CeO2-In2O3异质结复合材料的制备及其在三乙胺气敏监测中的应用

doi:10.16085/j.issn.1000-6613.2023-0495

摘要/Abstract

摘要：

以In(NO₃)₃∙4.5H₂O和Ce(NO₃)₃∙6H₂O为原料，对苯二甲酸为配体，N,N-二甲基甲酰胺为有机溶剂，通过热解金属有机骨架法（MOFs）成功制备了CeO₂-In₂O₃复合材料。采用X射线双晶粉末衍射仪（XRD）、透射电子显微镜（TEM）、扫描电子显微镜（SEM）、紫外-可见漫反射吸收光谱（UV-vis）和比表面积与孔隙度分析仪（BET）对材料的微观结构进行表征，研究了CeO₂-In₂O₃复合材料的气敏性能。结果表明，当In/Ce摩尔比为3∶1时，CeO₂-In₂O₃对1×10⁵μg/L三乙胺（TEA）的响应值（48.37）最高，是纯In₂O₃（9.45）的5倍，响应/恢复时间缩短至36s/22s，且该复合材料在173℃的最佳工作温度下具有优异的选择性和长期稳定性。复合材料传感性能的增强可归因于热解金属有机骨架法提供的大比表面积以及n-n异质结的形成。

关键词: CeO₂-In₂O₃, 三乙胺, 气敏性能, 气敏机理, 异质结

Abstract:

CeO₂-In₂O₃ composites were synthesized by pyrolysis metal-organic framework method (MOFs) using In(NO₃)₃∙4.5H₂O and Ce(NO₃)₃∙6H₂O as raw materials, terephthalic acid as ligand and N, N-dimethylformamide as organic solvent. The microstructure of the obtained materials was characterized by XRD, TEM, SEM, UV-vis and BET. The gas sensitive properties of obtained CeO₂-In₂O₃ composites were studied. The results indicated that when the molar ratio of In/Ce was 3∶1, CeO₂-In₂O₃ to 1×10⁵μg/L triethylamine (TEA) had the highest response values (48.37), which was 5 times that of pure In₂O₃ (9.45), response/recovery time was reduced to 36s/22s, and the composite had excellent selectivity and long-term stability at the optimum operating temperature of 173℃. The increased sensing performance can be attributed to the large specific surface area provided by pyrolytic metal-organic skeleton method and the formation of n-n heterojunction.

Key words: CeO₂-In₂O₃, triethylamine, gas sensitive performance, gas sensitive mechanism, heterojunction

中图分类号:

O649

钟彩丽, 莫秋莲, 孙建华, 丁宁宁, 廖丹葵, 孙丽霞. CeO₂-In₂O₃异质结复合材料的制备及其在三乙胺气敏监测中的应用[J]. 化工进展, 2024, 43(3): 1446-1455.

ZHONG Caili, MO Qiulian, SUN Jianhua, DING Ningning, LIAO Dankui, SUN Lixia. Preparation of CeO₂-In₂O₃ heterojunction composites for gas sensing monitoring of triethylamine[J]. Chemical Industry and Engineering Progress, 2024, 43(3): 1446-1455.

图/表 13

图1 CeO2-In2O3复合材料的制备流程图

图2 样品的XRD谱图

表1 In2O3和不同In/Ce摩尔比CeO2-In2O3复合材料的晶粒尺寸

材料名称	晶粒尺寸/nm
In₂O₃	16.60
5InCe	15.17
4InCe	12.42
3InCe	10.97
2InCe	11.98
InCe	14.95

图3 样品的微观形貌图

图4 样品的UV-vis谱图

图5 样品的氮气吸附脱附等温线图和孔径分布图

图6 In2O3和不同In/Ce摩尔比CeO2-In2O3复合材料在84~263℃时对1×105 μg/L三乙胺的响应

图7 In2O3和3InCe在173℃下对1×105μg/L各种气体的选择性曲线

图8 样品的暂态响应曲线和线性拟合图

图9 In2O3和3InCe在173℃下对1×105μg/L三乙胺的响应/恢复曲线（插图为In2O3和3InCe的电阻曲线）

图10 样品对三乙胺的重复性测试和稳定性测试

表2 本研究与其他文献中报道的三乙胺传感响应进行比较

传感材料	气体浓度/μg·L^-1	工作温度/℃	灵敏度	响应/恢复时间/s	参考文献
SnWO₄	2×10⁵	240	17.58	18/17	[26]
Fe₂O₃	0.5×10⁵	270	3.6	1/25	[27]
Fe₂O₃/ZnO	1×10⁵	260	14.5	1/14	[28]
BiOBr/ZnO	1×10⁵	200	20.75	4/198	[29]
CaFeO₃	2×10⁵	200	7.4	9/49	[30]
3InCe	1×10⁵	173	48.37	36/22	本工作

图11 3InCe的能带结构示意图

参考文献 32

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CeO₂-In₂O₃异质结复合材料的制备及其在三乙胺气敏监测中的应用

Preparation of CeO₂-In₂O₃ heterojunction composites for gas sensing monitoring of triethylamine

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