CN116790140B - 一种掺杂多孔碳纳米球的二氧化锡基气敏涂料的制备方法及应用 - Google Patents
一种掺杂多孔碳纳米球的二氧化锡基气敏涂料的制备方法及应用 Download PDFInfo
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Abstract
一种掺杂多孔碳纳米球的二氧化锡基气敏涂料的制备方法及应用。所述方法为:将多孔碳纳米球分散在去离子水中,加入二氧化锡粉末,先后进行搅拌、超声和涡旋振荡得到均匀的混合溶液;在混合溶液中加入硝酸银,在60℃下搅拌反应,随后进行离心、洗涤,得到SnO2/多孔碳纳米球@Ag材料;将所得材料溶解于无水乙醇中混匀,将混匀后的气敏涂料涂覆至带电极的陶瓷管表面,待涂料干燥后重复数次,得到SnO2/多孔碳纳米球@Ag气敏传感器。本发明的纳米涂料可在100℃的温度下对异丙醇具备良好的传感特性,可有效解决目前的传感器工作温度较高的问题。具有工艺简单、成本低廉的特点。
Description
技术领域
本发明属于气敏材料领域,具体涉及一种掺杂多孔碳纳米球的二氧化锡基气敏涂料的制备方法及应用。
背景技术
异丙醇(IPA)是一种无色透明、微乙醇气味、有毒的挥发性有机化合物(VOC),其蒸气的毒性为乙醇的二倍,广泛用于药品、化妆品、塑料、涂料、香料、电子工业中的清洗剂和农药的制造。由于70%异丙醇对细菌,真菌和病毒具有快速抗菌作用,它在日常消毒领域的应用激增。然而,接触高浓度IPA蒸气会出现头痛、倦睡、共济失调以及眼、鼻、喉刺激症状。口服可致恶心、呕吐、腹痛、腹泻、倦睡、昏迷甚至死亡。许多医生和学者认为长期接触IPA可能会增加癌症风险,IPA已被世界卫生组织国际癌症研究机构(IARC)认定为3类致癌物,且采用强酸生产的异丙醇在1类致癌物清单中。因此,设计并制备具有高效气敏性能的新型半导体材料对提高气体传感器的性能、保护人类的健康安全具有重要意义。
金属氧化物半导体(MOS),如CuO、ZnO、SnO2、In2O3等,由于其成本低、灵敏度高、稳定性好、选择性强,已成功用于IPA传感器。其中SnO2作为一种n型宽带隙半导体,已经被证明是一种有前途的检测IPA气体的材料。然而,目前针对IPA气体检测的SnO2基气敏传感器还需要在高于200℃的温度下工作,同时传感器的制备过程较为繁琐。尽管这些研究在气体检测方面取得了令人骄傲的进展,但在工作温度、灵敏度等反应性能方面和传感器制备工艺的简化方面仍有改进的空间。
发明内容
本发明的目的是为了解决用于IPA检测的SnO2基气敏传感器制备工艺繁琐,工作温度高、灵敏度低等问题,提供了一种掺杂多孔碳纳米球的二氧化锡基气敏涂料的制备方法及应用,制备的气敏纳米涂料可在100℃的温度下对异丙醇具备良好的传感特性。同时,这种纳米涂料可直接涂覆于带电极的陶瓷管、石英、聚酰亚胺(PI)、聚对苯二甲酸乙二醇酯(PET)等常见基底表面,直接制备出气敏传感器,具有工艺简单、成本低廉的特点。
本发明的目的是通过以下技术方案实现的:
一种掺杂多孔碳纳米球的二氧化锡基气敏涂料的制备方法,所述方法为:将多孔碳纳米球分散在无水乙醇中,加入纳米二氧化锡粉末,进行超声分散,使用磁力搅拌器和涡旋振荡器充分混匀,得到掺杂多孔碳纳米球的二氧化锡基气敏涂料(SnO2/多孔碳纳米球)。
进一步地,所述多孔碳纳米球与无水乙醇的混合比例为0.0005~0.005g:1mL;所述二氧化锡与多孔碳纳米球的质量比为2~200g:1g。
进一步地,所述超声分散时间为10~20min;磁力搅拌转速为800~1200rpm;涡旋振荡器转速3000rpm;混匀时间为30~90min。
一种上述方法制备的掺杂多孔碳纳米球的二氧化锡基气敏涂料的应用,所述应用具体为:将气敏涂料涂覆至基底表面,待涂料干燥后重复数次,将加热电阻丝与基底组装(结构如图3所示),得到SnO2/多孔碳纳米球气敏传感器。
进一步地,所述基底为陶瓷管、石英、聚酰亚胺(PI)或聚对苯二甲酸乙二醇酯(PET)中的一种,基底需要预先制备出电极。
一种掺杂多孔碳纳米球的二氧化锡基气敏涂料的制备方法,所述方法为:将多孔碳纳米球分散在去离子水中,加入纳米二氧化锡粉末,进行超声分散,使用磁力搅拌器和涡旋振荡器充分混匀,将所得溶液预热到60℃,加入硝酸银,磁力搅拌并保温10~30min,随后进行离心并采用无水乙醇洗涤2次,将所得产物置于烘箱中干燥,得到银修饰的掺杂多孔碳纳米球的二氧化锡基气敏涂料(SnO2/多孔碳纳米球@Ag,@是Ag在SnO2/多孔碳纳米球表面的意思,部分覆盖起修饰作用)。
进一步地,所述多孔碳纳米球与去离子水的混合比例为0.001~0.02g:1mL;所述硝酸银与二氧化锡的质量比为0.1~1g:1g;所述纳米二氧化锡粉末与多孔碳纳米球的质量比为40~200g:1g。
进一步地,所述超声分散时间为10~20min;磁力搅拌转速为800~1200rpm;涡旋振荡器转速3000rpm;混匀时间为30~90min。
一种上述方法制备的掺杂多孔碳纳米球的二氧化锡基气敏涂料的应用,所述应用具体为:将SnO2/多孔碳纳米球@Ag材料溶解于无水乙醇中,进行超声分散,使用磁力搅拌器和涡旋振荡器充分混匀,将混匀后的气敏涂料涂覆至基底表面,待涂料干燥后重复数次,将加热电阻丝与陶瓷管组装,得到SnO2/多孔碳纳米球@Ag气敏传感器。
进一步地,所述基底为陶瓷管、石英、聚酰亚胺(PI)或聚对苯二甲酸乙二醇酯(PET)中的一种,基底需要预先制备出电极。
相比于现有技术,本发明具有如下优点:
1、本发明利用二氧化锡独特的气敏性能和多孔碳纳米球高比表面积的结构特点,将二氧化锡和多孔碳纳米球材料复合,并在二氧化锡表面进行化学镀银修饰,制备出具有高灵敏度的低温气敏材料。二氧化锡对醇类气体尤其是异丙醇具有极高的吸附能,作为目标气体的吸附位点;多孔碳纳米球的电导率相对较高,在复合材料中为二氧化锡材料提供了导电通路,使得目标气体上的电荷可以迅速转移,产生明显的电阻变化。银的电子敏化作用和化学溢出效应有助于提高对异丙醇的灵敏度和选择性。此外,银具有大量自由电子,在低温甚至室温下很容易与氧反应生成氧离子,能使得气体传感器工作温度更低、反应更快。通过二氧化锡、多孔碳纳米球和银的协同作用,在100℃的温度下即可快速吸附异丙醇分子,具有极高的灵敏度,灵敏度定义为Ra/Rg(传感器在空气中的电阻与在目标气体中电阻的比值),对100ppm异丙醇的灵敏度为52.98,并且可以快速脱附,有利于在短时间内进行多次气敏响应。同时,该材料对异丙醇外其他醇类气体的响应很低,对非醇类气体几乎不响应。
2、本发明制备的气敏涂料,制作气敏传感器的工艺过程简单。无需叉指电极的参与,仅需涂覆于带电极的陶瓷管、石英、聚酰亚胺(PI)、聚对苯二甲酸乙二醇酯(PET)等常见基底表面,在和电阻加热丝组装后,即可直接制备出气敏传感器,具有工艺简单、成本低廉的特点。该发明可灵活应用于不同领域,在可穿戴柔性气敏传感设备、微型电子气敏传感设备等领域具有广阔的应用前景。该材料的制备方法具有快速,简便,可重复易于控制等优点。
附图说明
图1为实施例2所制备的SnO2/多孔碳纳米球@Ag气敏材料的结构示意图;
图2为实施例2中SnO2/多孔碳纳米球@Ag气敏材料的制作流程图;
图3为实施例3和实施例4所制备的气敏传感器结构示意图;
图4为实施例3所制备SnO2/多孔碳纳米球气敏传感器在160℃温度下对100ppm异丙醇气体的动态响应/恢复曲线图;
图5为实施例4所制备的SnO2/多孔碳纳米球@Ag气敏传感器在100℃温度下对100ppm异丙醇气体的动态响应/恢复曲线图;
图6为实施例3所制备的SnO2/多孔碳纳米球气敏传感器和实施例4所制备的SnO2/多孔碳纳米球@Ag气敏传感器在不同温度下对100ppm异丙醇的灵敏度折线图;
图7为实施例4所制备的SnO2/多孔碳纳米球@Ag气敏传感器在100℃温度下对浓度为100ppm的不同种类气体的灵敏度对比图;
图8为实施例4所制备的SnO2/多孔碳纳米球@Ag气敏传感器在100℃温度下对不同浓度的异丙醇气体的响应-恢复曲线图;
图9为实施例4所制备的SnO2/多孔碳纳米球@Ag气敏传感器在100℃温度下对不同浓度的异丙醇的灵敏度对比图;
图10为实施例4所制备的SnO2/多孔碳纳米球@Ag气敏传感器在100℃温度下对100ppm异丙醇气体的响应的可重复性曲线图。
具体实施方式
下面结合附图和实施例对本发明的技术方案作进一步的说明,但并不局限于此,凡是对本发明技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,均应涵盖在本发明的保护范围中。
本发明中多孔碳纳米球通过胶束-界面共聚与碳热还原的方法进行制备,具体制备方法为:
步骤1.1、将有机单体苯胺和吡咯加入到含有两性分子表面活性剂的水溶液中,搅拌并超声分散30~120min,得到均匀的混合溶液,其中:所述吡咯和苯胺的用量比为1.125~0.500mL:1mL;所述两性分子表面活性剂为聚乙二醇辛基苯基醚(Triton X-100),其与吡咯和苯胺总用量的比例为1g:7.3~15.0mL;所述吡咯和苯胺的总用量与两性分子表面活性剂的水溶液中的水的比例为0.8~3.2mg:1g;
步骤1.2、将混合溶液置于冰水浴中搅拌20~60min,加入引发剂水溶液剧烈搅拌20~50s后再在0~6℃的环境下反应12~36h,所得产物经洗涤、干燥,得到多孔碳纳米球材料前驱体,其中:所述引发剂水溶液中的引发剂为过硫酸铵,过硫酸铵与吡咯和苯胺总用量的比例为1.00~6.27g:1mL;所述引发剂水溶液在加入前预先冷却至0~5℃;所述洗涤是指将产物用去离子水多次洗涤,并减压过滤,直到滤液接近中性;
步骤1.3、将多孔碳纳米球材料前驱体进行高温炭化处理,即得到多孔碳纳米球材料,其中:所述高温炭化处理是在惰性气氛中以2~10℃/min的升温速率升温至600~1000℃,炭化3~20h。
实施例1:
步骤一:多孔碳纳米球的制备
取0.49mL苯胺、0.38mL吡咯,加入60mL含有Triton X-100(0.06g)的水溶液中,加入5mL含有0.6g氧化锡胶体的水溶液,搅拌并超声分散至得到均匀的混合溶液;然后将混合溶液置于冰水浴中搅拌30min,加入5mL含有2.47g过硫酸铵的水溶液,剧烈搅拌30s,然后在0~6℃的环境下反应24h,得到的产物用去离子水和乙醇洗涤、过滤,直至滤液为无色透明,干燥,得到多孔碳纳米球材料的前驱体;将上述多孔碳纳米球材料前驱体置于管式炉中,在氩气保护下以10℃/min的升温速率升温至800℃,炭化8h,得到多孔碳纳米球材料。
步骤二:SnO2/多孔碳纳米球纳米涂料的制备
将制得的多孔碳纳米球(0.005g)分散在无水乙醇中,加入0.6g纳米二氧化锡粉末,先后进行磁力搅拌20min、超声处理20min和涡旋振荡20min得到均匀的混合溶液。随后,在烘箱中干燥,得到SnO2/多孔碳纳米球材料。
实施例2:
SnO2/多孔碳纳米球@Ag纳米涂料的制备
将实施例1步骤一中得到的多孔碳纳米球(0.005g)分散在50mL去离子水中,加入0.6g纳米二氧化锡粉末,先后进行磁力搅拌20min、超声处理20min和涡旋振荡20min得到均匀的混合溶液。将混合溶液预热到60℃,加入0.3g硝酸银,在60℃下磁力搅拌20min进行反应,随后进行离心并采用无水乙醇洗涤2次,在60℃的烘箱中干燥后得到SnO2/多孔碳纳米球@Ag材料,其结构如图1所示,制作流程如图2所示。
实施例3:
SnO2/多孔碳纳米球气敏传感器的制备
将实施例1所制得的SnO2/多孔碳纳米球材料溶解于无水乙醇中,进行超声分散20min,使用磁力搅拌器和涡旋振荡器充分混匀;其中,磁力搅拌转速为1000rpm;涡旋振荡转速为3000rpm;混匀时间为60min。随后,将混匀后的气敏涂料涂覆至带电极的陶瓷管表面,待涂料干燥后重复数次,得到SnO2/多孔碳纳米球气敏传感器。气敏传感器结构示意图如图3所示;图4为实施例3所制备SnO2/多孔碳纳米球气敏传感器在160℃温度下对100ppm异丙醇气体的动态响应/恢复曲线,测试结果表明,该传感器在160℃下对异丙醇的响应迅速,灵敏度高,恢复时间也较快。
实施例4:
SnO2/多孔碳纳米球@Ag气敏传感器的制备
将实施例2所制得的SnO2/多孔碳纳米球@Ag材料溶解于无水乙醇中,进行超声分散20min,使用磁力搅拌器和涡旋振荡器充分混匀;其中,磁力搅拌转速为1000rpm;涡旋振荡转速为3000rpm;混匀时间为60min。随后,将混匀后的气敏涂料涂覆至带电极的陶瓷管表面,待涂料干燥后重复数次。然后将加热电阻丝与陶瓷管组装,得到SnO2/多孔碳纳米球@Ag气敏传感器。气敏传感器结构示意图如图3所示。图5为实施例4所制备的SnO2/多孔碳纳米球@Ag气敏传感器在100℃温度下对100ppm异丙醇气体的动态响应/恢复曲线;测试结果表明,该传感器在100℃下对异丙醇的响应迅速,灵敏度高,恢复时间也较快;相比于实施例3所制备SnO2/多孔碳纳米球气敏传感器,其工作温度更低,响应速度更快。
图6为实施例3所制备的制备SnO2/多孔碳纳米球气敏传感器和实施例4所制备的SnO2/多孔碳纳米球@Ag气敏传感器在不同温度下对100ppm异丙醇的灵敏度,测试结果表明,SnO2/多孔碳纳米球@Ag材料在合适的工作温度下(100℃~160℃)具备更良好的灵敏度
图7为实施例4所制备的SnO2/多孔碳纳米球@Ag气敏传感器在100℃温度下对浓度为100ppm的不同种类气体的灵敏度;测试结果表明,该传感器对异丙醇的灵敏度远高于除乙二醇外的其他气体,由于该传感器对乙二醇的响应速度极慢,相同浓度下的响应时间为异丙醇的10倍,因此对异丙醇传感的选择性不会产生干扰。
图8为实施例4所制备的SnO2/多孔碳纳米球@Ag气敏传感器在100℃温度下对不同浓度的异丙醇气体的响应-恢复曲线;图9为实施例4所制备的SnO2/多孔碳纳米球@Ag气敏传感器在100℃温度下对不同浓度的异丙醇的灵敏度;测试结果表明,该传感器对1ppm的异丙醇也能表现出稳定的反应,在检测低浓度的异丙醇方面有很大的潜力。
图10为实施例4所制备的SnO2/多孔碳纳米球@Ag气敏传感器在100℃温度下对100ppm异丙醇气体的循环响应曲线;显示了传感器对100ppm异丙醇的12个连续的响应瞬态,响应瞬态曲线表明,该传感器在整个传感测试中具有良好的可重复性。
Claims (10)
1.一种掺杂多孔碳纳米球的二氧化锡基气敏涂料的制备方法,其特征在于:所述方法为:将多孔碳纳米球分散在无水乙醇中,加入纳米二氧化锡粉末,进行超声分散,使用磁力搅拌器和涡旋振荡器充分混匀,得到掺杂多孔碳纳米球的二氧化锡基气敏涂料。
2.根据权利要求1所述的一种掺杂多孔碳纳米球的二氧化锡基气敏涂料的制备方法,其特征在于:所述多孔碳纳米球与无水乙醇的混合比例为0.0005~0.005g:1mL;所述二氧化锡与多孔碳纳米球的质量比为2~200g:1g。
3.根据权利要求1所述的一种掺杂多孔碳纳米球的二氧化锡基气敏涂料的制备方法,其特征在于:所述超声分散时间为10~20min;磁力搅拌转速为800~1200rpm;涡旋振荡器转速3000rpm;混匀时间为30~90min。
4.一种权利要求1~3任一项所述方法制备的掺杂多孔碳纳米球的二氧化锡基气敏涂料的应用,其特征在于:所述应用具体为:将气敏涂料涂覆至基底表面,待涂料干燥后重复数次,将加热电阻丝与基底组装,得到SnO2/多孔碳纳米球气敏传感器。
5.根据权利要求4所述的一种掺杂多孔碳纳米球的二氧化锡基气敏涂料的应用,其特征在于:所述基底为陶瓷管、石英、聚酰亚胺或聚对苯二甲酸乙二醇酯中的一种,基底需要预先制备出电极。
6.一种掺杂多孔碳纳米球的二氧化锡基气敏涂料的制备方法,其特征在于:所述方法为:将多孔碳纳米球分散在去离子水中,加入纳米二氧化锡粉末,进行超声分散,使用磁力搅拌器和涡旋振荡器充分混匀,将所得溶液预热到60℃,加入硝酸银,磁力搅拌并保温10~30min,随后进行离心并采用无水乙醇洗涤2次,将所得产物置于烘箱中干燥,得到银修饰的掺杂多孔碳纳米球的二氧化锡基气敏涂料。
7.根据权利要求6所述的一种掺杂多孔碳纳米球的二氧化锡基气敏涂料的制备方法,其特征在于:所述多孔碳纳米球与去离子水的混合比例为0.001~0.02g:1mL;所述硝酸银与二氧化锡的质量比为0.1~1g:1g;所述纳米二氧化锡粉末与多孔碳纳米球的质量比为40~200g:1g。
8.根据权利要求6所述的一种掺杂多孔碳纳米球的二氧化锡基气敏涂料的制备方法,其特征在于:所述超声分散时间为10~20min;磁力搅拌转速为800~1200rpm;涡旋振荡器转速3000rpm;混匀时间为30~90min。
9.一种权利要求6~8任一项所述方法制备的掺杂多孔碳纳米球的二氧化锡基气敏涂料的应用,其特征在于:所述应用具体为:将SnO2/多孔碳纳米球@Ag材料溶解于无水乙醇中,进行超声分散,使用磁力搅拌器和涡旋振荡器充分混匀,将混匀后的气敏涂料涂覆至基底表面,待涂料干燥后重复数次,将加热电阻丝与基底组装,得到SnO2/多孔碳纳米球@Ag气敏传感器。
10.根据权利要求9所述的一种掺杂多孔碳纳米球的二氧化锡基气敏涂料的应用,其特征在于:所述基底为陶瓷管、石英、聚酰亚胺或聚对苯二甲酸乙二醇酯中的一种,基底需要预先制备出电极。
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