硅酸盐学报

WS₂-CdSnO₃复合材料的制备及甲醛气敏性能

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刘醒醒 ¹ , 胡梦婷 ¹ , 刘翠翠 ¹ , 李佳豪 ¹ , 储向峰 ¹ , 梁士明 ²

硅酸盐学报 | 研究论文 2024,52(12): 3849-3855

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硅酸盐学报 |研究论文 2024 , 52 (12) : 3849 -3855

WS₂-CdSnO₃复合材料的制备及甲醛气敏性能

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刘醒醒¹, 胡梦婷¹, 刘翠翠¹, 李佳豪¹, 储向峰¹, 梁士明²

作者信息

^1．安徽工业大学化学与化工学院，安徽马鞍山 243002

^2．临沂大学材料科学与工程学院，山东临沂 276005

通讯作者:

储向峰（1966—），男，博士，教授；

梁士明（1983—），男，博士，副教授。

作者简介:

刘醒醒（1995—），女，硕士研究生。

Preparation and Formaldehyde Sensing Properties of WS₂-CdSnO₃ Composite Materials

Xingxing LIU¹, Mengting HU¹, Cuicui LIU¹, Jiahao LI¹, Xiangfeng CHU¹, Shiming LIANG²

Affiliations

^1.School of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan 243002, Anhui

^2.School of Materials Science and Engineering, Linyi University, Linyi 276005, Shandong, China

Corresponding Author:

CHU Xiangfeng (1966-), male, Ph.D., Professor; E-mail: xfchu99@ahut.edu.cn;

LIANG Shiming (1983-), male, Ph.D., Associate Professor. lsmwind@163.com

LIU Xingxing (1995-), female, Master candidate. E-mail: 1638708379@qq.com

出版时间: 2024-12-20 doi: 10.14062/j.issn.0454-5648.20240191

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摘要

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实现甲醛气体的高效检测对人类健康和环境污染十分重要。采用共沉淀-煅烧法制备了CdSnO₃，并利用超声分散法制备了一系列不同质量比的WS₂-CdSnO₃复合材料。用X射线衍射、扫描电子显微镜和X射线能谱等对CdSnO₃和复合材料WS₂-CdSnO₃的相结构、形貌和元素价态进行了表征，研究了WS₂对CdSnO₃的气体传感性能的影响，结果表明：与适量的WS₂复合可以提高CdSnO₃的气敏性能。在工作温度140 ℃条件下，3.5%（质量分数）的WS₂-CdSnO₃复合材料对0.01%甲醛气体的响应为15.7，是CdSnO₃的4.2倍。

关键词

二硫化钨 / 偏锡酸镉 / 甲醛 / 气敏性能

Abstract

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Introduction

Organic compound formaldehyde (HCHO) is a toxic volatile gas with an irritating odour, which is mainly derived from building materials, furniture and various adhesive coatings. Living in an environment containing formaldehyde gas for a long time can cause a series of hazards to human health, such as headaches, allergies, nausea, and even genetic mutations and leukaemia. It is thus necessary to design a gas sensor with a superior sensing performance to detect formaldehyde in real time. ABO₃ type chalcogenide metal oxides have attracted much attention in sensor research, but their application is restricted due to the drawbacks such as poor sensitivity and high operating temperature. Many studies indicate that the modification of metal oxides with two-dimensional transition metal dihalides (2D TMDs) is one of the effective strategies to improve the gas sensing performance, and among the 2D TMDs materials, WS₂ has aroused much interest in sensor research because of its high specific surface area, good thermal stability and excellent electron mobility. The gas sensor performance of metal oxides can be improved via the combination of WS₂ to form a novel nanocomposite material. Hence, in this paper, a series of WS₂-CdSnO₃ composites with different mass ratios were prepared by an ultrasonic mixing method. The microstructure, crystal structure, and valence state structure of WS₂-CdSnO₃ composite material were characterized, and the gas sensing performance of the composite material was analyzed.

Methods

CdSnO₃ was prepared with Cd(NO₃)₂·4H₂O (AR, Shanghai Sarn Chemical Technology, China) and SnCl₄·5H₂O (AR) (Shanghai Aladdin Reagent Co., China). CdSnO₃ was ultrasonically compounded with WS₂ (99.9%) to obtain WS₂-CdSnO₃ composites. The physical phase composition, surface morphology, elemental composition, valence and pore size distribution and specific surface area of the composites were characterized by a model SmartLab SE X-ray diffractometer (XRD, Rigaku Co.,), scanning electron microscope (SEM, Tescan Mira Lms), a model K-Alpha X-ray photoelectron spectrometer (XPS, Thermo Scientific Co., USA), and a model ASAP 2460 fully automated specific surface and porosity analyser (BET, Micromeritics Co., USA).

For the determination of gas sensing performance of WS₂-CdSnO₃ composite material, WS₂-CdSnO₃ composite material was put into a mortar with 1-2 drops of terpineol, and thoroughly mixed and ground. The paste was evenly applied to the outer wall of the alumina ceramic tube with a small brush, and an Ni-Cr heating wire put through the ceramic tube and welded firmly to the hexagonal base. The operating temperature was indirectly controlled via adjusting the amount of power added to the two sections of the heating wire. The sensitivity to gases is expressed as a ratio of the stable resistance value of the gas sensing material in air to a stable resistance value in the gas tested. The gas sensing performance of the composites was investigated at a relative humidity of 55% (except for humidity tests).

Results and discussion

From the SEM images, the microcube appeared is CdSnO₃, and the cubes structure is agglomerated on the surface of layered WS₂. Based on the EDS analysis, there are five elements Cd, Sn, O, W and S in the composites. It is indicated that WS₂-CdSnO₃ can be prepared. According to the XPS analysis, there are more oxygen vacancies in the sample WSC-2, which can provide more sites for oxygen adsorption, so that more target gases participate in the reaction on the surface of the material. The introduction of WS₂ increases the specific surface area of the sample WSC-2, and the material with a larger specific surface area has more gas adsorption active sites, thus improving the gas sensing performance of the sensor. The sample WSC-2 has the maximum response value of 15.7 for 0.01% formaldehyde at 140 ℃. To check the potential practical application of the prepared WSC-2 sensor, the selectivity and sensitivity of the sensor to different gases were investigated at 140 ℃. The results show that the sample WSC-2 has the optimum selectivity for 0.01% formaldehyde, and the response value is 4.2 times higher than that of CdSnO₃.

Conclusions

A series of WS₂-CdSnO₃ composites with different ratios were prepared via ultrasonic dispersion mixing. WS₂-CdSnO₃ had a large specific surface area, which was beneficial for gas adsorption and diffusion. The gas sensing performance of CdSnO₃ with different ratios of WS₂-CdSnO₃ composites were investigated, and the results showed that 3.5% WS₂-CdSnO₃ had the optimum selectivity for formaldehyde and the superior gas sensing performance at 140 ℃, and the sensitivity for 0.01% formaldehyde was 4.2 times higher than that of CdSnO₃ material, and the detection limit was 0.0001%. Therefore, the 3.5% WS₂-CdSnO₃ composite had potential applications in indoor formaldehyde detection. This study indicated that the modification of metal oxides by two-dimensional TMD could be one of the effective strategies to improve the gas sensing performance.

Key words

tungsten disulfide / cadmium metastantinate / formaldehyde / gas sensing

引用本文

刘醒醒, 胡梦婷, 刘翠翠, 李佳豪, 储向峰, 梁士明. WS₂-CdSnO₃复合材料的制备及甲醛气敏性能. 硅酸盐学报, 2024 , 52 (12) : 3849 -3855 . DOI: 10.14062/j.issn.0454-5648.20240191

Xingxing LIU, Mengting HU, Cuicui LIU, Jiahao LI, Xiangfeng CHU, Shiming LIANG. Preparation and Formaldehyde Sensing Properties of WS₂-CdSnO₃ Composite Materials[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (12) : 3849 -3855 . DOI: 10.14062/j.issn.0454-5648.20240191

基金

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国家自然科学基金项目(62371003)
山东省自然科学基金项目(ZR2020MF025)

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2024年第52卷第12期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240191

接收时间：2024-03-06
首发时间：2026-10-22
出版时间：2024-12-20

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收稿日期：2024-03-06
修回日期：2024-05-14

基金

国家自然科学基金项目(62371003)

山东省自然科学基金项目(ZR2020MF025)

作者信息

^1．安徽工业大学化学与化工学院，安徽马鞍山 243002

^2．临沂大学材料科学与工程学院，山东临沂 276005

通讯作者:

储向峰（1966—），男，博士，教授；

梁士明（1983—），男，博士，副教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240191

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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