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One-dimensional nanofibers can be transformed into hollow structures with larger specific surface area, which contributes to the enhancement of gas adsorption. We firstly fabricated Cu-doped In2O3 (Cu-In2O3) hollow nanofibers by electrospinning and calcination for detecting H2S. The experimental results show that the Cu doping concentration besides the operating temperature, gas concentration, and relative humidity can greatly affect the H2S sensing performance of the In2O3-based sensors. In particular, the responses of 6%Cu-In2O3 hollow nanofibers are 350.7 and 4201.5 to 50 and 100 ppm H2S at 250 ℃, which are over 20 and 140 times higher than those of pristine In2O3 hollow nanofibers, respectively. Moreover, the corresponding sensor exhibits excellent selectivity and good reproducibility towards H2S, and the response of 6%Cu-In2O3 is still 1.5 to 1 ppm H2S. Finally, the gas sensing mechanism of Cu-In2O3 hollow nanofibers is thoroughly discussed, along with the assistance of first-principles calculations. Both the formation of hollow structure and Cu doping contribute to provide more active sites, and meanwhile a little CuO can form p-n heterojunctions with In2O3 and react with H2S, resulting in significant improvement of gas sensing performance. The Cu-In2O3 hollow nanofibers can be tailored for practical application to selectively detect H2S at lower concentrations.


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Electrospun Cu-doped In2O3 hollow nanofibers with enhanced H2S gas sensing performance

Show Author's information Yu ZHANGa,Shuai HANa,Mingyuan WANGb,Siwei LIUaGuiwu LIUa( )Xianfeng MENGaZiwei XUaMingsong WANGaGuanjun QIAOa
School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, China
SEU-FEI Nano-Pico Center, Key Laboratory of MEMS of Ministry of Education, School of Electrical Science and Engineering, Southeast University, Nanjing 210096, China

† Yu Zhang, Shuai Han, and Mingyuan Wang contributed equally to this work.

Abstract

One-dimensional nanofibers can be transformed into hollow structures with larger specific surface area, which contributes to the enhancement of gas adsorption. We firstly fabricated Cu-doped In2O3 (Cu-In2O3) hollow nanofibers by electrospinning and calcination for detecting H2S. The experimental results show that the Cu doping concentration besides the operating temperature, gas concentration, and relative humidity can greatly affect the H2S sensing performance of the In2O3-based sensors. In particular, the responses of 6%Cu-In2O3 hollow nanofibers are 350.7 and 4201.5 to 50 and 100 ppm H2S at 250 ℃, which are over 20 and 140 times higher than those of pristine In2O3 hollow nanofibers, respectively. Moreover, the corresponding sensor exhibits excellent selectivity and good reproducibility towards H2S, and the response of 6%Cu-In2O3 is still 1.5 to 1 ppm H2S. Finally, the gas sensing mechanism of Cu-In2O3 hollow nanofibers is thoroughly discussed, along with the assistance of first-principles calculations. Both the formation of hollow structure and Cu doping contribute to provide more active sites, and meanwhile a little CuO can form p-n heterojunctions with In2O3 and react with H2S, resulting in significant improvement of gas sensing performance. The Cu-In2O3 hollow nanofibers can be tailored for practical application to selectively detect H2S at lower concentrations.

Keywords: electrospinning, Cu-doped In2O3, hollow nanofibers, H2S detection

References(62)

[1]
Kumar V, Majhi SM, Kim KH, et al. Advances in In2O3- based materials for the development of hydrogen sulfide sensors. Chem Eng J 2021, 404:126472.
[2]
Ali FIM, Awwad F, Greish YE, et al. Hydrogen sulfide (H2S) gas sensor: A review. IEEE Sens J 2019, 19:2394-2407.
[3]
Mirzaei A, Kim SS, Kim HW. Resistance-based H2S gas sensors using metal oxide nanostructures: A review of recent advances. J Hazard Mater 2018, 357:314-331.
[4]
Annanouch FE, Haddi Z, Vallejos S, et al. Aerosol-assisted CVD-grown WO3 nanoneedles decorated with copper oxide nanoparticles for the selective and humidity-resilient detection of H2S. ACS Appl Mater Interfaces 2015, 7:6842-6851.
[5]
Zhu LY, Yuan KP, Yang JH, et al. Hierarchical highly ordered SnO2 nanobowl branched ZnO nanowires for ultrasensitive and selective hydrogen sulfide gas sensing. Microsyst Nanoeng 2020, 6:30.
[6]
Wang MS, Luo Q, Hussain S, et al. Sharply-precipitated spherical assembly of ZnO nanosheets for low temperature H2S gas sensing performances. Mater Sci Semicond Process 2019, 100:283-289.
[7]
Reja SI, Sharma N, Gupta M, et al. A highly selective fluorescent probe for detection of hydrogen sulfide in living systems: In vitro and in vivo applications. Chem A Eur J 2017, 23:9872-9878.
[8]
Zhu L, Zeng W. Room-temperature gas sensing of ZnO- based gas sensor: A review. Sens Actuat A: Phys 2017, 267:242-261.
[9]
Ma JW, Fan HQ, Zheng XK, et al. Facile metal-organic frameworks-templated fabrication of hollow indium oxide microstructures for chlorine detection at low temperature. J Hazard Mater 2020, 387:122017.
[10]
Li R, Chen S, Lou Z, et al. Fabrication of porous SnO2 nanowires gas sensors with enhanced sensitivity. Sens Actuat B: Chem 2017, 252:79-85.
[11]
Liu SW, Wang MY, Liu GW, et al. Enhanced NO2 gas- sensing performance of 2D Ti3C2/TiO2 nanocomposites by in situ formation of Schottky barrier. Appl Surf Sci 2021, 567:150747.
[12]
Chethana DM, Thanuja TC, Mahesh HM, et al. Synthesis, structural, magnetic and NO2 gas sensing property of CuO nanoparticles. Ceram Int 2021, 47:10381-10387.
[13]
Liu D, Ren XW, Li YS, et al. Nanowires-assembled WO3 nanomesh for fast detection of ppb-level NO2 at low temperature. J Adv Ceram 2020, 9:17-26.
[14]
Wang MS, Jin CC, Luo Q, et al. Sol-gel derived TiO2-carbon composites with adsorption-enhanced photocatalytic activity and gas sensing performance. Ceram Int 2020, 46:18608-18613.
[15]
Xiong Y, Tang ZL, Wang Y, et al. Gas sensing capabilities of TiO2 porous nanoceramics prepared through premature sintering. J Adv Ceram 2015, 4:152-157.
[16]
Tan J, Hussain S, Ge CX, et al. ZIF-67 MOF-derived unique double-shelled Co3O4/NiCo2O4 nanocages for superior gas-sensing performances. Sens Actuat B: Chem 2020, 303:127251.
[17]
Ma JW, Fan HQ, Zhao N, et al. Synthesis of In2O3 hollow microspheres for chlorine gas sensing using yeast as bio-template. Ceram Int 2019, 45:9225-9230.
[18]
Song LF, Dou KP, Wang RR, et al. Sr-doped cubic In2O3/rhombohedral In2O3 homojunction nanowires for highly sensitive and selective breath ethanol sensing: Experiment and DFT simulation studies. ACS Appl Mater Interfaces 2020, 12:1270-1279.
[19]
Liu W, Xie YL, Chen TX, et al. Rationally designed mesoporous In2O3 nanofibers functionalized Pt catalysts for high-performance acetone gas sensors. Sens Actuat B: Chem 2019, 298:126871.
[20]
Araújo ES, Leão VNS. TiO2/WO3 heterogeneous structures prepared by electrospinning and sintering steps: Characterization and analysis of the impedance variation to humidity. J Adv Ceram 2019, 8:238-246.
[21]
Shen YB, Zhong XX, Zhang J, et al. In-situ growth of mesoporous In2O3 nanorod arrays on a porous ceramic substrate for ppb-level NO2 detection at room temperature. Appl Surf Sci 2019, 498:143873.
[22]
Tao ZH, Li YW, Zhang B, et al. Synthesis of urchin-like In2O3 hollow spheres for selective and quantitative detection of formaldehyde. Sens Actuat B: Chem 2019, 298:126889.
[23]
Zeng XG, Li S, He Y, et al. Gas sensors based on pearl- necklace-shaped In2O3 nanotubes with highly enhanced formaldehyde-sensing performance. J Mater Sci: Mater Electron 2019, 30:18362-18373.
[24]
Zhao CH, Gong HM, Niu GQ, et al. Electrospun Ca-doped In2O3 nanotubes for ethanol detection with enhanced sensitivity and selectivity. Sens Actuat B: Chem 2019, 299:126946.
[25]
Wei DD, Jiang WH, Gao HY, et al. Facile synthesis of La- doped In2O3 hollow microspheres and enhanced hydrogen sulfide sensing characteristics. Sens Actuat B: Chem 2018, 276:413-420.
[26]
Sun YJ, Zhao ZT, Suematsu K, et al. Rapid and stable detection of carbon monoxide in changing humidity atmospheres using clustered In2O3/CuO nanospheres. ACS Sens 2020, 5:1040-1049.
[27]
Li SH, Xie LL, He M, et al. Metal-organic frameworks- derived bamboo-like CuO/In2O3 heterostructure for high- performance H2S gas sensor with Low operating temperature. Sens Actuat B: Chem 2020, 310:127828.
[28]
Liang XS, Kim TH, Yoon JW, et al. Ultrasensitive and ultraselective detection of H2S using electrospun CuO-loaded In2O3 nanofiber sensors assisted by pulse heating. Sens Actuat B: Chem 2015, 209:934-942.
[29]
Park KR, Cho HB, Lee J, et al. Design of highly porous SnO2-CuO nanotubes for enhancing H2S gas sensor performance. Sens Actuat B: Chem 2020, 302:127179.
[30]
Momma K, Izumi F. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J Appl Cryst 2011, 44:1272-1276.
[31]
Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys Rev Lett 1996, 77:3865-3868.
[32]
Grimme S. Accurate description of van der Waals complexes by density functional theory including empirical corrections. J Comput Chem 2004, 25:1463-1473.
[33]
Seixas L, Carvalho A, Castro Neto AH. Atomically thin dilute magnetism in Co-doped phosphorene. Phys Rev B 2015, 91:155138.
[34]
Wang MY, Li LH, Zhao GH, et al. Influence of the surface decoration of phosphorene with Ag nanoclusters on gas sensing properties. Appl Surf Sci 2020, 504:144374.
[35]
Vikrant K, Kumar V, Ok YS, et al. Metal-organic framework (MOF)-based advanced sensing platforms for the detection of hydrogen sulfide. TrAC Trends Anal Chem 2018, 105:263-281.
[36]
Zhang C, Huan YC, Sun DJ, et al. Synthesis and NO2 sensing performances of CuO nanoparticles loaded In2O3 hollow spheres. J Alloys Compd 2020, 842:155857-155866.
[37]
Koo BR, Oh ST, Ahn HJ. Camphene effect for morphological change of electrospun SnO2 nanofibres: From dense to fibre-in-hollow and to hollow nanostructures. Mater Lett 2016, 178:288-291.
[38]
Zhang XL, Song DL, Liu Q, et al. Designed synthesis of Ag-functionalized Ni-doped In2O3 nanorods with enhanced formaldehyde gas sensing properties. J Mater Chem C 2019, 7:7219-7229.
[39]
Zhou JY, Bai JL, Zhao H, et al. Gas sensing enhancing mechanism via doping-induced oxygen vacancies for gas sensors based on indium tin oxide nanotubes. Sens Actuat B: Chem 2018, 265:273-284.
[40]
Liang QH, Zou XX, Chen H, et al. High-performance formaldehyde sensing realized by alkaline-earth metals doped In2O3 nanotubes with optimized surface properties. Sens Actuat B: Chem 2020, 304:127241.
[41]
Bai JL, Wang Q, Wang YR, et al. Role of nickel dopant on gas response and selectivity of electrospun indium oxide nanotubes. J Colloid Interface Sci 2020, 560:447-457.
[42]
Ri JS, Li XW, Shao CL, et al. Sn-doping induced oxygen vacancies on the surface of the In2O3 nanofibers and their promoting effect on sensitive NO2 detection at low temperature. Sens Actuat B: Chem 2020, 317:128194.
[43]
Wan K, Wang D, Wang F, et al. Hierarchical In2O3@SnO2 core-shell nanofiber for high efficiency formaldehyde detection. ACS Appl Mater Interfaces 2019, 11:45214-45225.
[44]
Vuong NM, Chinh ND, Huy BT, et al. CuO-decorated ZnO hierarchical nanostructures as efficient and established sensing materials for H2S gas sensors. Sci Rep 2016, 6:26736.
[45]
Chen KX, Lu H, Li G, et al. Surface functionalization of porous In2O3 nanofibers with Zn nanoparticles for enhanced low-temperature NO2 sensing properties. Sens Actuat B: Chem 2020, 308:127716.
[46]
Hittini W, Abu-Hani AF, Reddy N, et al. Cellulose-Copper Oxide hybrid nanocomposites membranes for H2S gas detection at low temperatures. Sci Rep 2020, 10:2940.
[47]
Wang YY, Duan GT, Zhu YD, et al. Room temperature H2S gas sensing properties of In2O3 micro/nanostructured porous thin film and hydrolyzation-induced enhanced sensing mechanism. Sens Actuat B: Chem 2016, 228:74-84.
[48]
Xu JQ, Wang XH, Shen JN. Hydrothermal synthesis of In2O3 for detecting H2S in air. Sens Actuat B: Chem 2006, 115:642-646.
[49]
Xu JQ, Wang XH, Li C. Electrochemical-deposited In2O3 nanocrystals for H2S detecting in air. Electrochem Solid- State Lett 2006, 9:H53.
[50]
Park S, Kim H, Jin C, et al. Enhanced gas sensing properties of multiple networked In2O3-core/ZnO-shell nanorod sensors. J Nanosci Nanotechnol 2013, 13:3427-3432.
[51]
Zheng W, Lu XF, Wang W, et al. Assembly of Pt nanoparticles on electrospun In2O3 nanofibers for H2S detection. J Colloid Interface Sci 2009, 338:366-370.
[52]
Liu B, Xu YM, Li K, et al. Pd-catalyzed reaction-producing intermediate S on a Pd/In2O3 surface: A key to achieve the enhanced CS2-sensing performances. ACS Appl Mater Interfaces 2019, 11:16838-16846.
[53]
Chen WW, Liu YK, Qin ZJ, et al. A single Eu-doped In2O3 nanobelt device for selective H2S detection. Sensors 2015, 15:29950-29957.
[54]
Kim SJ, Hwang IS, Kang YC, et al. Design of selective gas sensors using additive-loaded In2O3 hollow spheres prepared by combinatorial hydrothermal reactions. Sensors: Basel 2011, 11:10603-10614.
[55]
Zhao CH, Huang BY, Xie EQ, et al. Improving gas-sensing properties of electrospun In2O3 nanotubes by Mg acceptor doping. Sens Actuat B: Chem 2015, 207:313-320.
[56]
Wang C, Wang W, He K, et al. Pr-doped In2O3 nanocubes induce oxygen vacancies for enhancing triethylamine gas- sensing performance. Front Mater Sci 2019, 13:174-185.
[57]
Ma LG, Ai XQ, Lu YZ, et al. Facile and novel in situ low-temperature growth of Cu2S nanoarrays based on Cu substrates. Appl Phys A 2019, 125:373.
[58]
Boroun Z, Ghorbani M, Mohammadpour R, et al. Importance of N-P-N junction in H2S sensing process of SnO2-CuO heterostructures: A theoretical macroscopic approach. IEEE Sens J 2021, 21:7123-7129.
[59]
Sun LM, Zhuang Y, Yuan YS, et al. Nitrogen-doped carbon- coated CuO-In2O3 p-n heterojunction for remarkable photocatalytic hydrogen evolution. Adv Energy Mater 2019, 9:1902839.
[60]
Sun SJ, Zhang DS, Li CY, et al. DFT study on the adsorption and dissociation of H2S on CuO(111) surface. RSC Adv 2015, 5:21806-21811.
[61]
Stegmeier S, Fleischer M, Tawil A, et al. Sensing mechanism of room temperature CO2 sensors based on primary amino groups. Sens Actuat B: Chem 2011, 154:270-276.
[62]
Beheshtian J, Peyghan AA, Bagheri Z. Detection of phosgene by Sc-doped BN nanotubes: A DFT study. Sens Actuat B: Chem 2012, 171-172:846-852.
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Received: 12 July 2021
Revised: 28 September 2021
Accepted: 01 October 2021
Published: 06 January 2022
Issue date: March 2022

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© The Author(s) 2021.

Acknowledgements

This work was supported by the Key Research and Development Plan (BE2019094), Qing Lan Project ([2016]15), Six Talent Peaks Project (TD-XCL-004), and Graduate Research and Innovation Projects (5561220038) of Jiangsu Province. We are grateful for computational support from the High Performance Computing Platform of Jiangsu University, the Big Data Center of Southeast University, and the Advanced Computing East China Sub-center.

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