摘要
挥发性有机化合物(VOCs)是一类主要的大气污染物,对人体健康和环境均可造成危害,因此发展可快速、灵敏检测VOCs的技术具有重要意义.本文分别以乙二胺(ED)和乙醇胺(EA)修饰MIL-101(Cr),制得了MIL-101(Cr)-ED和MIL-101(Cr)-EA,采用滴涂法制备了3种负载MIL-101(Cr)材料的石英晶体微天平(QCM)气相传感器,研究了其对甲醇、乙醇、异丙醇、丙酮、环己烷、二乙胺、甲酸、甲醛、氨气和乙酸的传感性能.实验结果表明,与负载MIL-101(Cr)的传感器相比,负载MIL-101(Cr)-ED和MIL-101(Cr)-EA的QCM传感器对甲酸的吸附性能显著提高,在甲酸浓度为350 mg/L时,传感器的振荡频率分别下降至-375.6和-232.1 Hz.在甲酸浓度为5～350 mg/L时,负载MIL-101(Cr)-ED的QCM传感器对甲酸响应的灵敏度为0.95 Hz·L·mg-1,检测限为0.95 mg/L,表现出线性良好、灵敏度高、检测限低和重复性好的特点.这表明此类QCM气相传感器在VOCs实时检测方面具有良好的应用前景.
Abstract
Volatile organic compounds(VOCs)are considered as one of the major components in atmospheric pollutants,and pose serious hazards to both human health and the environment.It is urgent to develop new high-efficient detection techniques for VOCs.In this work,ethylenediamine(ED)and ethanolamine(EA)were grafted into MIL-101(Cr)to obtain ED-and EA-derived MIL-101(Cr)materials[labeled as MIL-101(Cr)-ED and MIL-101(Cr)-EA],respectively.Then,these three MIL-101(Cr)materials were loaded on the surface of quartz crystal through dip coating to assemble three kinds of MIL-101(Cr)-modified quartz crystal microbalance(QCM)gas sensors,respectively.Moreover,the sensing and recognition performance of these QCM sensors toward methanol,ethanol,2-propanol,acetone,cyclohexane,diethylamine,formic acid,formaldehyde,ammonia,and acetic acid were studied in detail.As indicated,MIL-101(Cr)-ED-and MIL-101(Cr)-EA-loaded QCM sensors showed better sensing performance for formic acid in comparison with the original MIL-101(Cr)-based sensor,and the oscillation frequency of these two sensors decreased by-375.6 and-232.1 Hz when the concentration of formic acid was 350 mg/L,respectively.Δf value was linearly related to the concentration of formic acid in the range of 5-350 mg/L.In addition,the sensitivity of MIL-101(Cr)-ED-loaded QCM gas sensor was estimated to be 0.95 Hz·L·mg-1 and the limit of detection was 0.95 mg/L.As a result,this MIL-101(Cr)-modified QCM gas sensor demonstrated high sensitivity,low detection limit,and good repeatability.In brief,this research would provide some useful information for developing new QCM gas sensors in real-time VOCs detection.
基金项目
国家自然科学基金(92356303)
国家自然科学基金(22073032)
广东省自然科学基金(2021A1515010211)
广东省科技创新战略专项(pdjh2022a0127)
清远市科技计划(2023KJJ013)
国家科技期刊平台
NSTL
万方数据