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Kinetic study on preparation of substoichiometric tungsten oxide WO2.72 via hydrogen reduction process

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Abstract

Controlling the conditions of the oxygen partial pressure and temperature to prepare the WO2.72 (W18O49) via reduction was possible through thermodynamic consideration. WO2.72 was synthesized via heating to 1073 K in 5% H2–95% Ar mixture gas flow from ammonium tungstate which was prepared by hydrothermal process. With the reducing prolonging time, the products were changed from WO2.72 to WO2 and then metal W. Thermogravimetric (TG) analysis showed ammonium tungstate decomposed completely to WO3 at 773 K. Isothermal reductions using TG analysis were carried out at 905 K, 925 K, 945 K and 973 K in 5% H2–95% Ar mixture gas flow, respectively. The whole reduction from WO3 to WO2.72 divided into three parts: initial nucleation and growth stage, final interfacial reaction stage and intermediate stage, was controlled jointly by both mechanisms. Fitting results showed that the initial stage obey the one-dimensional Avrami–Erofeev equation, the apparent activation energy was 132.7 ± 1.1 kJ mol−1 and the pre-exponent factor was 4.82 × 105 min−1; the final stage expressed by 2-dimensional interfacial reaction, the apparent activation energy was 144.0 ± 2.1 kJ mol−1 and the pre-exponent factor was 3.20 × 105 min−1.

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Abbreviations

A :

Pre-exponential factor (min−1)

E :

Activation energy (kJ mol−1)

\(G\left( \alpha \right)\) :

Integral form of kinetic mechanism function

m :

Mass (mg)

n :

Coefficients in the kinetic equation

R :

Gas constant, 8.314 J (mol K)−1

t :

Time (min)

\(t^{\prime}\) :

Real reaction time (min)

\(t_{\text{i}}\) :

The time at the beginning of the final stage

T :

Absolute temperature (K)

\(\alpha\) :

Conversion rate

\(\alpha^{\prime}\) :

Real isothermal conversion rate

\(\alpha_{\text{i}}\) :

Conversion rate at the beginning of the final stage

\(\alpha_{0}\) :

Conversion rate of pre-reduction

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Acknowledgements

This work is financially supported by National Natural Science Foundation of China (NSFC 51472009, 51534001, 51172007) and Beijing Municipal High Level Innovative Team Building Program (IDHT20170502). Authors express thanks to large-scale instrument and equipment sharing forum of Beijing University of Technology for providing the excellent analysis conditions.

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  1. Qiao Dan and Wang Yue have contributed equally to this work.

Authors and Affiliations

  1. Beijing Key Laboratory for Green Catalysis and Separation, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing, 100124, China

    Dan Qiao, Yue Wang & Fan Li

  2. Department of Physical Chemistry of Metallurgy, School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing, 10083, China

    Daya Wang & Baijun Yan

Authors
  1. Dan Qiao
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  2. Yue Wang
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  3. Fan Li
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  4. Daya Wang
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  5. Baijun Yan
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Correspondence to Fan Li.

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Qiao, D., Wang, Y., Li, F. et al. Kinetic study on preparation of substoichiometric tungsten oxide WO2.72 via hydrogen reduction process. J Therm Anal Calorim 137, 389–397 (2019). https://doi.org/10.1007/s10973-018-7966-4

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  • DOI: https://doi.org/10.1007/s10973-018-7966-4

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