Fe0.01O3, h-W0.97Fe0.03O3, h-W0.94Fe0.06O3 with respect to 20 ppm acetone (b). Concentration dependence of the sensory response of m-WO3 and h-WO3 relative to CH3COCH3 at 300°C (c). Concentration dependence of the sensory response of m-WO3 and h-WO3 relative to NO2 at 100°C (d).

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9. Rice. 8. Sensory response m-WO3, h-WO3, h-Co0.01WO3, h-Co0.03WO3, h-Co0.09WO3, h-W0.99Fe0.01O3, h-W0.97Fe0.03O3 h-W0.94Fe0.06O3 relative to NO2 at 100°C and reducing gases CO, NH3, H2S, CH3COCH3, CH3OH, CH2O, C6H6 at 300°C.

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10. Fig. 9. Temperature dependences of the rate of ammonia desorption from the surface of samples (a) and temperature-programmed desorption (TPD) of ammonia, mass spectra of the desorbed gas from the surface of h-WO3 (b).

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