Abstract
This study report on a sonochemical synthesis of 1- and 3-dimensional hierarchical nanostructured cobalt oxide systems (Co3O4) and their application in ammonia sensing at room temperature (i.e., 30 °C). The Co3O4 nanostructures were synthesized via a room temperature-assisted precipitation and subsequent thermal treatment of the oxalate precursor. The resulted nanostructures were characterized by SEM, XRD, TEM, FTIR spectroscopy, BET, and TGA/DTA. The synthesis mechanism was proposed on the basis of morphology analyzed at various stages of the particle growth. It was observed that the final hierarchical microspheres structure resulted from the self-aggregation of the initially formed nanorods. The microspheres and nanorods were used as efficient room temperature gas sensors for ammonia detection in the concentration range of 0.01–500 ppm. The nanorod-based sensor showed an unusual n-type sensing behavior to ammonia in a temperature range of 30–300 °C. This transition of p to n-type was correlated to the formation of successive layers of physisorbed water molecules at the surface of the synthesized Co3O4. However, in case of the microspheres, the n-type behavior and superior sensitivity were observed at 30 °C followed by a negligible response up to 200 °C, while the intrinsic p-type behavior was recorded at an elevated temperature (200–300 °C). The observed unusual sensing performance may be associated with the crystallographic nature and lattice strain in the material structures. Additionally, the large specific surface area and the change in crystalline structure with temperature made the as prepared novel hierarchical Co3O4 structures a distinctive material for sensing ammonia at 30 °C.
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The datasets generated or analyzed during the current study are available from the corresponding author on reasonable request.
References
Y. Gui, L. Yang, K. Tian, H. Zhang, S. Fang, P-type Co3O4 nanoarrays decorated on the surface of n-type flower-like WO3 nanosheets for high-performance gas sensing. Sens. Actuators B Chem. 288, 104–112 (2019). https://doi.org/10.1016/j.snb.2019.02.101
S. Vladimirova, V. Krivetskiy, M. Rumyantseva, A. Gaskov, N. Mordvinova, O. Lebedev, M. Martyshov, P. Forsh, Co3O4 as p-type material for CO sensing in humid air. Sensors. 17, 2216–2221 (2017)
M. Wang, T. Hou, X. Zhao, H. Yu, H. Ji, Crucial structural effects of porous Co3O4 derived from prussian blue analogue on the enhanced gas sensing performance. Mater. Lett. 242, 83–86 (2019). https://doi.org/10.1016/J.MATLET.2019.01.076
M. Govindhan, B. Sidhureddy, A. Chen, High-temperature hydrogen gas sensor based on three-dimensional hierarchical-nanostructured nickel–cobalt oxide. ACS Appl. Nano Mater. 1, 6005–6014 (2018). https://doi.org/10.1021/acsanm.8b00835
C. Su, L. Zhang, Y. Han, X. Chen, S. Wang, M. Zeng, N. Hu, Y. Su, Z. Zhou, H. Wei, Z. Yang, Glucose-assisted synthesis of hierarchical flower-like Co3O4 nanostructures assembled by porous nanosheets for enhanced acetone sensing. Sens. Actuators B Chem. 288, 699–706 (2019). https://doi.org/10.1016/J.SNB.2019.03.004
Y. Li, N. Luo, G. Sun, B. Zhang, H. Jin, L. Lin, H. Bala, J. Cao, Z. Zhang, Y. Wang, Synthesis of porous nanosheets-assembled ZnO/ZnCo2O4 hierarchical structure for TEA detection. Sens. Actuators B Chem. 287, 199–208 (2019). https://doi.org/10.1016/J.SNB.2019.02.055
H. Liu, Y. He, K. Nagashima, G. Meng, T. Dai, B. Tong, Z. Deng, S. Wang, N. Zhu, T. Yanagida, X. Fang, Discrimination of VOCs molecules via extracting concealed features from a temperature-modulated p-type NiO sensor. Sens. Actuators B Chem. 293, 342–349 (2019). https://doi.org/10.1016/J.SNB.2019.04.078
Z. Jin, L.-P. Wang, Y. Zhang, J. Fan, M.-H. Liao, X.-F. Wang, Y. Ding, Highly sensitive and selective ethanol sensors based on porous Co3O4 nanobelts synthesized through a facile wet-chemistry method. J. Nanoparticle Res. 21, 115–121 (2019). https://doi.org/10.1007/s11051-019-4549-7
B. Sakthivel, G. Nammalvar, Selective ammonia sensor based on copper oxide/reduced graphene oxide nanocomposite. J. Alloys Compd. 788, 422–428 (2019). https://doi.org/10.1016/J.JALLCOM.2019.02.245
J. Tan, M. Dun, L. Li, J. Zhao, W. Tan, Z. Lin, X. Huang, Synthesis of hollow and hollowed-out Co3O4 microspheres assembled by porous ultrathin nanosheets for ethanol gas sensors: responding and recovering in one second. Sens. Actuators B Chem. 249, 44–52 (2017). https://doi.org/10.1016/J.SNB.2017.04.063
B.K. Satpathy, A.K. Nayak, C.R. Raj, D. Pradhan, Morphology-dependent charge storage performance of Co3O4 nanostructures in an all-solid-state flexible supercapacitor, New. J. Chem. 43, 15177–15186 (2019). https://doi.org/10.1039/C9NJ03070K
P.M. Ette, K. Selvakumar, S.M. Senthil Kumar, K. Ramesha, Ordered 1D and 3D mesoporous Co3O4 structures: effect of morphology on Li-ion storage and high rate performance. Electrochim. Acta. 310, 184–194 (2019). https://doi.org/10.1016/J.ELECTACTA.2019.04.105
U.T. Nakate, P. Patil, S.P. Choudhury, S.N. Kale, Microwave assisted synthesis of Co3O4 and NiO nanoplates and structural, optical, magnetic characterizations. Nano-Struct Nano-Obj. 14, 66–72 (2018). https://doi.org/10.1016/J.NANOSO.2018.01.007
Y. Bai, J. Dong, Y. Hou, Y. Guo, Y. Liu, Y. Li, X. Han, Z. Huang, Co3O4 @PC derived from ZIF-67 as an efficient catalyst for the selective catalytic reduction of NOx with NH3 at low temperature. Chem. Eng. J. 361, 703–712 (2019). https://doi.org/10.1016/J.CEJ.2018.12.109
S. Deng, X. Liu, N. Chen, D. Deng, X. Xiao, Y. Wang, A highly sensitive VOC gas sensor using p-type mesoporous Co3O4 nanosheets prepared by a facile chemical coprecipitation method. Sens. Actuators B Chem. 233, 615–623 (2016). https://doi.org/10.1016/J.SNB.2016.04.138
J.M. Xu, J.P. Cheng, The advances of Co3O4 as gas sensing materials: a review. J. Alloys Compd. 686, 753–768 (2016). https://doi.org/10.1016/J.JALLCOM.2016.06.086
Z. Li, Z. Lin, N. Wang, J. Wang, W. Liu, K. Sun, Y.Q. Fu, Z. Wang, High precision NH3 sensing using network nano-sheet Co3O4 arrays based sensor at room temperature. Sens. Actuators B Chem. 235, 222–231 (2016). https://doi.org/10.1016/J.SNB.2016.05.063
U.V. Patil, N.S. Ramgir, N. Karmakar, A. Bhogale, A.K. Debnath, D.K. Aswal, S.K. Gupta, D.C. Kothari, Room temperature ammonia sensor based on copper nanoparticle intercalated polyaniline nanocomposite thin films. Appl. Surf. Sci. 339, 69–74 (2015). https://doi.org/10.1016/J.APSUSC.2015.02.164
D. Kwak, Y. Lei, R. Maric, Ammonia gas sensors: a comprehensive review. Talanta 204, 713–730 (2019). https://doi.org/10.1016/J.TALANTA.2019.06.034
R. Sankar Ganesh, E. Durgadevi, M. Navaneethan, V.L. Patil, S. Ponnusamy, C. Muthamizhchelvan, S. Kawasaki, P.S. Patil, Y. Hayakawa, Low temperature ammonia gas sensor based on Mn-doped ZnO nanoparticle decorated microspheres. J. Alloys Compd. 721, 182–190 (2017). https://doi.org/10.1016/J.JALLCOM.2017.05.315
J. Deng, R. Zhang, L. Wang, Z. Lou, T. Zhang, Enhanced sensing performance of the Co3O4 hierarchical nanorods to NH3 gas. Sens. Actuators B Chem. 209, 449–455 (2015). https://doi.org/10.1016/J.SNB.2014.11.141
N. Zubair, K. Akhtar, High performance room temperature gas sensor based on novel morphology of zinc oxide nanostructures. Trans. Nonferrous Met. Soc. China. 29, 143–156 (2019). https://doi.org/10.1016/S1003-6326(18)64923-4
K. Akhtar, I.U. Haq, K. Malook, Gas sensing properties of semiconducting copper oxide nanospheroids. Powder Technol. 283, 505–511 (2015). https://doi.org/10.1016/j.powtec.2015.06.023
J. Camargo et al., Controlled synthesis: nucleation and growth in solution. Met. Nanostruct. 28, 49–74 (2015). https://doi.org/10.1007/978-3-319-11304-3_2
F. Mohandes, M. Salavati-Niasari, Sonochemical synthesis of silver vanadium oxide micro/nanorods: solvent and surfactant effects. Ultrason. Sonochem. 20, 354–365 (2013). https://doi.org/10.1016/j.ultsonch.2012.05.002
S.F. Wang, F. Gu, M.K. Lu, Sonochemical synthesis of hollow. PbS Nanospheres 22, 398–401 (2005). https://doi.org/10.1021/LA0518647
S. Ali, V.S. Myasnichenko, E.C. Neyts, Size-dependent strain and surface energies of gold nanoclusters. Phys. Chem. Chem. Phys. 18, 792–800 (2016). https://doi.org/10.1039/C5CP06153A
L. Ren, P. Wang, Y. Han, C. Hu, B. Wei, Synthesis of CoC2O4·2H2O nanorods and their thermal decomposition to Co3O4 nanoparticles. Chem. Phys. Lett. 476, 78–83 (2009). https://doi.org/10.1016/J.CPLETT.2009.06.015
D. Wang, Q. Wang, T. Wang, Morphology-controllable synthesis of cobalt oxalates and their conversion to mesoporous Co3O4 nanostructures for application in supercapacitors. Inorg. Chem. 50, 6482–6492 (2011). https://doi.org/10.1021/ic200309t
M. Salavati-Niasari, N. Mir, F. Davar, Synthesis and characterization of Co3O4 nanorods by thermal decomposition of cobalt oxalate. J. Phys. Chem. Solids. 70, 847–852 (2009). https://doi.org/10.1016/J.JPCS.2009.04.006
Q. Guo, X. Guo, Q. Tian, Optionally ultra-fast synthesis of CoO/Co3O4 particles using CoCl2 solution via a versatile spray roasting method. Adv. Powder Technol. 21, 529–533 (2010). https://doi.org/10.1016/J.APT.2010.02.003
A. Pan, Y. Wang, W. Xu, Z. Nie, S. Liang, Z. Nie, C. Wang, G. Cao, J.-G. Zhang, High-performance anode based on porous Co3O4 nanodiscs. J. Power Sources. 255, 125–129 (2014). https://doi.org/10.1016/J.JPOWSOUR.2013.12.131
P.N. Shelke, Y.B. Khollam, P.N. Pabrekar, P.S. More, A.M. Datir, S.D. Chakane, K.C. Mohite, P. Koinkar, Synthesis and characterization of Co3O4 powders for humidity sensing. Int. J. Mod. Phys. Conf. Ser. 06, 197–202 (2012). https://doi.org/10.1142/S2010194512003170
Z. Fan, W. Fang, Z. Zhang, M. Chen, W. Shangguan, Highly active rod-like Co3O4 catalyst for the formaldehyde oxidation reaction. Catal. Commun. 103, 10–14 (2018). https://doi.org/10.1016/J.CATCOM.2017.09.003
R.K. Bedi, I. Singh, Room-temperature ammonia sensor based on cationic surfactant-assisted nanocrystalline CuO. ACS Appl Mater. Interfaces. 2, 1361–1368 (2010). https://doi.org/10.1021/am900914h
A. Hakim, J. Hossain, K.A. Khan, Temperature effect on the electrical properties of undoped NiO thin films. Renew. Energy. 34, 2625–2629 (2009). https://doi.org/10.1016/j.renene.2009.05.014
R.S. Devan, Y.D. Kolekar, B.K. Chougule, Effect of cobalt substitution on the properties of nickel-copper ferrite. J. Phys. Condens. Matter. 18, 9809–9821 (2006). https://doi.org/10.1088/0953-8984/18/43/004
M. Caglar, S. Ilican, Y. Caglar, F. Yakuphanoglu, Electrical conductivity and optical properties of ZnO nanostructured thin film. Appl. Surf. Sci. 255, 4491–4496 (2009). https://doi.org/10.1016/j.apsusc.2008.11.055
I. Jiménez, M.A. Centeno, R. Scotti, F. Morazzoni, J. Arbiol, A. Cornet, J.R. Morante, NH3 interaction with chromium-doped WO3 nanocrystalline powders for gas sensing applications. J. Mater. Chem. 14, 2412–2420 (2004). https://doi.org/10.1039/b400872c
J. Cao, S. Wang, H. Zhang, T. Zhang, Facile construction of Co3O4 porous microspheres with enhanced acetone gas sensing performances. Mater. Sci. Semicond. Process. 101, 10–15 (2019). https://doi.org/10.1016/j.mssp.2019.05.014
S. Wang, J. Cao, W. Cui, L. Fan, X. Li, D. Li, Facile synthesis of bamboo raft-like Co3O4 with enhanced acetone gas sensing performances. J. Alloys Compd. 758, 45–53 (2018). https://doi.org/10.1016/j.jallcom.2018.05.139
X. Zhang, J. Wang, L. Xuan, Z. Zhu, Q. Pan, K. Shi, G. Zhang, Novel Co3O4 nanocrystalline chain material as a high performance gas sensor at room temperature. J. Alloys Compd. 768, 190–197 (2018). https://doi.org/10.1016/j.jallcom.2018.07.240
D.R. Miller, S.A. Akbar, P.A. Morris, Nanoscale metal oxide-based heterojunctions for gas sensing: a review. Sens. Actuators, B Chem. 204, 250–272 (2014). https://doi.org/10.1016/j.snb.2014.07.074
Z. Dai, C.S. Lee, Y. Tian, I.D. Kim, J.H. Lee, Highly reversible switching from p- to n-type NO2 sensing in a monolayer Fe2O3 inverse opal film and the associated p-n transition phase diagram. J. Mater. Chem. A. 3, 3372–3381 (2015). https://doi.org/10.1039/c4ta05438e
P. Gupta, T. Dutta, S. Mal, J. Narayan, Controlled p-type to n-type conductivity transformation in NiO thin films by ultraviolet-laser irradiation. J. Appl. Phys. 111, 0137061–0137067 (2012). https://doi.org/10.1063/1.3671412
R. Molaei, R. Bayati, J. Narayan, Crystallographic characteristics and p -type to n -type transition in epitaxial Nio thin film. Cryst. Growth Des. 13, 5459–5465 (2013). https://doi.org/10.1021/cg401408f
J.M. Tulliani, A. Cavalieri, S. Musso, E. Sardella, F. Geobaldo, Room temperature ammonia sensors based on zinc oxide and functionalized graphite and multi-walled carbon nanotubes. Sens. Actuators B Chem. 152, 144–154 (2011). https://doi.org/10.1016/j.snb.2010.11.057
N. Zubair, K. Akhtar, High performance room temperature gas sensor based on novel morphology of zinc oxide nanostructures. Trans. Nonferrous Met. Soc. 29, 143–156 (2019). https://doi.org/10.1016/S1003-6326(18)64923-4
J.W. Yoon, H.J. Kim, H.M. Jeong, J.H. Lee, Gas sensing characteristics of p-type Cr2O3 and Co3O4 nanofibers depending on inter-particle connectivity. Sens. Actuators B Chem. 202, 263–271 (2014). https://doi.org/10.1016/j.snb.2014.05.081
X. Liu, M. Hu, Y. Wang, J. Liu, Y. Qin, High sensitivity NO2 sensor based on CuO/p-porous silicon heterojunction at room temperature. J. Alloys Compd. 685, 364–369 (2016). https://doi.org/10.1016/j.jallcom.2016.05.215
L. Gao, Z. Cheng, Q. Xiang, Y. Zhang, J. Xu, Porous corundum-type In2O3 nanosheets: synthesis and NO2 sensing properties. Sens. Actuators B Chem. 208, 436–443 (2015). https://doi.org/10.1016/j.snb.2014.11.053
Q. Li, Y. Du, X. Li, G. Lu, W. Wang, Y. Geng, Z. Liang, X. Tian, Different Co3O4 mesostructures synthesised by templating with KIT-6 and SBA-15 via nanocasting route and their sensitivities toward ethanol. Sens. Actuators B Chem. 235, 39–45 (2016). https://doi.org/10.1016/j.snb.2016.05.033
T. Li, W. Zeng, H. Long, Z. Wang, Nanosheet-assembled hierarchical SnO2 nanostructures for efficient gas-sensing applications. Sens. Actuators B Chem. 231, 120–128 (2016). https://doi.org/10.1016/j.snb.2016.03.003
T.R. Reina, A.Á. Moreno, S. Ivanova, J.A. Odriozola, M.A. Centeno, Influence of vanadium or cobalt oxides on the CO oxidation behavior of Au/MO x/CeO2-Al2O3 systems. Chem. Cat. Chem. 4, 512–520 (2012). https://doi.org/10.1002/cctc.201100373
H.J. Kim, J.H. Lee, Highly sensitive and selective gas sensors using p-type oxide semiconductors: overview. Sens. Actuators B Chem. 192, 607–627 (2014). https://doi.org/10.1016/j.snb.2013.11.00
Acknowledgements
The authors are thankful to the National Centre of Excellence in Physical Chemistry (NCEPC), University of Peshawar, Khyber Pakhtunkhwa, and the Higher Education Commission of Pakistan (HEC), for facilitating this research work.
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This study was funded by National Centre of Excellence in Physical Chemistry (NCEPC), University of Peshawar, Khyber Pakhtunkhwa, and the Higher Education Commission of Pakistan (HEC).
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Khalid, H., Akhtar, K. Room temperature synthesis and ammonia sensing of monodispersed hierarchical 1 and 3-dimensional Co3O4 nanostructures: switching from p to n-type sensing. J Mater Sci: Mater Electron 33, 3361–3383 (2022). https://doi.org/10.1007/s10854-021-07535-5
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DOI: https://doi.org/10.1007/s10854-021-07535-5