硅酸盐学报

La³⁺掺杂ZnFe₂O₄材料的制备及其气敏性能

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刘韧 ¹ , 白玉莹 ¹ , 胡梦婷 ¹ , 刘翠翠 ¹ , 储向峰 ¹ , 梁士明 ²

硅酸盐学报 | 研究论文 2026,54(6): 2072-2079

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硅酸盐学报 |研究论文 2026 , 54 (6) : 2072 -2079

La³⁺掺杂ZnFe₂O₄材料的制备及其气敏性能

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刘韧¹, 白玉莹¹, 胡梦婷¹, 刘翠翠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:

刘韧（2001—），男，硕士研究生。

Gas-Sensing Properties of La³⁺ Doped ZnFe₂O₄ Materials

Ren LIU¹, Yuying BAI¹, Mengting HU¹, Cuicui LIU¹, 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 Ren (2001-), male, Master candidate. E-mail: 3011714468@qq.com

出版时间: 2026-05-13 doi: 10.14062/j.issn.0454-5648.20250563

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摘要

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呼出气中挥发性有机物（VOCs）浓度低，实现其精准检测至关重要。本工作采用静电纺丝法制备了La³⁺掺杂ZnFe₂O₄材料，通过X射线衍射（XRD）、扫描电子显微镜（SEM）和X射线光电子能谱（XPS）对材料的晶体结构、表面形貌和元素价态进行分析。结果表明，8%（质量分数）La³⁺掺杂的ZnFe₂O₄材料在室温下对0.1 g/L丙酮的灵敏度为21.3，是纯ZnFe₂O₄的11.5倍，最低检测限为0.000 01 g/L，该复合材料制备的气体传感器能够在室温下检测低浓度丙酮气体，对人体呼出气体中丙酮的检测具有良好应用前景。

关键词

气体传感器 / 室温传感 / 丙酮 / 铁酸锌

Abstract

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Introduction

Exhaled breath analysis technology enables the preliminary diagnosis of certain diseases via detecting the concentration of volatile organic compounds (VOCs) in human breath. Some studies indicate that acetone can serve as a biomarker to assist in the diagnosis of diabetes. Developing acetone gas sensors with low detection limits and high selectivity is thus crucial for achieving early screening of diabetes. In recent years, spinel ferrites, as an important class of metal oxides, have attracted much attention in the gas sensing field due to their low cost and excellent stability. Among them, ZnFe₂O₄ can improve the number of active sites on the material surface via tailoring its microstructure, thereby exhibiting a high sensitivity to VOCs like acetone. However, single-component ZnFe₂O₄ gas sensors suffer from issues such as high operating temperatures and low gas-sensing selectivity in practical detection. The existing research shows that ion doping is a modification method that induces lattice distortion in metal oxides, thereby regulating surface defects on the material. The generation of surface defects can provide more active centers for gas-sensing reactions and promote the adsorption of oxygen molecules on the material surface, thus improving its gas-sensing properties. Furthermore, doping rare-earth elements into MOS materials can enhance their catalytic activity and increase electron migration rates, leading to an improved sensing performance. This study was to prepare a series of La³⁺-doped ZnFe₂O₄ composites via electrospinning. Their morphology, surface chemical composition, and elemental valence states were characterized, and the gas-sensing properties of the composites were analyzed.

Methods

0.808 g Fe(NO₃)₃·9H₂O (AR, Sinopharm Chemical Reagent Co., Ltd., China), 0.297 g Zn(NO₃)₂·6H₂O (AR, Sinopharm Chemical Reagent Co., Ltd., China), and varying mass ratios of La(NO₃)₃·nH₂O (AR, Sinopharm Chemical Reagent Co., Ltd., China) were accurately weighed. Each mixture was put into respective 10 mL beakers, add 5 mL of DMF (AR, Sinopharm Chemical Reagent Co., Ltd., China), and stir to dissolve. 0.85 g of PVP (AR, Shanghai Aladdin Biochemical Technology Co., Ltd., China) was added slowly to each solution and continue stirring for over 12 h until complete dissolution of PVP. After stirring no visible bubbles remained in the solution. The solutions were transferred into 10 mL syringes and mounted onto a horizontal electrospinning apparatus. The needle tip was set as an anode (11-13 kV) and the aluminum foil collector as a cathode, with an electrode distance of 15 cm. The ambient humidity was maintained at 30%-50% and the solution was fed at a rate of 3 μL/min. The electrospun fibers collected were calcined in a muffle furnace at 600 ℃ for 2 h (at a heating rate of 1 ℃/min). The phase composition was analyzed by X-ray diffraction (XRD, Bruker D8 Advance, 40 kV, 40 mA, Cu-K_α, 5(°)/min, 10°-80°). The microstructure of the samples was determined by scanning electron microscope (SEM) with an accelerating voltage of 15 kV. The elemental valence states of the materials were analyzed by a X-ray photoelectron spectroscopy (XPS, Al K_α, hν=1486 eV).

For the determination of the gas-sensitive properties of La doping ZnFe₂O₄ composite material, the sample was placed in a mortar, and 1-2 drops of turpentine penetration alcohol were added. The mixture was ground until a uniform paste was formed. The paste was then evenly applied onto the surface of an alumina ceramic tube using a small brush. Afterwards, a nickel-chromium heating wire was passed through the ceramic tube and welded to the base of the gas sensor. Finally, the gas sensor was aged at 200 ℃ for 12 h before conducting gas-sensing performance tests.

Results and Discussion

The XRD patterns show that the grain size is significantly reduced and the gas-sensing performance is improved, indicating that La³⁺ doping inhibits the crystallization process and hinders crystal growth. A reduction in grain size leads to an increase in the specific surface area of the sensor, providing more acetone active sites on the surface of the material. The SEM images show that the surface of La³⁺-doped ZnFe₂O₄ nanomaterials is relatively smooth and cross-linked to form a network structure. The EDS results indicate that the composite material is composed of elements La, Zn, Fe, and O. According to the XPS analysis, La³⁺doping causes a lattice distortion, resulting in an increase in adsorbed oxygen on the material surface. The more oxygen is adsorbed on the surface of the material, which in turn improves the gas-sensing performance. Based on the analysis of UV-visible absorption spectroscopy and the corresponding band gap, the sample LZF-8 has a narrower band gap, indicating that the energy required for electron transition is lower, which is beneficial to electron migration, thereby shortening the response/recovery time. The response value of sample LZF-8 to 0.1 g/L acetone at room temperature is 21.3, which is 11.5 times greater than that of pure ZnFe₂O₄. Meanwhile, the selectivity and sensitivity of the material to different gases at room temperature are investigated. The results show that the sample LZF-8 has good selectivity and detection limit for acetone, with the minimum detection limit of 0.00001 g/L, proving that the prepared sensor LZF-8 has a great application potential.

Conclusions

ZnFe₂O₄ composites doped with different proportions of La³⁺ were prepared via electrospinning. Based on the analysis of the XRD patterns, SEM images, and XPS spectra, La³⁺ was successfully doped into ZnFe₂O₄. The results of gas-sensing test showed that as 8% La³⁺ was doped, the response value (i.e., R_a/R_g = 21.3) to 0.1 g/L acetone at room temperature was approximately 11.5 times greater than that of pure ZnFe₂O₄ (R_a/R_g = 1.7), with the response/recovery time of 27.0 s/10.7 s, and the minimum detection limit of acetone concentration of 0.00001 g/L. This composite gas sensor could have a great potential for efficient detection of acetone gas under room temperature conditions.

Key words

gas sensor / room temperature detection / acetone / zinc ferrite

引用本文

刘韧, 白玉莹, 胡梦婷, 刘翠翠, 储向峰, 梁士明. La³⁺掺杂ZnFe₂O₄材料的制备及其气敏性能. 硅酸盐学报, 2026 , 54 (6) : 2072 -2079 . DOI: 10.14062/j.issn.0454-5648.20250563

Ren LIU, Yuying BAI, Mengting HU, Cuicui LIU, Xiangfeng CHU, Shiming LIANG. Gas-Sensing Properties of La³⁺ Doped ZnFe₂O₄ Materials[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (6) : 2072 -2079 . DOI: 10.14062/j.issn.0454-5648.20250563

基金

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

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2026年第54卷第6期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250563

接收时间：2025-07-18
首发时间：2026-10-22
出版时间：2026-05-13

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收稿日期：2025-07-18
修回日期：2025-09-16

基金

国家自然科学基金(62371003)

山东省自然科学基金(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。

参考文献

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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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