纳米Pt/ZnO异质结构的制备及其气敏性能

doi:10.16085/j.issn.1000-6613.2022-1976

摘要/Abstract

摘要：

三乙胺（TEA）作为挥发性有机化合物（VOCs）的一种重要组成，会对人体和环境造成严重的危害，因此检测三乙胺具有十分重要的意义。然而目前三乙胺实际检测存在高成本和操作耗时的问题，因此迫切需要一种制备简单以及便于监测和检测三乙胺的方法。本文采用水热法设计合成了半导体氧化物Pt/ZnO异质结构，并对其气敏性能进行了系统研究。用X射线衍射（XRD）、透射电子显微镜（TEM）、扫描电子显微镜（SEM）、BET氮吸附、紫外-可见光光谱（UV-vis）和X射线光电子能谱（XPS）分别表征了样品的晶体结构和微观形貌、孔结构、能带结构以及分子结构和表面元素价态结构。研究表明，形貌以不规则的纳米颗粒形式存在、孔径分布主要在3.5nm左右，属于介孔结构。气敏研究表明：在研究范围内，纳米Pt/ZnO最佳工作温度持续上升，因此选取在ZnO最佳工作温度下（180℃）去探讨Pt的掺杂对ZnO气敏性能的影响。在ZnO最佳工作温度下，Pt摩尔分数为0.5%的Pt/ZnO样品对100μL/L的TEA的灵敏度相比ZnO提高了66倍，吸附脱附时间分别提高118s和19s。气敏机理研究表明，复合材料中异质结的生成是气敏性能提升的重要原因。

关键词: 气敏材料, Pt/ZnO, 氧化锌, 三乙胺, 灵敏度

Abstract:

As an important component of volatile organic compounds (VOCs), triethylamine (TEA) can cause serious harm to human body and the environment, and thus the detection of triethylamine is of great significance. In this paper, the semiconductor oxide Pt/ZnO heterostructures were designed and synthesized by hydrothermal method, and their gas sensitive properties were systematically studied. The crystal structure and microstructure of the sample, pore structure, element valence band structure and the molecular structure and surface structure were characterized by using X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM) and BET nitrogen adsorption, ultraviolet-visible spectra (UV-vis) and X-ray photoelectron spectroscopy (XPS), respectively. The results showed that the morphology existed in the form of irregular nanoparticles and the pore size distribution was mainly about 3.5nm, which belonged to the mesoporous structure. Gas sensing studies found that the optimal working temperature of Pt/ZnO nanoparticles continued to increase in the studied range, and thus the doping of Pt at the optimal working temperature of ZnO (180℃) was chosen to explore the effect of Pt on the gas-sensitive properties of ZnO. At the optimum operating temperature of ZnO, the sensitivity of Pt/ZnO sample with Pt content of 0.5% to 100μL/L TEA was improved by 66 times compared with ZnO at the optimal working temperature of ZnO, and the adsorption and desorption times were improved by 118s and 19s, respectively. The gas-sensitive mechanism study indicated that the generation of heterojunctions in the composite was an important reason for the improved gas-sensitive performance.

Key words: gas sensor, Pt/ZnO, zinc oxide, triethylamine, gas sensitivity

中图分类号:

TM23

杨斌, 王晓冬, 王燕, 仪桂云, 王铁狼, 时闯, 张战营. 纳米Pt/ZnO异质结构的制备及其气敏性能[J]. 化工进展, 2023, 42(9): 4817-4827.

YANG Bin, WANG Xiaodong, WANG Yan, YI Guiyun, WANG Tielang, SHI Chuang, ZHANG Zhanying. Preparation of nano-Pt/ZnO heterostructures and gas sensitive properties[J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4817-4827.

图/表 13

图1 ZnO及Pt/ZnO-2的XRD图

表1 由谢乐公式计算的ZnO和Pt/ZnO样品的晶粒尺寸

样品	晶粒尺寸/nm
ZnO	30.520
Pt/ZnO-2	28.913

图2 ZnO和Pt/ZnO-2的SEM图[(a),(b)]和(b)中标记区域的EDS图[(c)]

图3 Pt/ZnO-2的(a)TEM及(b)HRTEM图

图4 ZnO和Pt/ZnO-2样品的氮气吸附脱附等温线及孔径分布图

图5 ZnO及Pt/ZnO-2的UV-vis吸收光谱图以及(αhν)2和hν的关系线

图6 ZnO和Pt/ZnO-2的XPS全谱(a)、Zn 2p高分辨谱(b)以及ZnO和Pt/ZnO-2的O 1s高分辨谱(c)

表2 ZnO和Pt/ZnO-2的O1s中不同种类的氧含量

样品	晶格氧/%	空位氧/%	化学吸附氧/%
ZnO	44.98	40.66	14.36
Pt/ZnO-2	39.49	39.14	21.37

图7 Pt/ZnO传感器气敏性能

图8 传感器在180℃对不同气体的响应(a)以及Pt/ZnO-2传感器的长期稳定性测试(b)

表3 基于不同材料的TEA传感性能

材料	最佳工作温度 /℃	浓度 /μL·L^-1	响应值	参考文献
NiO-ZnO纳米片	320	100	300	[26]
Pr/ZnO纳米棒	200	50	158	[18]
Au/ZnO半球	260	100	104.8	[27]
α-Fe₂O₃微球	275	100	11.8	[28]
TiO₂-SnO₂纳米片	260	100	52.3	[29]
SnO₂-Zn₂SnO₄纳米球	250	100	48	[30]
TiO₂纳米棒	290	100	14.2	[31]
V₂O₅空心球	370	100	7.2	[32]
Au@SnO₂/MoS₂	300	100	96	[33]
Au@ZnO/SnO₂	300	100	115	[34]
Pt/ZnO-2	180	100	521.7	本研究

图9 ZnO和Pt/ZnO-2分别暴露于空气及TEA中的气体传感机制

图10 ZnO在空气中和三乙胺中的能带结构图和Pt/ZnO-2在空气中和三乙胺中的能带结构图

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