CN108355652B - 一种用于co氧化反应中的金钯纳米催化剂的制备方法 - Google Patents
一种用于co氧化反应中的金钯纳米催化剂的制备方法 Download PDFInfo
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- 239000004408 titanium dioxide Substances 0.000 claims abstract description 10
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- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
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- 238000005406 washing Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
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Abstract
本发明公开了一种用于CO氧化反应中的金钯纳米催化剂的制备方法,具体步骤为:将100mg二氧化钛载体、4‑6mL摩尔浓度为2.0mmol L‑1的HAuCl4前驱体溶液和4‑6mL摩尔浓度为2.0mmol L‑1的H2PdCl4前驱体溶液混合均匀,于25℃搅拌反应4h,之后将混合物通过离心分离,并用去离子水洗涤催化剂去除氯离子和表面其它杂质,再置于50℃烘箱中干燥,干燥后的样品在惰性气氛中于300℃热处理,然后自然降温制得金钯纳米催化剂。本发明制得的金钯纳米催化剂分散性好,催化剂颗粒分布均匀,活性组分利用率高,在CO氧化反应中金钯纳米催化剂的催化活性较高且稳定性较好。
Description
技术领域
本发明属于双金属纳米催化剂的制备技术领域,具体涉及一种用于CO氧化反应中的金钯纳米催化剂的制备方法。
背景技术
经济高速发展带来各种含碳燃料的不完全燃烧,一氧化碳(CO)的排放越来越多。CO是一种气体,虽然没有颜色和气味,但是对人体具有危害性,一旦从呼吸道进入人体后,极易导致机体组织缺氧,引起窒息或死亡,而常温常压下CO气体密度与空气密度接近,会导致人们在毫无察觉的情况下中毒。因此,一方面要减少CO的产生与排放,另一方面要利用有效的方法对CO进行消除。目前,通过催化氧化法消除CO应用广泛,因此制备高活性、高稳定性的CO催化剂成为亟待解决的技术问题。
负载型Au-Pd双金属催化剂在CO氧化反应中表现出良好的催化效果。然而,金钯纳米颗粒活泼不稳定,在催化剂制备过程中容易发生团聚或者在反应过程发生流失等,造成催化活性降低。因此,通过改进制备方法控制合成高分散和高稳定的金钯纳米催化剂,仍是提高催化剂活性的关键,对消除CO也具有十分重要的意义。
发明内容
本发明解决的技术问题是提供了一种用于CO氧化反应中的金钯纳米催化剂的制备方法,该方法制得的金钯纳米催化剂分散性好,催化剂颗粒分布均匀,活性组分利用率高,在CO氧化反应中金钯纳米催化剂的催化活性较高且稳定性较好。
本发明为解决上述技术问题采用如下技术方案,一种用于CO氧化反应中的金钯纳米催化剂的制备方法,其特征在于具体步骤为:将100mg二氧化钛载体、4-6mL摩尔浓度为2.0mmol L-1的HAuCl4前驱体溶液和4-6mL摩尔浓度为2.0mmol L-1的H2PdCl4前驱体溶液混合均匀,于25℃搅拌反应4h,之后将混合物通过离心分离,并用去离子水洗涤催化剂去除氯离子和表面其它杂质,再置于50℃烘箱中干燥,干燥后的样品在惰性气氛中于300℃热处理,然后自然降温制得金钯纳米催化剂。
进一步优选,所述二氧化钛载体、摩尔浓度为2.0mmol L-1的HAuCl4前驱体溶液与摩尔浓度为2.0mmol L-1的H2PdCl4前驱体溶液的投料配比优选为100mg:5mL:5mL。
进一步优选,所述金钯纳米催化剂的平均粒度为3nm且分布均匀,在CO氧化反应中,在100℃条件下CO的转化率达到90%。
本发明将金、钯两种金属混合形成合金结构,相比于其相应的单金属催化剂,由于双金属之间存在协同作用能明显提高催化剂的催化活性和稳定性。本发明以多级孔结构二氧化钛为载体,利用其介孔孔道限制贵金属纳米粒子团聚,通过浸渍法负载金钯前驱体溶液,经过惰性气氛热处理制备金钯双金属纳米催化剂。通过CO氧化反应评价催化剂性能,通过调控活性组分的负载方法,控制合成金钯纳米颗粒,探索制备高活性催化剂的制备工艺条件。
与先行技术相比,本发明的主要优势体现在:工艺简单、操作方便,有利于工业化生产;本发明催化剂金钯纳米颗粒高分散且均匀分布在载体上,金钯纳米颗粒的平均粒度为3nm且分布均匀,与反应物CO接触面积大,反应充分,克服了现有催化剂颗粒团聚,催化活性低的问题;金钯纳米催化剂在CO氧化反应中活性高,在温度为100℃时CO的转化率可达到90%,且具有较好的稳定性。
附图说明
图1是本发明实施例1制得金钯纳米催化剂的TEM图;
图2是本发明实施例1制得金钯纳米催化剂的XRD图;
图3是本发明实施例1制得金钯纳米催化剂在CO氧化反应中的活性结果图。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明,但不应该将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明上述内容实现的技术均属于本发明的范围。
催化剂活性评价方法:原料气体的体积组成为1%CO、20%O2和79%N2,系统稳定后,调整反应温度至指定温度,稳定10min后采样分析。测试中的载气采用高纯氢气,反应产物利用色谱柱进行分离,经镍转化炉转化为甲烷后用FID检测器进行检测。反应产物采用气相色谱仪在线分析,催化剂的活性以CO的转化率表示。
实施例1
将100mg二氧化钛载体、5mL摩尔浓度为2.0mmol L-1的HAuCl4前驱体溶液和5mL摩尔浓度为2.0mmol L-1的H2PdCl4前驱体溶液混合均匀,于25℃搅拌反应4h,之后将混合物通过离心分离,并用去离子水洗涤催化剂去除氯离子和表面其它杂质,再置于50℃烘箱中干燥,干燥后的样品在惰性气氛中于300℃热处理,然后自然降温制得金钯纳米催化剂,该金钯纳米催化剂在CO氧化反应中,在100℃条件下CO的转化率为90%。
实施例2
将100mg二氧化钛载体、4mL摩尔浓度为2.0mmol L-1的HAuCl4前驱体溶液和6mL摩尔浓度为2.0mmol L-1的H2PdCl4前驱体溶液混合均匀,于25℃搅拌反应4h,之后将混合物通过离心分离,并用去离子水洗涤催化剂去除氯离子和表面其它杂质,再置于50℃烘箱中干燥,干燥后的样品在惰性气氛中于300℃热处理,然后自然降温制得金钯纳米催化剂,该金钯纳米催化剂在CO氧化反应中,在100℃条件下CO的转化率为84%。
实施例3
将100mg二氧化钛载体、6mL摩尔浓度为2.0mmol L-1的HAuCl4前驱体溶液和4mL摩尔浓度为2.0mmol L-1的H2PdCl4前驱体溶液混合均匀,于25℃搅拌反应4h,之后将混合物通过离心分离,并用去离子水洗涤催化剂去除氯离子和表面其它杂质,再置于50℃烘箱中干燥,干燥后的样品在惰性气氛中于300℃热处理,然后自然降温制得金钯纳米催化剂,该金钯纳米催化剂在CO氧化反应中,在100℃条件下CO的转化率为75%。
实施例4
将100mg二氧化钛载体、4.5mL摩尔浓度为2.0mmol L-1的HAuCl4前驱体溶液和5.5mL摩尔浓度为2.0mmol L-1的H2PdCl4前驱体溶液混合均匀,于25℃搅拌反应4h,之后将混合物通过离心分离,并用去离子水洗涤催化剂去除氯离子和表面其它杂质,再置于50℃烘箱中干燥,干燥后的样品在惰性气氛中于300℃热处理,然后自然降温制得金钯纳米催化剂,该金钯纳米催化剂在CO氧化反应中,在100℃条件下CO的转化率为82%。
以上实施例描述了本发明的基本原理、主要特征及优点,本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明原理的范围下,本发明还会有各种变化和改进,这些变化和改进均落入本发明保护的范围内。
Claims (1)
1.一种用于CO氧化反应中的金钯纳米催化剂的制备方法,其特征在于具体步骤为:将100mg二氧化钛载体、5mL摩尔浓度为2.0mmol L-1的HAuCl4前驱体溶液和5mL摩尔浓度为2.0mmol L-1的H2PdCl4前驱体溶液混合均匀,于25℃搅拌反应4h,之后将混合物通过离心分离,并用去离子水洗涤催化剂去除氯离子和表面其它杂质,再置于50℃烘箱中干燥,干燥后的样品在惰性气氛中于300℃热处理,然后自然降温制得金钯纳米催化剂,催化剂中金钯纳米颗粒的平均粒度为3nm且分布均匀,在CO氧化反应中,原料气体的体积组成为1% CO、20%O2和79% N2,在100℃条件下CO的转化率达到90%。
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