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Frontiers of Materials Science

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Front. Mater. Sci.    2019, Vol. 13 Issue (2) : 174-185    https://doi.org/10.1007/s11706-019-0462-3
RESEARCH ARTICLE
Pr-doped In2O3 nanocubes induce oxygen vacancies for enhancing triethylamine gas-sensing performance
Chao WANG, Wu WANG, Ke HE, Shantang LIU()
School of Chemistry and Environmental Engineering, Key Laboratory for Green Chemical Process (Ministry of Education), Hubei Key Lab of Novel Reactor & Green Chemical Technology, Wuhan Institute of Technology, Wuhan 430073, China
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Abstract

Nanocubes derived from pure In2O3 and xPr-In2O3 (x= 1, 2, 3 and 5 mol.%) were synthesized using a facile hydrothermal method, followed by calcination. The morphological and structural characterization demonstrated that as-synthesized samples presented regular cubes that decreased in size with the increase of the Pr doping. The data showed that the sensing performances of sensors based on In2O3 were notably improved after the Pr doping. Among them, the sensor based on 2 mol.% Pr-In2O3 had the best sensing performance towards the triethylamine (TEA) gas, including a high response (Ra/Rg = 260 to 100 ppm TEA gas, which is about 12 times higher than that of the sensor based on pure In2O3), a short response time (2 s), and a low detection limit (0.2 ppm) at 350 °C. The mechanism responsible for the enhancement of sensing performance was attributed to the improvement of the vacancy content of 2 mol.% Pr-In2O3, which promoted the oxidation–reduction reaction with the TEA gas that occurred on the materials surface.
Keywords gas sensor      Pr-dope In2O3      triethylamine      oxygen vacancy     
Corresponding Author(s): Shantang LIU   
Online First Date: 24 May 2019    Issue Date: 19 June 2019
 Cite this article:   
Chao WANG,Wu WANG,Ke HE, et al. Pr-doped In2O3 nanocubes induce oxygen vacancies for enhancing triethylamine gas-sensing performance[J]. Front. Mater. Sci., 2019, 13(2): 174-185.
 URL:  
https://academic.hep.com.cn/foms/EN/10.1007/s11706-019-0462-3
https://academic.hep.com.cn/foms/EN/Y2019/V13/I2/174
Fig.1  (a) XRD patterns of pure In2O3 and xPr-In2O3 (x = 1, 2, 3 and 5 mol.%) nanocubes. (b) Magnified (211) peaks from XRD patterns in (a).
Sample (hkl) FWHM β/(° ) Position, 2θ/(° ) Interplanar spacing, d/Å Average grain size/Å Average lattice constant/Å
Pure In2O3 (222) 0.157 30.66 2.9136 717 10.0891
(211) 0.131 21.568 4.1168
1 mol.% Pr-In2O3 (222) 0.231 30.614 2.9178 416 10.1076
(211) 0.213 21.533 4.1235
2 mol.% Pr-In2O3 (222) 0.195 30.649 2.9188 406 10.1110
(211) 0.227 21.548 4.1131
3 mol.% Pr-In2O3 (222) 0.267 30.608 2.9193 331 10.1128
(211) 0.194 21.530 4.1145
5 mol.% Pr-In2O3 (222) 0.421 30.592 2.9227 206 10.1245
(211) 0.367 21.525 4.1176
Tab.1  Average grain sizes and lattice constants of as-synthesized samples estimated by XRD data
Fig.2  (a)(b)(c)(d)(e) TEM images of pure In2O3, 1 mol.% Pr-In2O3, 2 mol.% Pr-In2O3, 3 mol.% Pr-In2O3 and 5 mol.% Pr-In2O3. (f) HRTEM image of 2 mol.% Pr-In2O3.
Fig.3  (a) N2 adsorption–desorption isotherms of the products. (b) The pore size distributions calculated by the NLDFT method from the adsorption branch.
Sample Average pore size /nm BET specific surface area /(m2·g−1)
Pure In2O3 19.61 15.98
1 mol.% Pr-In2O3 22.87 24.93
2 mol.% Pr-In2O3 9.40 56.70
3 mol.% Pr-In2O3 12.31 40.79
5 mol.% Pr-In2O3 6.43 18.14
Tab.2  Average pore sizes and specific surface areas of pure In2O3 and xPr-In2O3 (x = 1, 2, 3 and 5 mol.%)
Fig.4  The response of five sensors based on pure In2O3 and xPr-In2O3 (x = 1, 2, 3 and 5 mol.%) to 100 ppm TEA gas at various working temperatures (150–400 °C).
Fig.5  (a) Responses of five sensors based on pure In2O3 and xPr-In2O3 (x = 1, 2, 3 and 5 mol.%) to TEA gases with different concentrations (0.2–500 ppm) at 350 °C (the inset: magnified response curves in the range of 0.2–10 ppm). (b) Dynamic response transients of the sensor based on 2 mol.% Pr-In2O3 to 0.2–10 ppm TEA gas at 350 °C.
Fig.6  The response and recovery time of sensors based on (a) pure In2O3 and (b) 2 mol.% Pr-In2O3.
Fig.7  (a) The response of sensors based on pure In2O3 and 2 mol.% Pr-In2O3 to various gas with the same concentration (100 ppm) at 350 °C. (b) Long-term reproducibility of the sensor based on 2 mol.% Pr-In2O3 to 100 ppm TEA gas at 350 °C.
Sensing material TEA gas concentration/ppm Operating temperature/°C Response, Ra/Rg Response time/s Limit of detection/ppm Refs.
Au/Mg doped TiO2/SnO2 50 260 30.43 9 2 [38]
MoO3 microsheets 100 275 27.1 3 5 [39]
Broken In2O3 microtubes 100 300 72.5 103 0.1 [15]
Al2O3/Fe2O3 nanofibers 100 250 15.9 1 0.5 [40]
SnO2/Zn2SnO4 porous sphere 100 250 48 2 0.5 [41]
ZnO flower 50 280 83 8 2 [42]
2 mol.% Pr-In2O3 100 350 260 2 0.2 this work
Tab.3  Comparison of sensor performance towards the TEA gas in literature and the present work
Fig.8  (a) XPS spectra of pure In2O3 and 2 mol.% Pr-In2O3. (b) The Pr 3d spectrum of 2 mol.% Pr-In2O3. (c) The O 1s spectrum of 2 mol.% Pr-In2O3. (d) The O 1s spectrum of pure In2O3.
Fig.9  The response as a function of the unit surface area of sensors based on pure In2O3 and 2 mol.% Pr-In2O3 towards 100 ppm TEA gas at 350 °C.
Fig.10  (a) Schematic view of the sensing surface process in the TEA gas. (b) Schematic of the gas sensing mechanism using an electron depletion layer.
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