不同金属掺杂的SnO2基气体传感器对挥发性有机物的检测性能及机制

doi:10.16085/j.issn.1000-6613.2024-1099

摘要/Abstract

摘要：

我国近地面臭氧（O₃）污染日益严重，“十四五”生态环境规划把O₃列为控制重点，因此，作为O₃前驱物质的挥发性有机物（VOCs）测量成为了一个焦点。本研究以VOCs的便携监测为需求，制备基于SnO₂的气体传感器，并分别用Sb、Co、Zn掺杂改善SnO₂的气敏性能。利用SEM和XRD表征材料，纯SnO₂材料为球状颗粒；Sb-SnO₂材料为碎屑状并聚集成团；Co-SnO₂材料似麦片状；Zn-SnO₂材料为规则的矩形薄片。对各传感器进行VOCs气敏测试，结果表明，SnO₂气体传感器对乙醇有最高的响应值；而Co-SnO₂气体传感器的目标气体变为丙酮；Sb-SnO₂与Zn-SnO₂气体传感器均对三乙胺有选择性。其中，Zn-SnO₂气体传感器对三乙胺响应速度快（6s）、选择性好、稳定性佳、检测下限低（<1μL/L）。Zn-SnO₂传感器在最适工作温度250℃下对50μL/L三乙胺的灵敏度为49.6，较SnO₂气体传感器的灵敏度提升了8.1倍。最后，简要分析了气体传感器的敏感机理，以期为痕量大气VOCs环境检测提供一定的技术支持。

关键词: 挥发性有机物, 气体传感器, 金属掺杂, 二氧化锡, 气敏性能

Abstract:

Near-surface ozone (O₃) pollution in China is becoming more and more serious, and the "14th Five-Year" ecological and environmental plan has listed O₃ as a priority for control, so the measurement of volatile organic compounds (VOCs), which is a precursor of O₃, has become a focus. In order to meet the demand for portable monitoring of VOCs, SnO₂-based gas sensors were prepared and the gas-sensitive properties of SnO₂ were improved by doping with Sb, Co and Zn, respectively. The materials were characterized using SEM and XRD. The pure SnO₂ materials were spherical particles, the Sb-SnO₂ materials were crumbly and aggregated into clusters, the Co-SnO₂ materials appeared to be wheat flakes and the Zn-SnO₂ materials were regular rectangular flakes. The VOCs gas sensitivity test was performed for each sensor, and the results showed that the SnO₂ gas sensor had the highest response value for ethanol while the target gas of the Co-SnO₂ gas sensor was changed to acetone, and both the Sb-SnO₂ and Zn-SnO₂ gas sensors were selective for triethylamine. Among them, the Zn-SnO₂ gas sensor showed fast response (6s), good selectivity, good stability and low detection limit (<1μL/L) for triethylamine. The sensitivity of the Zn-SnO₂ sensor for 50μL/L triethylamine at the optimum operating temperature of 250℃ was 49.6, which was 8.1 times higher than that of the SnO₂ gas sensor. Finally, the sensitivity mechanism of the gas sensors was briefly analyzed in order to provide certain technical support for the environmental detection of trace atmospheric VOCs.

Key words: volatile organic compounds (VOCs), gas sensors, metal doping, stannic oxide (SnO₂), gas-sensitive properties

中图分类号:

X511

程静雯, 陈庆彩, 于博, 刘欢, 徐腾飞, 呼宇坤, 刘思彤. 不同金属掺杂的SnO₂基气体传感器对挥发性有机物的检测性能及机制[J]. 化工进展, 2025, 44(9): 5140-5149.

CHENG Jingwen, CHEN Qingcai, YU Bo, LIU Huan, XU Tengfei, HU Yukun, LIU Sitong. Detection performance and mechanism of VOCs by different metal-doped SnO₂-based gas sensors[J]. Chemical Industry and Engineering Progress, 2025, 44(9): 5140-5149.

图/表 14

图1 气敏材料的XRD谱图

图2 各材料的XPS能谱图

图3 各气敏材料的扫描电镜（SEM）图像

图4 SnO2及3种掺杂材料的氮气吸附和解吸等温线

表1 孔径和比表面积

样品	平均孔径/nm	孔容积/cm³·g^-1	比表面积/m²·g^-1
SnO₂	4.1999	0.0908	86.5241
Sb-SnO₂	19.8434	0.2244	45.2376
Co-SnO₂	23.5044	0.1558	26.5188
Zn-SnO₂	26.1887	0.2291	34.9946

图5 不同工作温度下各气体传感器对不同 VOCs气体（50μL/L）的响应

图6 纯SnO2和不同金属掺杂的气体传感器对不同浓度目标气体的响应

图7 最佳工作状态下各传感器对不同浓度目标气体的线性工作曲线

图8 各气体传感器在最佳温度下对1μL/L其目标气体的灵敏度响应

图9 各气体传感器在最佳工作温度下对其目标气体(50μL/L)的响应恢复曲线

图10 最佳工作温度下各气体传感器对不同VOCs气体（50μL/L）的响应

图11 各气体传感器在最佳工作温度下对其目标气体（50μL/L）的长期稳定性

图12 气敏材料对VOCs的气敏机理

图13 各材料的EPR能谱

参考文献 44

[1]	李万勇, 黄浩瑜, 王艳振, 等. 聊城市城区夏季VOCs污染特征及来源解析[J]. 环境科学, 2023, 44(12): 6564-6575.
	LI Wanyong, HUANG Haoyu, WANG Yanzhen, et al. Pollution characteristics and source apportionment of VOCs in urban areas of Liaocheng in summer[J]. Environmental Science, 2023, 44(12): 6564-6575.
[2]	ZHANG Kai, DING Honglei, PAN Weiguo, et al. Research progress of a composite metal oxide catalyst for VOC degradation[J]. Environmental Science & Technology, 2022, 56(13): 9220-9236.
[3]	WANG Shuyi, ZHAO Yilong, HAN Yu, et al. Spatiotemporal variation, source and secondary transformation potential of volatile organic compounds (VOCs) during the winter days in Shanghai, China[J]. Atmospheric Environment, 2022, 286: 119203.
[4]	DAI Mingjun, ZHAO Liupeng, GAO Hongyu, et al. Hierarchical assembly of α -Fe₂O₃ nanorods on multiwall carbon nanotubes as a high-performance sensing material for gas sensors[J]. ACS Applied Materials & Interfaces, 2017, 9(10): 8919-8928.
[5]	WANG Qingji, KOU Xueying, LIU Chang, et al. Hydrothermal synthesis of hierarchical CoO/SnO₂ nanostructures for ethanol gas sensor[J]. Journal of Colloid and Interface Science, 2018, 513: 760-766.
[6]	HSIAO Yu-Jen, NAGARJUNA Yempati, TSAI Chun-An, et al. High selectivity Fe₃O₄ nanoparticle to volatile organic compound (VOC) for MEMS gas sensors[J]. Materials Research Express, 2020, 7(6): 065013.
[7]	LIU Yaning, GAO Lilin, FU Shiyang, et al. Highly efficient VOC gas sensors based on Li-doped diamane[J]. Applied Surface Science, 2023, 611: 155694.
[8]	TIAN Qinghua, CHEN Yanbin, ZHANG Feng, et al. Hierarchical carbon-riveted 2D@0D TiO₂ nanosheets@SnO₂ nanoparticles composite for an improved lithium-ion battery anode[J]. Applied Surface Science, 2020, 511: 145625.
[9]	GAILLARD Nicolas, PRASHER Dixit, CHONG Marina, et al. Wide-bandgap Cu(In, Ga)S₂ photocathodes integrated on transparent conductive F:SnO₂ substrates for chalcopyrite-based water splitting tandem devices[J]. ACS Applied Energy Materials, 2019, 2(8): 5515-5524.
[10]	HUANG Shahua, Nasir ALI, HUAI Zhaoxiang, et al. A facile strategy for enhanced performance of inverted organic solar cells based on low-temperature solution-processed SnO₂ electron transport layer[J]. Organic Electronics, 2020, 78: 105555.
[11]	张清. SnO₂气体传感器选择性改善研究进展[J]. 微纳电子技术, 2022, 59(12): 1263-1270.
	ZHANG Qing. Research progress on selectivity improvement of SnO₂ gas sensors[J]. Micronanoelectronic Technology, 2022, 59(12): 1263-1270.
[12]	BAIK Nam Seok, SAKAI Go, MIURA Norio, et al. Preparation of stabilized nanosized tin oxide particles by hydrothermal treatment[J]. Journal of the American Ceramic Society, 2000, 83(12): 2983-2987.
[13]	LIU X M, WU S L, CHU Paul K, et al. Characteristics of nano Ti-doped SnO₂ powders prepared by sol-gel method[J]. Materials Science and Engineering: A, 2006, 426(1/2): 274-277.
[14]	ZENG Yi, WANG Yanzhe, QIAO Liang, et al. Synthesis and the improved sensing properties of hierarchical SnO₂ hollow nanosheets with mesoporous and multilayered interiors[J]. Sensors and Actuators B: Chemical, 2016, 222: 354-361.
[15]	胡瑞金, 王兢, 朱慧超. PdO, Au, CdO修饰SnO₂纳米纤维的制备及其气敏特性[J]. 物理化学学报, 2015, 31(10): 1997-2004.
	HU Ruijin, WANG Jing, ZHU Huichao. Preparation and gas sensing properties of PdO, Au, CdO coatings on SnO₂ nanofibers[J]. Acta Physico-Chimica Sinica, 2015, 31(10): 1997-2004.
[16]	YANG Jiaqi, HAN Wenjiang, MA Jian, et al. Sn doping effect on NiO hollow nanofibers based gas sensors about the humidity dependence for triethylamine detection[J]. Sensors and Actuators B: Chemical, 2021, 340: 129971.
[17]	FAN Yaru, XU Yanyan, WANG Yuxuan, et al. Fabrication and characterization of Co-doped ZnO nanodiscs for selective TEA sensor applications with high response, high selectivity and ppb-level detection limit[J]. Journal of Alloys and Compounds, 2021, 876: 160170.
[18]	MA Longtao, FAN Huiqing, TIAN Hailin, et al. The n-ZnO/n-In₂O₃ heterojunction formed by a surface-modification and their potential barrier-control in methanal gas sensing[J]. Sensors and Actuators B: Chemical, 2016, 222: 508-516.
[19]	WANG Yun, ZHANG Hui, SUN Xuhui. Electrospun nanowebs of NiO/SnO₂ p-n heterojunctions for enhanced gas sensing[J]. Applied Surface Science, 2016, 389: 514-520.
[20]	WANG Dongxue, GU Kuikun, ZHANG Jing, et al. MOF-derived NiWO₄@NiO p-p heterostructure for distinguish detection of TEA and xylene by temperature regulation[J]. Journal of Alloys and Compounds, 2021, 875: 160015.
[21]	璩光明, 杨莹丽, 王国东, 等. 金属氧化物半导体气体传感器改性研究进展[J]. 传感器与微系统, 2022, 41(2): 1-4.
	QU Guangming, YANG Yingli, WANG Guodong, et al. Research progress in properties modification of metal oxide semiconductor gas sensors[J]. Transducer and Microsystem Technologies, 2022, 41(2): 1-4.
[22]	WANG Li, MA Shuyi, LI Jianpeng, et al. Mo-doped SnO₂ nanotubes sensor with abundant oxygen vacancies for ethanol detection[J]. Sensors and Actuators B: Chemical, 2021, 347: 130642.
[23]	TOMER Vijay K, SINGH Kulvinder, KAUR Harmanjit, et al. Rapid acetone detection using indium loaded WO₃/SnO₂ nanohybrid sensor[J]. Sensors and Actuators B: Chemical, 2017, 253: 703-713.
[24]	FAN Guijun, NIE Linfeng, WANG Hang, et al. Ce doped SnO/SnO₂ heterojunctions for highly formaldehyde gas sensing at low temperature[J]. Sensors and Actuators B: Chemical, 2022, 373: 132640.
[25]	于丹, 田振玉, 杜利军, 等. 国内VOCs来源、排放标准及脱除技术分析[J]. 工程热物理学报, 2024, 45(6): 1825-1837.
	YU Dan, TIAN Zhenyu, DU Lijun, et al. Source, emission standard and abatement technique of VOCs in China[J]. Journal of Engineering Thermophysics, 2024, 45(6): 1825-1837.
[26]	翟增秀, 李佳音, 杨伟华, 等. 典型化学制品企业OVOCs排放特征及环境影响[J]. 环境科学学报, 2024, 44(10): 111-120.
	ZHAI Zengxiu, LI Jiayin, YANG Weihua, et al. Emission characteristics and environmental impact of OVOCs in typical chemical product enterprises[J]. Acta Scientiae Circumstantiae, 2024, 44(10): 111-120.
[27]	SHAO Ping, AN Junlin, XIN Jinyuan, et al. Source apportionment of VOCs and the contribution to photochemical ozone formation during summer in the typical industrial area in the Yangtze River Delta, China[J]. Atmospheric Research, 2016, 176: 64-74.
[28]	TONG Dan, CHEN Jiangyao, QIN Dandan, et al. Mechanism of atmospheric organic amines reacted with ozone and implications for the formation of secondary organic aerosols[J]. Science of the Total Environment, 2020, 737: 139830.
[29]	苑雪玲. 热解金属有机骨架法制备SnO₂基复合材料及其气敏性能研究[D]. 南宁: 广西大学, 2021.
	YUAN Xueling. Preparation by pyrolyzation of metallic organic frameworks and gas-sensing properties of SnO₂-based composites [D]. Nanning: Guangxi University, 2021.
[30]	张晓, 徐瑶华, 刘皓, 等. 基于金属氧化物的乙醇检测气敏材料的研究进展[J]. 化工进展, 2019, 38(7): 3207-3226.
	ZHANG Xiao, XU Yaohua, LIU Hao, et al. Recent advances of ethanol detection materials based on metal oxides[J]. Chemical Industry and Engineering Progress, 2019, 38(7): 3207-3226.
[31]	LUO Yifan, Ahmadou LY, LAHEM Driss, et al. Role of cobalt in Co-ZnO nanoflower gas sensors for the detection of low concentration of VOCs[J]. Sensors and Actuators B: Chemical, 2022, 360: 131674.
[32]	曾文, 林志东, 高俊杰. 金属离子掺杂纳米SnO₂材料的气敏性能及掺杂机理[J]. 纳米技术与精密工程, 2008(3): 174-179.
	ZENG Wen, LIN Zhidong, GAO Junjie. Gas sensitivity and the mechanism of nano-SnO₂ doped by metallic ions[J]. Nanotechnology and Precision Engineering, 2008(3): 174-179.
[33]	LI Yuxiu, CHEN Nan, DENG Dongyang, et al. Formaldehyde detection: SnO₂ microspheres for formaldehyde gas sensor with high sensitivity, fast response/recovery and good selectivity[J]. Sensors and Actuators B: Chemical, 2017, 238: 264-273.
[34]	徐林婕. 基于传感器阵列的多组分VOCs检测及工业应用验证研究[D]. 杭州: 浙江大学, 2023.
	XU Linjie. Research on multi-component VOCs detection based on sensor array and its industrial application verification[D]. Hangzhou: Zhejiang University, 2023.
[35]	LIU Fangmeng, YANG Zijie, HE Junming, et al. Ultrafast-response stabilized zirconia-based mixed potential type triethylamine sensor utilizing CoMoO₄ sensing electrode[J]. Sensors and Actuators B: Chemical, 2018, 272: 433-440.
[36]	金士成, 闫爽. 金属氧化物室温气敏材料的结构调控及传感机理[J]. 化学进展, 2021, 33(12): 2348-2361.
	JIN Shicheng, YAN Shuang. Nanostructure construction and sensing mechanism of metal oxides for room temperature gas sensing[J]. Progress in Chemistry, 2021, 33(12): 2348-2361.
[37]	XU Keng, ZOU Jingping, TIAN Shouqin, et al. Single-crystalline porous nanosheets assembled hierarchical Co₃O₄ microspheres for enhanced gas-sensing properties to trace xylene[J]. Sensors and Actuators B: Chemical, 2017, 246: 68-77.
[38]	HU Jie, YANG Jie, WANG Wenda, et al. Synthesis and gas sensing properties of NiO/SnO₂ hierarchical structures toward ppb-level acetone detection[J]. Materials Research Bulletin, 2018, 102: 294-303.
[39]	WANG Wanjing, XIAN Jianbiao, LI Jin, et al. Construction of Co₃O₄/SnO₂ yolk-shell nanofibers for acetone gas detection[J]. Sensors and Actuators B: Chemical, 2024, 398: 134724.
[40]	MENG Xiaoning, YAO Mengxia, MU Shifang, et al. Oxygen vacancies enhance triethylamine sensing properties of SnO₂ nanoparticles[J]. ChemistrySelect, 2019, 4(38): 11268-11274.
[41]	ZHAO Liupeng, LI Yiwen, ZHOU Yue, et al. Mechanism of high- and low-valence doping on adsorbed oxygen of SnO₂-based gas sensors and a strategy to combine the advantages of both dopants[J]. Sensors and Actuators B: Chemical, 2022, 371: 132603.
[42]	WANG Mengjie, LIU Hongyan, SUN Caixuan, et al. High efficiency toluene sensor based on iron-doped nickel oxide triple-shell microspheres with high moisture resistance[J]. Materials Science and Engineering: B, 2024, 299: 117001.
[43]	WANG Yanzhe, LIU Chunbao, QIAO Liang, et al. Localized inside-out Ostwald ripening of hybrid double-shelled cages into SnO₂ triple-shelled hollow cubes for improved toluene detection[J]. Nanoscale, 2020, 12(3): 2011-2021.
[44]	RAMANATHAN Ramarajan, NAGARAJAN Selvakumar, SATHIYAM OORTHY Surya, et al. A highly sensitive and room temperature ethanol gas sensor based on spray deposited Sb doped SnO₂ thin films[J]. Materials Advances, 2024, 5(1): 293-305.

不同金属掺杂的SnO₂基气体传感器对挥发性有机物的检测性能及机制

Detection performance and mechanism of VOCs by different metal-doped SnO₂-based gas sensors

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