Preparation of zinc cobalt composite microstructures derived from metal-organic-framwork and gas-sensing properties of cyclohexanone

Sun Yong-Jiao; Wang Shi-Zhen; Zhang Wen-Lei; Wang Wen-Da; Zhang Wen-Dong; Hu Jie

doi:10.7498/aps.71.20212114

Abstract

Metal-organic-framework(MOF)-derived pure ZnO and ZnO/Co₃O₄ composite microstructures with different ratios are prepared by the sol-vothermal method. The crystalline structure, morphology and chemical composition for each of the prepared micro-structures are analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscope (XPS), and surface area analyzer respectively. The Gas sensors based on the as-prepared materials are fabricated and their performances of sensing various gases are investigated. The measurement results show that most of the gas sensors exhibit the highest responses to cyclohexanone gas within the test temperature range, and the composite with an appropriate amount of Co₃O₄ can obviously promote the cyclohexanoe-sensing property of ZnO microstructure. The response values of ZnO/Co₃O₄ composite microstructures to cyclohexanone first increase and then decrease with Co₃O₄ content increasing. The ZnO/Co₃O₄ composite microstructure sensor with a zinc-to-obalt ratio of 1∶0.1 shows that its value of response to cyclohexanone with a volume fraction of 100 × 10^–6 at the optimum working temperature (250 ℃) can arrive at 161, which is 6.4 times higher than that of ZnO microstructure under the same condition. Besides, its response and recovery time are 30 s and 35 s, respectively. This excellent detection performance is attributed mainly to the synergy effect between ZnO and Co₃O₄. The work has an important application value in the high-performance detection of cyclohexanone.

Keywords:

Authors and contacts

College of Information and Computer, Taiyuan University of Technology, Tiayun 030600, China

Corresponding author: Hu Jie, hujie@tyut.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 61904122, 62171308) and the Natural Science Foundation of Shanxi Province, China (Grant No. 201901D111090)

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References

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Cited By

图 1 ZnO和ZnO/Co₃O₄复合微结构的XRD图谱

Figure 1. XRD patterns of ZnO and ZnO/Co₃O₄ composite microstructures.

DownLoad: Full-Size Img PowerPoint

图 2 (a) ZnO, (b) Zn₁Co_0.05, (c) Zn₁Co_0.1, (d) Zn₁Co_0.2和(e) Zn₁Co₁复合微结构的SEM图和(f) Zn₁Co_0.1的EDS图谱

Figure 2. SEM images of (a) ZnO, (b) Zn₁Co_0.05, (c) Zn₁Co_0.1, (d) Zn₁Co_0.2 and (e) Zn₁Co₁ composite microstructures and EDS patterns of (f) Zn₁Co_0.1.

DownLoad: Full-Size Img PowerPoint

图 3 Zn₁Co_0.1复合微结构的氮吸附-脱附等温曲线与孔径分布曲线(插图)

Figure 3. Nitrogen adsorption-desorption isotherm and pore-size distribution curve (inset) of Zn₁Co_0.1 composite microstructure.

DownLoad: Full-Size Img PowerPoint

图 4 Zn₁Co_0.1复合微结构的XPS图谱(a), Zn 2p (b), O 1s (c)和Co 2p (d)

Figure 4. XPS spectra of Zn₁Co_0.1 composite microstructure (a), Zn 2p (b), O 1s (c) and Co 2p (d).

DownLoad: Full-Size Img PowerPoint

图 5 (a)—(e)ZnO和ZnO/Co₃O₄复合微结构的在不同温度下对7种体积分数为100 × 10^–6不同气体的响应值, (f)在不同温度下对体积分数为100 × 10^–6环己酮气体的响应曲线

Figure 5. (a)–(e) Response vaules of ZnO and ZnO/Co₃O₄ composite microstructures to 100 × 10^–6 (volume fraction) 7 kinds of different gases at different temperatures, and (f) response curves to 100 × 10^–6 (volume fraction) cyclohexanone gas at different temperatures.

DownLoad: Full-Size Img PowerPoint

图 6 ZnO和ZnO/Co₃O₄复合微结构的在250 ℃时对体积分数为100 × 10^–6环己酮气体的响应恢复曲线

Figure 6. Response-recovery curves of ZnO and ZnO/Co₃O₄ composite microstructures to 100 × 10^–6 (volume fraction) cyclohexanone at 250 ℃.

DownLoad: Full-Size Img PowerPoint

图 7 (a) ZnO和ZnO/Co₃O₄复合微结构在250 ℃时对不同浓度环己酮气体的响应恢复曲线, (b)传感器响应-环己酮浓度关系及(c)其对数形式关系

Figure 7. (a) Response-recovery curves of ZnO and ZnO/Co₃O₄ composite microstructures to various concentration of cyclohexanone at 250 ℃; (b) the relationship curves of the responses-cyclohexanone concentrations and (c) relationship in logarithm form.

DownLoad: Full-Size Img PowerPoint

图 8 ZnO/Co₃O₄复合微结构在(a)空气中和(b)环己酮气体中的能带示意图

Figure 8. The energy band diagrams of ZnO/Co₃O₄ composite microstructures (a) in air and (b) in cyclohexanone.

DownLoad: Full-Size Img PowerPoint

[1]	陈小梅, 陈颖, 袁霞 2021 无机材料学报 Google Scholar Chen X M, Chen Y, Yuan X 2021 J. Inorg. Mater.Google Scholar
[2]	王志峰 2013 中国化工贸易 5 127 Google Scholar Wang Z F 2013 China Chem. Trade 5 127 Google Scholar
[3]	Li Z 2018 Chemosensors 6 34 Google Scholar
[4]	Grazier K M, Swager T M 2013 Anal. Chem. 85 7154 Google Scholar
[5]	Ong C N, Sia G L, Chia S E 1991 J. Anal. Toxicl. 15 13 Google Scholar
[6]	Deelder R S, Hendricks P J H 1973 J. Chromatogr. A 83 343 Google Scholar
[7]	Pijolat C, Pupier C, Sauvan M, Tournier G, Lalauze R 1999 Sens. Actuators B:Chem. 59 195 Google Scholar
[8]	Gardon M, Guilemany J M 2013 J. Mater. Sci:Mater. Electron. 24 1410 Google Scholar
[9]	Franke M E, Koplin T J, Simon U 2006 Small 2 36 Google Scholar
[10]	Liu X, Cheng S T, Liu H, Hu S, Zhang D Q, Ning H S 2012 Sensors 12 9635 Google Scholar
[11]	Katoch A, Abideen Z U, Kim J H, Kim S S 2016 Sens. Actuators B:Chem. 232 698 Google Scholar
[12]	Yi G C, Wang C, Park W I 2005 Semicond. Sci. Tech. 20 S22 Google Scholar
[13]	Meng D, Liu D Y, Wang G S, Shen B, San Y B, Si J P, Meng F L 2019 Appl. Surf. Sci. 463 348 Google Scholar
[14]	Zhou T T, Zhang T 2021 Small Methods 5 2100515 Google Scholar
[15]	Rothschild A, Komem Y 2004 J. Appl. Phys. 95 6374 Google Scholar
[16]	Koo A, Yoo R, Woo S P, Lee H S, Lee W Y 2019 Sens. Actuators B: Chem. 280 109 Google Scholar
[17]	Qi T, Yang X, Sun J 2019 Sens. Actuators B:Chem. 283 93 Google Scholar
[18]	Lee C S, Dai Z F, Jeong S Y, Kwak C H, Kim B Y, Kim D H, Jang H W, Park J S, Lee J H 2016 Chem. Eur. J. 22 7102 Google Scholar
[19]	Nie S, Dastan D, Li J, Zhou W D, Wu S S, Zhou Y W, Yin X T 2021 J. Phys. Chem. Solid 150 109864 Google Scholar
[20]	Li B, Liu J Y, Liu Q, Chen R R, Zhang H S, Yu J, Song D L, Li J Q, Zhang M L, Wang J 2019 Appl. Surf. Sci. 475 700 Google Scholar
[21]	Xiong Y, Liu W D, Qiao X R, Song X J, Wang S C, Zhang X L, Wang X Z, Tian J 2021 Sens. Actuators B: Chem. 346 130486 Google Scholar
[22]	Bai S L, Guo J, Xiang X, Luo R X, Li D Q, Chen A F, Liu C C 2017 Sens. Actuators B: Chem. 245 359 Google Scholar
[23]	Shingange K, Tshbalala Z P, Nteaeaborwa O M, Motaung D E, Mhlongo G H 2016 J. Colloid Interf. Sci. 479 127 Google Scholar
[24]	Yun S, Lee J, Chung J, Lim S 2010 J. Phys. Chem. Solid 71 1724 Google Scholar
[25]	Jing H Y, Song X D, Ren S Z, Shi Y T, An Y L, Yang Y, Feng M Q, Ma S B, Hao C 2016 Electrochim. Acta 213 252 Google Scholar
[26]	Sakai G, Matsunaga N, Shimanoe K, Yamzoe N 2001 Sens. Actuators B 80 125 Google Scholar
[27]	Suematsu K, Shin Y, Hua Z Q, Yoshida K, Yuasa M, Kida T, Shimanoe K 2014 ACS Appl. Mater. Interfaces 6 5319 Google Scholar
[28]	Kida T, Kuroiwa T, Yuasa M, Shimanoe K, Yamazoe N 2008 Sens. Actuators B:Chem. 134 928 Google Scholar
[29]	Ahn M W, Park K S, Heo J H, Kim D W, Choi K J, Park J G 2009 Sens. Actuators B:Chem. 138 168 Google Scholar
[30]	Scott R W J, Yang S M, Chabanis G, Coombs N, Williams D E, Ozin G A 2001 Adv. Mater. 13 1468 Google Scholar
[31]	Liu L, Li S C, Zhuang J, Wang L Y, Zhang J B, Li H Y, Liu Z, Han Y, Jiang X X, Zhang P 2011 Sens. Actuators B: Chem. 155 728
[32]	Sahay P P, Nath R K 2008 Sens. Actuators B: Chem. 133 222 Google Scholar
[33]	Zhou T T, Zhang T, Deng J N, Zhang R, Lou Z, Wang L L 2017 Sens. Actuators B: Chem. 242 369 Google Scholar
[34]	Doan T L H, Kim J Y, Lee J H, Nguyen L H T, Dang Y T, Bui K B T, Pham A T T, Mirzaei A, Phan T B, Kim S S 2021 Sens. Actuators B: Chem. 348 130684 Google Scholar
[35]	Kim H R, Haensch A, Kim II D, Barsan N, Weimar U, Lee J H 2011 Adv. Funct. Mater. 21 4456 Google Scholar

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