Pr-doped In₂O₃ nanocubes induce oxygen vacancies for enhancing triethylamine gas-sensing performance

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 (R_a/R_g = 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 In ₂O ₃ / triethylamine / oxygen vacancy

References

[1] Lu H, Zhang H, Zhang X, . Transformation of carbon-encapsulated metallic Co into ultrafine Co/CoO nanoparticles exposed on N-doped graphitic carbon for high-performance rechargeable zinc-air battery. Applied Surface Science, 2018, 448: 369–379

[2] Dutta M M, Phukan P. Cu-doped CoFe₂O₄ nanoparticles as magnetically recoverable catalyst for C–N cross-coupling reaction. Catalysis Communications, 2018, 109: 38–42

[3] Song X, Xu Q, Xu H, . Highly sensitive gold-decorated zinc oxide nanorods sensor for triethylamine working at near room temperature. Journal of Colloid and Interface Science, 2017, 499: 67–75

[4] Bai S, Ma Y, Luo R, . Room temperature triethylamine sensing properties of polyaniline–WO₃ nanocomposites with p–n heterojunction. RSC Advances, 2016, 6(4): 2687–2694

[5] Wu Y P, Zhou W, Dong W W, . Temperature-controlled synthesis of porous CuO particles with different morphologies for highly sensitive detection of triethylamine. Crystal Growth & Design, 2017, 17(4): 2158–2165

[6] Cao J, Xu Y, Sui L, . Highly selective low-temperature triethylamine sensor based on Ag/Cr₂O₃ mesoporous microspheres. Sensors and Actuators B: Chemical, 2015, 220: 910–918

[7] Cai T, Chen L, Ren Q, . The biodegradation pathway of triethylamine and its biodegradation by immobilized Arthrobacter protophormiae cells. Journal of Hazardous Materials, 2011, 186(1): 59–66

[8] Zhai T, Xu H, Li W, . Low-temperature in-situ growth of SnO₂ nanosheets and its high triethylamine sensing response by constructing Au-loaded ZnO/SnO₂ heterostructure. Journal of Alloys and Compounds, 2018, 737: 603–612

[9] Perkins F K, Friedman A L, Cobas E, . Chemical vapor sensing with monolayer MoS₂. Nano Letters, 2013, 13(2): 668–673

[10] Yang W, Wan P, Zhou X, . Additive-free synthesis of In₂O₃ cubes embedded into graphene sheets and their enhanced NO₂ sensing performance at room temperature. ACS Applied Materials & Interfaces, 2014, 6(23): 21093–21100

[11] Wang S, Xiao B, Yang T, . Enhanced HCHO gas sensing properties by Ag-loaded sunflower-like In₂O₃ hierarchical nanostructures. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2014, 2(18): 6598–6604

[12] Huang F, Yang W, He F, . Controlled synthesis of flower-like In₂O₃ microrods and their highly improved selectivity toward ethanol. Sensors and Actuators B: Chemical, 2016, 235: 86–93

[13] Shu S, Wang C, Liu S. Facile synthesis of perfect ZnSn(OH)₆ octahedral microcrystallines with controlled size and high sensing performance towards ethanol. Frontiers of Materials Science, 2018, 12(2): 176–183

[14] Shanmugasundaram A, Ramireddy B, Basak P, . Hierarchical In(OH)₃ as a precursor to mesoporous In₂O₃ nanocubes: a facile synthesis route, mechanism of self-assembly, and enhanced sensing response toward hydrogen. The Journal of Physical Chemistry C, 2014, 118(13): 6909–6921

[15] Yang W, Feng L, He S, . A density gradient strategy for preparation of broken In₂O₃ microtubes with remarkably selective detection of triethylamine vapor. ACS Applied Materials & Interfaces, 2018, 10(32): 27131–27140

[16] Liang Q, Xu H, Zhao J, . Micro humidity sensors based on ZnO–In₂O₃ thin films with high performances. Sensors and Actuators B: Chemical, 2012, 165(1): 76–81

[17] Xing R, Sheng K, Xu L, . Three-dimensional In₂O₃–CuO inverse opals: synthesis and improved gas sensing properties towards acetone. RSC Advances, 2016, 6(62): 57389–57395

[18] Rai P, Yoon J W, Kwak C H, . Role of Pd nanoparticles in gas sensing behaviour of Pd@In₂O₃ yolk–shell nanoreactors. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2016, 4(1): 264–269

[19] Zhao C, Huang B, Xie E, . Improving gas-sensing properties of electrospun In₂O₃ nanotubes by Mg acceptor doping. Sensors and Actuators B: Chemical, 2015, 207: 313–320

[20] Wang S, Cao J, Cui W, . Oxygen vacancies and grain boundaries potential barriers modulation facilitated formaldehyde gas sensing performances for In₂O₃ hierarchical architectures. Sensors and Actuators B: Chemical, 2018, 255: 159–165

[21] Gu F, Li C, Han D, . Manipulating the defect structure (V_O) of In₂O₃ nanoparticles for enhancement of formaldehyde detection. ACS Applied Materials & Interfaces, 2018, 10(1): 933–942

[22] Zhang Y, Zhou L, Liu Y, . Gas sensor based on samarium oxide loaded mulberry-shaped tin oxide for highly selective and sub ppm-level acetone detection. Journal of Colloid and Interface Science, 2018, 531: 74–82

[23] Zhou J Y, Bai J L, Zhao H, . Gas sensing enhancing mechanism via doping-induced oxygen vacancies for gas sensors based on indium tin oxide nanotubes. Sensors and Actuators B: Chemical, 2018, 265: 273–284

[24] Liu L, Shu S, Zhang G, . Highly selective sensing of C₂H₆O, HCHO, and C₃H₆O gases by controlling SnO₂ nanoparticle vacancies. ACS Applied Nano Materials, 2018, 1(1): 31–37

[25] Shu S, Wang M, Yang W, . Synthesis of surface layered hierarchical octahedral-like structured Zn₂SnO₄/SnO₂ with excellent sensing properties toward HCHO. Sensors and Actuators B: Chemical, 2017, 243: 1171–1180

[26] Xu W, Wang Y, Bai X, . Controllable synthesis and size-dependent luminescent properties of YVO₄:Eu³⁺ nanospheres and microspheres. The Journal of Physical Chemistry C, 2010, 114(33): 14018–14024

[27] Yathisha R O, Arthoba Nayaka Y, Manjunatha P, . Doping, structural, optical and electrical properties of Ni²⁺ doped CdO nanoparticles prepared by microwave combustion route. Microchemical Journal, 2019, 145: 630–641

[28] Wei D, Jiang W, Gao H, . Facile synthesis of La-doped In₂O₃ hollow microspheres and enhanced hydrogen sulfide sensing characteristics. Sensors and Actuators B: Chemical, 2018, 276: 413–420

[29] Wei D, Huang Z, Wang L, . Hydrothermal synthesis of Ce-doped hierarchical flower-like In₂O₃ microspheres and their excellent gas-sensing properties. Sensors and Actuators B: Chemical, 2018, 255: 1211–1219

[30] Xiao B, Wang F, Zhai C, . Facile synthesis of In₂O₃ nanoparticles for sensing properties at low detection temperature. Sensors and Actuators B: Chemical, 2016, 235: 251–257

[31] Bing Y, Liu C, Qiao L, . Multistep synthesis of non-spherical SnO₂@SnO₂ yolk–shell cuboctahedra with nanoparticle-assembled porous structure for toluene detection. Sensors and Actuators B: Chemical, 2016, 231: 365–375

[32] Liu X, Jiang L, Jiang X, . Design of superior ethanol gas sensor based on indium oxide/molybdenum disulfide nanocomposite via hydrothermal route. Applied Surface Science, 2018, 447: 49–56

[33] Ju D X, Xu H Y, Qiu Z W, . Near room temperature, fast-response, and highly sensitive triethylamine sensor assembled with Au-loaded ZnO/SnO₂ core–shell nanorods on flat alumina substrates. ACS Applied Materials & Interfaces, 2015, 7(34): 19163–19171

[34] Jeong H M, Kim J H, Jeong S Y, . Co₃O₄–SnO₂ hollow heteronanostructures: facile control of gas selectivity by compositional tuning of sensing materials via galvanic replacement. ACS Applied Materials & Interfaces, 2016, 8(12): 7877–7883

[35] Nie M. Organic Chemistry. Beijing: Metallurgical Industry Press, 2008 (In Chinese)

[36] Zhang L, Zhao J, Lu H, . Highly sensitive and selective dimethylamine sensors based on hierarchical ZnO architectures composed of nanorods and nanosheet-assembled microspheres. Sensors and Actuators B: Chemical, 2012, 171–172: 1101–1109

[37] Wu L, He F, Luo J, . Synthesis of three-dimensional ordered mesoporous MnO_x/CeO₂ bimetal oxides for the catalytic combustion of chlorobenzene. RSC Advances, 2017, 7(43): 26952–26959

[38] Xu H, Ju D, Chen Z, . A novel hetero-structure sensor based on Au/Mg-doped TiO₂/SnO₂ nanosheets directly grown on Al₂O₃ ceramic tubes. Sensors and Actuators B: Chemical, 2018, 273: 328–335

[39] Jiang W, Wei D, Zhang S, . The facile synthesis of MoO₃ microsheets and their excellent gas-sensing performance toward triethylamine: high selectivity, excellent stability and superior repeatability. New Journal of Chemistry, 2018, 42(18): 15111–15120

[40] Guo L, Wang C, Kou X, . Detection of triethylamine with fast response by Al₂O₃/α-Fe₂O₃ composite nanofibers. Sensors and Actuators B: Chemical, 2018, 266: 139–148

[41] Yang X, Yu Q, Zhang S, . Highly sensitive and selective triethylamine gas sensor based on porous SnO₂/Zn₂SnO₄ composites. Sensors and Actuators B: Chemical, 2018, 266: 213–220

[42] Li W, Xu H, Yu H, . Different morphologies of ZnO and their triethylamine sensing properties. Journal of Alloys and Compounds, 2017, 706: 461–469

[43] Patil S J, Patil A V, Dighavkar C G, . Semiconductor metal oxide compounds based gas sensors: A literature review. Frontiers of Materials Science, 2015, 9(1): 14–37

[44] Chen K H, Pu Y C, Chang K D, . Ag-nanoparticle-decorated SiO₂ nanospheres exhibiting remarkable plasmon-mediated photocatalytic properties. The Journal of Physical Chemistry C, 2012, 116(35): 19039–19045

[45] Florea M, Postole G, Matei-Rutkovska F, . Influence of Gd and Pr doping on the properties of ceria: texture, structure, redox behaviour and reactivity in CH₄/H₂O reactions in the presence of H₂S. Catalysis Science & Technology, 2018, 8(5): 1333–1348

[46] Guo D, Yang Q, Chen P, . The influence of micronization on the properties of Pr-ZrSiO₄ pigment. Dyes and Pigments, 2018, 153: 74–83

[47] Wang C, Cui X, Liu J, . Design of superior ethanol gas sensor based on Al-doped NiO nanorod-flowers. ACS Sensors, 2016, 1(2): 131–136

[48] Chen M, Wang Z, Han D, . Porous ZnO polygonal nanoflakes: synthesis, use in high-sensitivity NO₂ gas sensor, and proposed mechanism of gas sensing. The Journal of Physical Chemistry C, 2011, 115(26): 12763–12773

[49] Batzill M, Diebold U. Surface studies of gas sensing metal oxides. Physical Chemistry Chemical Physics, 2007, 9(19): 2307–2318

[50] Liu J, Dai M, Wang T, . Enhanced gas sensing properties of SnO₂ hollow spheres decorated with CeO₂ nanoparticles heterostructure composite materials. ACS Applied Materials & Interfaces, 2016, 8(10): 6669–6677

[51] Ma Y, Yang J, Yuan Y, . Enhanced gas sensitivity and sensing mechanism of network structures assembled from α-Fe₂O₃ nanosheets with exposed {104} facets. Langmuir, 2017, 33(35): 8671–8678

[52] Wang D, Wan K, Zhang M, . Constructing hierarchical SnO₂ nanofiber/nanosheets for efficient formaldehyde detection. Sensors and Actuators B: Chemical, 2019, 283: 714–723

[53] Tricoli A, Righettoni M, Teleki A. Semiconductor gas sensors: dry synthesis and application. Angewandte Chemie International Edition, 2010, 49(42): 7632–7659

[54] Xiao L, Shu S, Liu S. A facile synthesis of Pd-doped SnO₂ hollow microcubes with enhanced sensing performance. Sensors and Actuators B: Chemical, 2015, 221: 120–126

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