收稿日期: 2020-02-26
网络出版日期: 2021-05-10
基金资助
国家自然科学基金资助项目(21671128);国家自然科学基金资助项目(21671130);国家自然科学基金资助项目(41807304);国家自然科学基金资助项目(21805181);中国博士后科学基金资助项目(2017M611529)
Synthesis of Ce-doped Co3O4 nanoflowers with rich oxygen vacancies based on MOF template method for enhancing gas sensing performance
Received date: 2020-02-26
Online published: 2021-05-10
Co3O4 纳米材料在气体传感器应用中, 存在灵敏度不高、响应恢复时间长等问题. 采用简单的溶剂热法制备了 Ce 掺杂的 Co 基金属有机骨架 (metal organic framework, MOF) 前体. 通过热处理成功合成了 Ce 掺杂 Co3O4 纳米花, 并通过 X 射线衍射 (X-ray diffraction, XRD)、扫描电子显微镜 (scanning electron microscope, SEM)、X 射线光电子能谱 (X-ray photoelectron spectroscope, XPS)、能量色散光谱 (energy dispersive spectroscope, EDS) 等表征方法, 对材料进行了物相形貌分析. 结果显示: Ce 掺杂能有效改变 Co3O4 的氧分布态, 提高其氧空位含量, 由此材料制成的传感器显示出了优异的传感性能; 在 190 °C 操作温度下, 该传感器对 100×10-6 正丁醇的响应值可达 87.79, 且其计算所得理论检出限可达 122×10-9 .
何永超, 李飞, 颜炳君, 何新华, 浦娴娟, 宁珠凯, 程伶俐, 焦正 . 基于 MOF 模板法合成 Ce 掺杂 Co3O4 富氧空位纳米花及其气敏性能[J]. 上海大学学报(自然科学版), 2022 , 28(1) : 19 -30 . DOI: 10.12066/j.issn.1007-2861.2284
Co3O4 nanomaterials have low sensitivity and long response/recovery time in gas sensor applications. Ce-doped Co-based metal organic framework (MOF) precursors were prepared by a simple solvothermal method and Ce-doped Co3O4 nanoflowers were then successfully synthesised by heat treatment. The morphology and composition of the materials were analysed by X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscope (XPS), energy dispersive spectroscope (EDS), and other characterization methods. The results indicated that Ce doping could effectively change the oxygen distribution and increase the number of oxygen vacancies in Co3O4 . The sensor made of this material exhibited an excellent sensing performance. At an operating temperature of 190 °C, the response to 100×10-6 n-butanol could reach 87.79 and the calculated theoretical detection limit could reach 122×10-9.
Key words： Ce-doped; Co3O4 ; gas sensors; oxygen vacancies
| [1] | Wang M J, Shen Z R, Zhao X D, et al. Rational shape control of porous Co$_{3}$O$_{4}$ assemblies derived from MOF and their structural effects on n-butanol sensing[J]. Journal of Hazardous Materials, 2019, 371: 352-361. |
| [2] | Zhang X C, Wang J, Xuan L C, et al. Novel Co$_{3}$O$_{4}$ nanocrystalline chain material as a high performance gas sensor at room temperature[J]. Journal of Alloys and Compounds, 2018, 768: 190-197. |
| [3] | Han D M, Ji Y, Gu F B, et al. Cobalt oxide nanorods with special pore structure for enhanced ethanol sensing performance[J]. Journal of Colloid and Interface Science, 2018, 531: 320-330. |
| [4] | Zheng F C, Yin Z C, Xia H Y, et al. MOF-derived porous Co$_{3}$O$_{4}$ cuboids with excellent performance as anode materials for lithium-ion batteries[J]. Materials Letters, 2017, 197: 188-191. |
| [5] | Zhang C, Wei J, Chen L Y, et al. All-solid-state asymmetric supercapacitors based on Fe-doped mesoporous Co$_{3}$O$_{4}$ and three-dimensional reduced graphene oxide electrodes with high energy and power densities[J]. Nanoscale, 2017, 9(40): 15423-15433. |
| [6] | Xu X L, Sun X F, Han H, et al. Improving water tolerance of Co$_{3}$O$_{4}$ by SnO$_{2}$ addition for CO oxidation[J]. Applied Surface Science, 2015, 355: 1254-1260. |
| [7] | Dong X Q, Su Y Y, Lu T, et al. MOFs-derived dodecahedra porous Co$_{3}$O$_{4}$: an efficient cataluminescence sensing material for H$_{2}$S[J]. Sensors and Actuators B: Chemical, 2018, 258: 349-357. |
| [8] | Jiang R, Jia L H, Guo X F, et al. Dimethyl sulfoxide-assisted hydrothermal synjournal of Co$_{3}$O$_{4}$-based nanorods for selective and sensitive diethyl ether sensing[J]. Sensors and Actuators B: Chemical, 2019, 290: 275-284. |
| [9] | Koo W T, Yu S, Choi S J, et al. Nanoscale PdO catalyst functionalized Co$_{3}$O$_{4}$ hollow nanocages using MOF templates for selective detection of acetone molecules in exhaled breath[J]. ACS Applied Materials & Interfaces, 2017, 9(9): 8201-8210. |
| [10] | Hwang S J, Choi K I, Yoon J W, et al. Pure and palladium-loaded Co$_{3}$O$_{4}$ hollow hierarchical nanostructures with giant and ultraselective chemiresistivity to xylene and toluene[J]. Chemistry A: European Journal, 2015, 21(15): 5872-5878. |
| [11] | Xiao J, Diao K D, Zheng Z, et al. MOF-derived porous ZnO/Co$_{3}$O$_{4}$ nanocomposites for high performance acetone gas sensing[J]. Journal of Materials Science Materials in Electronics, 2018, 29(10): 8535-8546. |
| [12] | Guo L L, Chen F, Xie N, et al. Metal-organic frameworks derived tin-doped cobalt oxide yolk-shell nanostructures and their gas sensing properties[J]. Journal of Colloid and Interface Science, 2018, 528: 53-62. |
| [13] | Zhang N, Qin Q X, Ma X H, et al. One-step synjournal and gas sensing properties of hierarchical Fe doped Co$_{3}$O$_{4}$, nanostructures[J]. Journal of Alloys and Compounds, 2017, 723: 779-786. |
| [14] | Mai H X, Sun L D, Zhang Y W, et al. Shape-selective synjournal and oxygen storage behavior of ceria nanopolyhedra, nanorods, and nanocubes[J]. The Journal of Physical Chemistry B, 2005, 109(51): 24380-24385. |
| [15] | Zhang J, Kumagai H, Yamamuar K, et al. Extra-low-temperature oxygen storage capacity of CeO$_{2}$ nanocrystals with cubic facets[J]. Nano Letters, 2011, 11(2): 361-364. |
| [16] | Zhang Y Q, Liu Y Y, Zhou L S, et al. The role of Ce doping in enhancing sensing performance of ZnO-based gas sensor by adjusting the proportion of oxygen species[J]. Sensors and Actuators B: Chemical, 2018, 273: 991-998. |
| [17] | Li L, Liu M M, He S J, et al. Freestanding 3D mesoporous Co$_{3}$O$_{4}$@carbon foam nanostructures for ethanol gas sensing[J]. Analytical Chemistry, 2014, 86(15): 7996-8002. |
| [18] | Deng J N, Zhang R, Wang L L, et al. Enhanced sensing performance of the Co$_{3}$O$_{4}$ hierarchical nanorods to NH$_{3}$ gas[J]. Sensors and Actuators B: Chemical, 2015, 209: 449-455. |
| [19] | Li Q Q, Huang Z, Guan P F, et al. Simultaneous Ni doping at atom scale in ceria and assembling into well-defined lotus-like structure for enhanced catalytic performance[J]. ACS Applied Materials & Interfaces, 2017, 9(19): 16243-16251. |
| [20] | Motaung D E, Mhlongo G H, Makgwane P R, et al. Ultra-high sensitive and selective H$_{2}$ gas sensor manifested by interface of n-n heterostructure of CeO$_{2}$-SnO$_{2}$ nanoparticles[J]. Sensors and Actuators B: Chemical, 2017, 254: 984-995. |
| [21] | Force C, Roman E, Guil J M, et al. XPS and 1H-NMR study of thermally stabilized Rh/CeO$_{2}$ catalysts submitted to reduction/oxidation treatments[J]. Langmuir the ACS Journal ofSurfaces & Colloids, 2007, 23(8): 4569-4574. |
| [22] | Wang X, Wan T K, Si G K, et al. Oxygen vacancy defects engineering on Ce-doped α-Fe$_{2}$O$_{3}$ gas sensor for reducing gases[J]. Sensors and Actuators B: Chemical, 2020, 302: 127165. |
| [23] | Chen Y, Zhou M M, Dong Z G, et al. Enhanced acetone detection performance using facile CeO$_{2}$-SnO$_{2}$ nanosheets[J]. Applied Physics A, 2020, 126(1): 33. |
| [24] | Hu J, Zou C, Su Y J, et al. One-step synjournal of 2D C$_{3}$N$_{4}$-tin oxide gas sensors for enhanced acetone vapor detection[J]. Sensors and Actuators B: Chemical, 2017, 253: 641-651. |
| [25] | Barsan N, Weimar U. Conduction model of metal oxide gas sensors[J]. Journal of Electroceramics, 2001, 7(3): 143-167. |
| [26] | Zhang Y Q, Liu Y Y, Zhou L S, et al. The role of Ce doping in enhancing sensing performance of ZnO-based gas sensor by adjusting the proportion of oxygen species[J]. Sensors and Actuators B: Chemical, 2018, 273: 991-998. |
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