CN106324200A - 一种痕量Pt修饰的多孔ZnO复合材料对苯类气体检测 - Google Patents
一种痕量Pt修饰的多孔ZnO复合材料对苯类气体检测 Download PDFInfo
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- 239000007789 gas Substances 0.000 title abstract 5
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- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 claims description 3
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Abstract
一种痕量Pt修饰的多孔ZnO复合材料能够实时快速地检测微量的苯类气体,属于气体传感技术领域。这种复合气体敏感材料对苯类气体有超高的灵敏度,并且检测限能达到安全检测限以下,同时其工作温度明显低于传统的气敏材料,有利于提高气敏元件的使用寿命和测试信号的可靠性,符合环保节能的指标。本发明所制备的Pt修饰的ZnO复合材料用于制作苯类气体传感器件,该器件经200℃老化24小时后,对100ppm苯、甲苯、二甲苯的响应值能分别达到70、84、88,并且能快速的响应和恢复,其响应时间分别为3s、2s、2s。
Description
技术领域
本发明属于气体传感技术领域,具体涉及一种Pt修饰的多孔ZnO复合材料在快速准确地检测微量苯类气体中的应用。
技术背景
苯类气体作为一类典型的挥发性有机污染物,是最常见的室内污染气体。其广泛的用作溶剂,建筑材料、家居产品、工业生产的原材料,因此普遍存在于住宅区和工业环境中。苯类气体的剧毒性和致癌性,使得人们即使处于低浓度的氛围中也会受到严重的伤害,因此,研究苯类气体敏感材料是气敏传感领域里一个重要的分支。
金属氧化物气体传感器基于其便于实时监测、操作简单、成本低廉等优点,成为一种检测有毒有害气体的有效技术手段。综合考虑材料的各方面因素,ZnO纳米材料成为研究最广泛的金属氧化物气体敏感材料之一。由于苯类分子具有很好的稳定性和高的活化能使其检测难度大大增加,大多数基于ZnO气敏材料的半导体气体传感器对苯类气体的灵敏度都很低,并且响应时间较长,工作温度较高。例如,朱等人(Materials Letters,2004年58卷624-629页)提出的TiO2修饰的ZnO传感器,黄等人(Sensors and Actuators B:Chemical,2013年188卷249-256)制备的ZnO传感器用于检测苯类气体,但都存在着上述的缺陷。同时用我们这种方法所制备得纯的ZnO材料对苯类气体的灵敏度也很低,响应时间长,并且无法恢复。(如对100ppm苯的响应值为12,响应时间为20s)。因此,制备出基于ZnO材料的低温度、快速响应、高灵敏度特性的苯类气体传感材料成为一项挑战性的任务。
近年来,科研工作者们研究发现在金属氧化物中负载修饰贵金属能有效的提高材料对苯类气体的灵敏度,如王等人(Phys.Chem.Chem.Phys,2013年15卷17179-17186)通过在ZnO纳米线上负载一定量的Au来优化材料对苯类气体的灵敏度,然而这些方案所使用的贵金属含量都比较高,不利于降低生产成本,而且工作温度较高,制备过程复杂。
发明内容
本发明的目的是针对以往气敏材料的缺陷,提供了一种对苯类气体有较高灵敏度,低检测限(100ppb),快速响应恢复的Pt修饰的多孔ZnO复合材料,这种复合材料不仅能快速实时的检测空气中的微量苯类气体,同时其工作温度明显低于传统的气体敏感材料的工作温度,有利于提高气敏元件的使用寿命和测试信号的可靠性,并且符合环保节能的指标。
本发明所述的苯类气体敏感材料是Pt修饰的多孔ZnO复合材料,其制备过程如下:
(1)将0.30g的二水合醋酸锌和0.15mg~0.60mg的六水合氯铂酸溶解到13~15mL的甘油和40~45mL的异丙醇组成的混合溶剂中,然后转移到反应釜中于160℃反应2小时,之后自然冷却至室温,用乙醇离心处理得到Pt修饰的ZnO前驱体;
(2)将上述前驱体粉末置于马弗炉中,在空气氛围中于400℃煅烧2小时,即可得到本发明所述的Pt修饰的多孔ZnO复合材料。
将上述Pt修饰的多孔ZnO复合材料用于制作苯类气体传感器,该器件经200℃老化24小时后,对100ppm苯的响应值在35~70之间,响应时间为2~4s,恢复时间为200~400s,较佳的工作温度范围为230~280℃,其中最佳工作温度为250℃。对苯类气体的检测极限为100~500ppb。(响应值为Ra/Rg,Ra:传感器件在新鲜空气中的电阻值,Rg:传感器件在目标气体中的电阻值;响应时间:传感器件置于目标气体后,电阻值达到极值90%所需的时间;恢复时间:器件重新置于新鲜空气后,电阻值恢复到原阻值90%所需的时间)。
本发明中铂的修饰量为0.05wt%~0.2wt%,用量少,对成本影响较小。
本发明所制备的Pt修饰的多孔ZnO复合材料对100ppm苯的响应值为35~70。
本发明所制备的Pt修饰的多孔ZnO复合材料在苯类气体检测中的应用时,其工作温度为230~280℃。
本发明所制备的Pt修饰的多孔ZnO复合材料在苯类气体检测中的应用时,其检测限为100~500ppb。
附图说明
图1:实施例1中所获得Pt修饰的多孔ZnO复合材料的SEM照片;
图2:实施例1中所获得Pt修饰的多孔ZnO复合材料的XRD图谱;
图3:实施例1中所获得Pt修饰的多孔ZnO复合材料对苯的浓度梯度图;
图4:实施例1中所获得Pt修饰的多孔ZnO复合材料对苯,甲苯,二甲苯,三甲苯的选择性图。
具体实施方式
实施例1
1)Pt修饰的ZnO前驱体的制备:将0.30g的二水合醋酸锌和0.30mg的六水合氯铂酸溶解到13mL的甘油和40mL的异丙醇组成的混合溶剂中,然后转移到反应釜中于160℃下反应2小时,之后自然冷却至室温,用乙醇离心处理得到Pt修饰的ZnO前驱体;
2)Pt修饰的多孔ZnO复合材料的制备:将上述前驱体粉末置于马弗炉中在空气氛围中于400℃煅烧2小时,即可得到所述的Pt修饰的多孔ZnO微米球复合材料(如图1)。对上述样品进行了组成和结构的分析,图2为Pt修饰的多孔ZnO微米球的XRD谱图,从图中可观察到,所有衍射峰的峰位与PDF#36-1451相匹配,由于样品中Pt修饰量极少,所以没有观察到任何Pt及其氧化物的衍射峰。
3)传感器件的制备过程:以陶瓷管为基底,镍铬合金丝为加热元件,4只Pt丝为测试端导线。具体制备步骤如下:将20mg的Pt修饰的多孔ZnO复合材料分散在2mL的乙醇中形成糊状物,之后将其均匀的涂在陶瓷管外表面,等晾干后将镍铬合金丝穿过陶瓷管,并将加热丝和陶瓷管两端的Pt丝分别焊接在底座上,然后将器件在200℃下老化24小时。
4)工作温度为250℃时,对100ppm苯的响应值为70,响应时间为3s,恢复时间为300s,对苯的检测限为100ppb。
实施例2
与实施例1相同,只是将六水合氯铂酸的用量变为0.60mg。该复合材料对100ppm苯的响应值为35,响应时间为4s,恢复时间为200s,对苯的检测限为500ppb。
实施例3
与实施例1相同,只是将六水合氯铂酸的用量变为0.45mg。该复合材料对100ppm苯的响应值为48,响应时间为4s,恢复时间为250s,对苯的检测限为500ppb。
实施例4
与实施例1相同,只是将六水合氯铂酸的用量变为0.15mg。该复合材料对100ppm苯的响应值为60,响应时间为2s,恢复时间为400s,对苯的检测限为100ppb。
实施例5
与实施例1相同,只是将工作温度设为240℃。该复合材料对100ppm苯的响应值为62,响应时间为4s,恢复时间为370s,对苯的检测限为100ppb。
实施例6
与实施例1相同,只是将工作温度设为260℃。该复合材料对100ppm苯的响应值为51,响应时间为2s,恢复时间为220s,对苯的检测限为100ppb。
Claims (6)
1.一种痕量Pt修饰的多孔ZnO复合材料的制备方法,其步骤如下:
(1)将0.30g的二水合醋酸锌和0.15mg~0.60mg的六水合氯铂酸溶解到13~15mL的甘油和40~45mL的异丙醇组成的混合溶剂中,然后转移到反应釜中于160℃反应2小时,之后自然冷却至室温,用乙醇离心处理得到Pt修饰的ZnO前驱体;
(2)将上述前驱体粉末置于马弗炉中,在空气氛围中于400℃煅烧2小时,即可得到Pt修饰的多孔ZnO复合材料;
2.如权利要求1所述的一种Pt修饰的多孔ZnO复合材料,其特征在于:铂的修饰量为0.05wt%~0.2wt%;
3.如权利要求1所述的一种Pt修饰的多孔ZnO复合材料在苯类气体检测中的应用;
4.如权利要求3所述的一种Pt修饰的多孔ZnO复合材料在苯类气体检测中的应用,其特征在于:该器件对100ppm苯的响应值为35~70;
5.如权利要求3所述的一种Pt修饰的多孔ZnO复合材料在苯类气体检测中的应用,其特征在于:该器件的工作温度为230~280℃;
6.如权利要求3所述的一种Pt修饰的多孔ZnO复合材料在苯类气体检测中的应用,其特征在于:该器件对苯类气体的检测限为100~500ppb。
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CN115676872A (zh) * | 2022-08-25 | 2023-02-03 | 昆明理工大学 | 一种气敏材料的高通量制备方法、产品及应用 |
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