CN116216771A - SnO2/Pdatom、SnO2/AuPdalloys及其制备方法和应用 - Google Patents
SnO2/Pdatom、SnO2/AuPdalloys及其制备方法和应用 Download PDFInfo
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title description 13
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 73
- 239000002105 nanoparticle Substances 0.000 claims abstract description 28
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Abstract
本发明提供了一种Pd单原子修饰的SnO2纳米颗粒及其制备方法和应用、Au/Pd双金属纳米晶修饰的SnO2中空球及其制备方法和应用,属于敏感材料技术领域。本发明提供的Pd单原子修饰的SnO2纳米颗粒(即SnO2/Pdatom纳米敏感材料)具有良好的氢气敏感性,为高性能H2传感器的研制提供了材料基础。
Description
技术领域
本发明涉及敏感材料技术领域,尤其涉及一种SnO2/Pdatom、SnO2/AuPdalloys高性能纳米敏感材料及其制备方法和应用。
背景技术
随着现代社会对能源结构的多元化追求和传统化石燃料的有限性及其带来的温室效应和环保问题,使得清洁新能源成为研究热门。氢气作为一种储量丰富、可再生、无污染的能源形式,是目前最具发展前景的二次能源。然而氢气作为一种扩散速率高、点火能量低、爆炸极限广、无色无味的气体,一旦泄露爆炸将产生严重后果。因此,开发一种具有高灵敏度,快速响应时间的氢传感器对于检测生产、储存、运输和实际应用中的氢泄漏至关重要。
金属氧化物半导体气敏传感器由于具有稳定性高、操作方便、体积小、成本低廉、响应时间和恢复时间短等优点,而在氢气的检测中占据重要地位。一般而言,二氧化锡的氢气传感机制是由于氢气与二氧化锡表面吸附的氧气发生氧化还原反应,从而导致二氧化锡的电阻发生变化。而二氧化锡的气体传感器通过贵金属的掺杂,有机材料的负载等操作可以起到气体吸附的催化剂或表面位点的作用,提高了表面吸附作用,从而改善了传感器的传感性能。现有传统的氢气传感器稳定性较差、制备工艺复杂、成本较高、响应时间和恢复时间较长,对氢气的选择性差的问题,满足不了现代工业的需要。因此开发一种材料新颖,灵敏度高、反应快,选择性高,检测下限低的氢气传感器拥有重要意义。
发明内容
本发明的目的在于提供一种SnO2/Pdatom、SnO2/AuPdalloys高性能纳米敏感材料及其制备方法和应用,具有良好的氢气敏感性,为高性能H2传感器的研制提供了材料基础。
为了实现上述发明目的,本发明提供以下技术方案:
本发明提供了一种Pd单原子修饰的SnO2纳米颗粒的制备方法,包括以下步骤:
将SnCl4·H2O加入到乙醇与去离子水的混合溶液,经过超声分散后,加入盐酸并室温搅拌,然后在200℃反应12小时,离心干燥得到SnO2纳米颗粒;
将所述SnO2纳米颗粒和二氯四氨钯混合,并在室温下搅拌,然后经离心洗涤干燥后得到Pd单原子修饰的SnO2纳米颗粒。
优选的,所述混合溶液中乙醇和去离子水的体积比为10:1。
本发明提供了上述方案所述制备方法制备得到的Pd单原子修饰的SnO2纳米颗粒,平均粒径为750~780nm。
优选的,Pd的质量百分含量为0.15%。
本发明提供了上述方案所述Pd单原子修饰的SnO2纳米颗粒在检测H2中的应用。
本发明提供了一种Au/Pd双金属纳米晶修饰的SnO2中空球的制备方法,包括以下步骤:
取0.1g氨基化的SnO2中空球加入到35mL去离子水中,超声分散5分钟,然后向所得分散液中依次加入10mL浓度为0.5mg/mL的HAuCl4和10mL浓度为0.5mg/mL的Na2PdCl4,室温下搅拌12小时,然后用去离子水对所得样品离心洗涤3次,将洗涤后的样品重新分散到40mL去离子水中,加入3mL浓度为1mol/mL的NaBH4水溶液,在室温下搅拌6小时,随后用去离子水和无水乙醇对产物进行离心洗涤,将产物置于60℃干燥箱干燥,得到Au/Pd双金属纳米晶修饰的SnO2中空球。
本发明提供了上述方案所述制备方法制备得到的Au/Pd双金属纳米晶修饰的SnO2中空球,包括SnO2中空球和负载在所述SnO2中空球表面的Au/Pd合金颗粒。
本发明提供的Pd单原子修饰的SnO2纳米颗粒(即SnO2/Pdatom纳米敏感材料)具有良好的氢气敏感性,为高性能H2传感器的研制提供了材料基础。
附图说明
图1为实施例1制备的SnO2/Pdatom纳米敏感材料的扫描电镜图;
图2为实施例1制备的SnO2/Pdatom纳米敏感材料的粒径分布图;
图3为实施例1制备的SnO2/Pdatom纳米敏感材料的粒径分析结果;
图4为本发明Au/Pd双金属纳米晶修饰的SnO2中空球的制备过程图;
图5为实施例2制备的Au/Pd双金属纳米晶修饰的SnO2中空球的电镜图;
图6为实施例2制备的Au/Pd双金属纳米晶修饰的SnO2中空球的高分辨XPS图;
图7为纯SnO2、SnO2/PdO、SnO2/Pdatom和SnO2/Pdnano四种敏感材料对H2的气敏测试图;
图8为实施例1制备的SnO2/Pdatom纳米敏感材料的电阻值、响应/恢复时间、重复性、低浓度分辨能力、湿度影响和稳定性测试结果图。
具体实施方式
本发明提供了一种Pd单原子修饰的SnO2纳米颗粒的制备方法,包括以下步骤:
将SnCl4·H2O加入到乙醇与去离子水的混合溶液,经过超声分散后,加入盐酸并室温搅拌,然后在200℃反应12小时,离心干燥得到SnO2纳米颗粒;
将所述SnO2纳米颗粒和二氯四氨钯混合,并在室温下搅拌,然后经离心洗涤干燥后得到Pd单原子修饰的SnO2纳米颗粒。
在本发明中,未经特殊说明,所用原料均为本领域熟知的市售商品。
在本发明中,所述混合溶液中乙醇和去离子水的体积比优选为10:1。本发明对所述混合溶液的用量没有特殊要求,能够将SnCl4·H2O分散均匀即可。
本发明提供了上述方案所述制备方法制备得到的Pd单原子修饰的SnO2纳米颗粒,平均粒径为750~780nm。在本发明中,所述Pd单原子修饰的SnO2纳米颗粒中Pd的质量百分含量优选为0.15%。
本发明提供了上述方案所述Pd单原子修饰的SnO2纳米颗粒在H2传感器中的应用。
本发明提供了一种Au/Pd双金属纳米晶修饰的SnO2中空球的制备方法,包括以下步骤:
取0.1g氨基化的SnO2中空球加入到35mL去离子水中,超声分散5分钟,然后向所得分散液中依次加入10mL浓度为0.5mg/mL的HAuCl4和10mL浓度为0.5mg/mL的Na2PdCl4,室温下搅拌12小时,然后用去离子水对所得样品离心洗涤3次,将洗涤后的样品重新分散到40mL去离子水中,加入3mL浓度为1mol/mL的NaBH4水溶液,在室温下搅拌6小时,随后用去离子水和无水乙醇对产物进行离心洗涤,将产物置于60℃干燥箱干燥,得到Au/Pd双金属纳米晶修饰的SnO2中空球。
在本发明中,所述氨基化的SnO2中空球采用本领域熟知的方法制备得到。例如,可以采用本领域熟知的水热法先制备SnO2中空球,然后对其表面进行氨基化处理。鉴于所制备SnO2中空球表面带有大量羟基,所以需要对其表面进行氨基化处理,以使其表面呈现正电性。
图4为本发明Au/Pd双金属纳米晶修饰的SnO2中空球的制备过程图。如图4所示,利用MPS作为表面修饰剂,使其表面键接大量氨基官能团。随后,以HAuCl4和Na2PdCl4为前驱体,在静电吸附的作用下,SnO2-NH2表面会同时吸附AuCl4-和PdCl4-。最后,以NaBH4作为还原剂,通过原位还原的方法制备出Au/Pd双金属纳米晶修饰的SnO2中空球复合物。
本发明提供了一种Au/Pd双金属纳米晶修饰的SnO2中空球的制备方法,包括以下步骤:
取0.1g氨基化的SnO2中空球加入到35mL去离子水中,超声分散5分钟,然后向所得分散液中依次加入10mL浓度为0.5mg/mL的HAuCl4和10mL浓度为0.5mg/mL的Na2PdCl4,室温下搅拌12小时,然后用去离子水对所得样品离心洗涤3次,将洗涤后的样品重新分散到40mL去离子水中,加入3mL浓度为1mol/mL的NaBH4水溶液,在室温下搅拌6小时,随后用去离子水和无水乙醇对产物进行离心洗涤,将产物置于60℃干燥箱干燥,得到Au/Pd双金属纳米晶修饰的SnO2中空球。
本发明提供了上述方案所述制备方法制备得到的Au/Pd双金属纳米晶修饰的SnO2中空球。包括SnO2中空球和负载在所述SnO2中空球表面的Au/Pd合金颗粒。
本发明提供了上述方案所述Au/Pd双金属纳米晶修饰的SnO2中空球在H2传感器中的应用。
下面结合实施例对本发明提供的SnO2/Pdatom、SnO2/AuPdalloys高性能纳米敏感材料及其制备方法和应用进行详细的说明,但是不能把它们理解为对本发明保护范围的限定。
实施例1
将一定量的SnCl4·H2O加入到110mL乙醇与去离子水的混合溶液(体积比为10:1),经过超声分散后,加入1mL盐酸并室温搅拌1小时,然后在200℃反应12小时,离心干燥得到SnO2纳米颗粒。将一定量的SnO2纳米颗粒和二氯四氨钯混合,并在室温下搅拌48小时,然后经离心洗涤干燥后得到Pd单原子修饰的SnO2纳米颗粒(即SnO2/Pdatom纳米敏感材料),其中Pd的质量比为0.15%。
1、SnO2/Pdatom的结构表征及对氢气的气敏性性能验证
图1为实施例1制备的SnO2/Pdatom纳米敏感材料的扫描电镜图,由图1可知,其粒径均匀。
对敏感材料的粒径分布进行了表征,结果如图2所示。图2表明SnO2/Pdatom颗粒具有良好的尺寸均匀性,颗粒平均尺寸为~770nm,粒径尺寸呈正态分布,且具有一个主峰,详细的分析结果如图3所示。以上结果表明合成的纳米SnO2/Pdatom综合性能十分优异,为后续自组装成膜的发展及工艺一致性奠定了基础。
测量了纯SnO2、PdO的SnO2敏感材料、Pd单原子修饰的SnO2和Pd纳米颗粒修饰的SnO2这四种敏感材料(分别标记为纯SnO2、SnO2/PdO、SnO2/Pdatom和SnO2/Pdnano)对H2的气敏性能,结果如图7所示。首先,SnO2/Pdatom敏感材料表现出最佳的工作温度为175℃,明显要低于其余三种材料,这有利于降低传感器的功耗;其次,其对不同浓度H2的响应时间均在10s以内,也远低于其余三种材料,而且满足项目最终的考核指标要求。在对0.5~100ppmH2浓度的响应值和电阻测试中发现,其电阻范围适中,响应值也最高尤其是对0.05ppm的H2也具有一定的响应(响应值为1.05左右),表明SnO2经过Pd原子修饰后具有较低的检测下限,其检测下限可以达到0.05ppm左右。这些结果均表明,相对于纯SnO2、SnO2/PdO和SnO2/Pdnano材料,SnO2/Pdatom材料表现出最佳的气敏性能,其中这为高性能H2传感器的研制提供了材料基础和技术支持。
进一步对SnO2/Pdatom材料的电阻值、响应/恢复时间、重复性、低浓度分辨能力、湿度和稳定性进行研究,结果如图8所示。首先,SnO2/Pdatom材料的电阻值在4~6MΩ之间,与现有的工业氢气传感器电阻值相当,有利于实现传感器的工业化应用。同时其对10pmm的H2响应和恢复时间分别为3s和37s,表面该材料具有很好的响应和恢复能力。同时其还表现出较好的重复性,尤其是对100ppb浓度的H2具有很好的分辨能力,可以实现超低浓度检测,并确保具有较高的精度。而传感器的响应值随着湿度的增加,发生明显的降低,表明在高湿度环境下由于水汽和H2竞争吸附,导致传感器的响应值有所降低。最后经过15天的连续测试和老化后,该材料仍然表现出较高的响应值,具有良好的长程稳定性。
实施例2
Au/Pd双金属纳米晶修饰的SnO2中空球的制备:
取0.1g氨基化的SnO2中空球加入到35mL去离子水中,超声分散5分钟,然后向分散液中依次加入10mL浓度为0.5mg/mL的HAuCl4和10mL浓度为0.5mg/mL的Na2PdCl4,室温下搅拌12小时,然后用去离子水对样品离心洗涤3次。将洗涤后的样品重新分散到40mL去离子水中,加入3mL浓度为1mol/mL的NaBH4水溶液,在室温下搅拌6小时。随后用去离子水和无水乙醇对产物进行离心洗涤。最终,将产物置于60℃干燥箱干燥,得到Au/Pd双金属纳米晶修饰的SnO2中空球。
对Au/Pd双金属纳米晶修饰的SnO2中空球进行电镜观察,结果如图5所示,其中,(a)SEM图,(b)TEM图,(c)高倍率TEM图,(d)HRTEM图,(e)高角度圆形暗场图像,(f)EDS线扫描图,(g)EDS面扫描图。从(a)和(b)中可以看到,制备出的SnO2呈球形,具有中空结构,同时尺寸均一;从样品的高倍率TEM图像中可以清晰观察到,在SnO2表面存在尺寸较小的颗粒。为了确定该小颗粒是否为Au/Pd合金颗粒,对其进行了HRTEM表征,如图5中(d)所示。图5中(d)显示,除了SnO2位于0.334nm晶格条纹外,还明显观察到了另外一种晶格条纹(0.23nm处)。通过仔细分析发现,该晶格条纹在Au((111)(JCPDS96-901-1613,0.234nm)和Pd(111)(JCPDS96-101-1109,0.228nm)之间,这说明该颗粒为Au/Pd合金颗粒。为了进一步证实这个观点,对样品又进行了EDS线扫描和面扫描。从EDS线扫描图中可以发现,对于选定的单个纳米颗粒,很明显观察到Pd和Au两种元素,并且这两种元素分布相一致,这证明了Au/Pd合金颗粒的存在。此外,从EDS面扫图,可以观察到Au和Pd均匀分布在SnO2中空球表面,并且Au和Pd元素的位置高度重合,这与EDS线扫结果相一致,进一步证明了SnO2成功担载了超小Au/Pd合金颗粒。
图6为SnO2/AuPdalloys合金颗粒的高分辨XPS图,其中(a)Sn3d,(b)O1s,(c)Au4f,(d)Pd3d。如图6所示,很明显出现了494.9和486.5eV两个特征峰,这对应于Sn3d3/2和Sn3d5/2。同时,还出现了O2-1s(530.4eV)和O2-1s(531.3eV)特征峰。进一步地,通过高分辨率XPS谱图,明显发现位于83.1和86.8eV两个特征峰,这源于Au4f7/2和Au4f5/2,这表明SnO2表面存在Au元素。此外,在335.1和340.2eV处也出现了两个显著特征峰,通过分析发现这两个峰分别对应于Pd3d5/2和Pd3d3/2,这意味着Pd元素存在于SnO2表面。进一步地,为了识别Au与Pd元素是否以合金形式存在于SnO2的表面,又进行了对比测试。
如图7所示,对于单纯SnO2/Au而言,其Au4f7/2和Au4f5/2特征峰值分别出现在83.4和87.1eV,这明显高于所制备样品中的Au4f峰值。同时,对于单纯SnO2/Pd,Pd3d3/2峰值位于340.42eV,明显高于所制备样品中Pd3d3/2峰值。根据上述对比结果发现,所制备样品中的Au4f和Pd3d3/2特征峰均向更低结合能发生位移,这是由于Au和Pd形成合金引起的电子转移所造成,即电子从Pd原子转移到Au原子。根据Pauling电负性规则,Au的电负性为2.54,其高于Pd的电负性2.20,所以当Au和Pd形成合金时,电子会从Pd原子转移到Au原子,从而引起结合能向低处位移,这证明了SnO2表面确实形成了Au/Pd合金颗粒。因此,根据以上测试结果,证实本申请成功得到了Au/Pd合金颗粒修饰的SnO2复合材料。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (8)
1.一种Pd单原子修饰的SnO2纳米颗粒的制备方法,其特征在于,包括以下步骤:
将SnCl4·H2O加入到乙醇与去离子水的混合溶液,经过超声分散后,加入盐酸并室温搅拌,然后在200℃反应12小时,离心干燥得到SnO2纳米颗粒;
将所述SnO2纳米颗粒和二氯四氨钯混合,并在室温下搅拌,然后经离心洗涤干燥后得到Pd单原子修饰的SnO2纳米颗粒。
2.根据权利要求1所述的制备方法,其特征在于,所述混合溶液中乙醇和去离子水的体积比为10:1。
3.权利要求1或2所述制备方法制备得到的Pd单原子修饰的SnO2纳米颗粒,平均粒径为750~780nm。
4.根据权利要求3所述的Pd单原子修饰的SnO2纳米颗粒,其特征在于,Pd的质量百分含量为0.15%。
5.权利要求3或4所述Pd单原子修饰的SnO2纳米颗粒在H2传感器中的应用。
6.一种Au/Pd双金属纳米晶修饰的SnO2中空球的制备方法,其特征在于,包括以下步骤:
取0.1g氨基化的SnO2中空球加入到35mL去离子水中,超声分散5分钟,然后向所得分散液中依次加入10mL浓度为0.5mg/mL的HAuCl4和10mL浓度为0.5mg/mL的Na2PdCl4,室温下搅拌12小时,然后用去离子水对所得样品离心洗涤3次,将洗涤后的样品重新分散到40mL去离子水中,加入3mL浓度为1mol/mL的NaBH4水溶液,在室温下搅拌6小时,随后用去离子水和无水乙醇对产物进行离心洗涤,将产物置于60℃干燥箱干燥,得到Au/Pd双金属纳米晶修饰的SnO2中空球。
7.权利要求6所述制备方法制备得到的Au/Pd双金属纳米晶修饰的SnO2中空球,包括SnO2中空球和负载在所述SnO2中空球表面的Au/Pd合金颗粒。
8.权利要求7所述Au/Pd双金属纳米晶修饰的SnO2中空球在H2传感器中的应用。
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