CN106890640A - 一种核壳结构Pd‑Sn@SiO2催化剂及制备方法 - Google Patents
一种核壳结构Pd‑Sn@SiO2催化剂及制备方法 Download PDFInfo
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Abstract
一种核壳结构Pd‑Sn@SiO2催化剂及制备方法,该催化剂是采用反相微乳液法制备的Pd‑Sn@SiO2核壳材料。该催化剂是经过室温搅拌反应、离心、真空干燥、高温焙烧制得的。该方法制备的Pd‑Sn@SiO2催化剂,在常压下、反应气组成为1%CO,21%O2,N2平衡气,空速为3,6000ml.gcat ‑1.h‑1的条件下150℃将CO完全催化燃烧。本发明具有制备工艺简单、对环境无二次污染、低温高活性和高温抗烧结等优点。
Description
技术领域
本发明属于纳米催化剂制备工艺和环境保护技术领域。
背景技术
日前,环境恶化日益突出,而CO是空气中有毒气体污染物之一。由于其无色、无味,故易于忽略而致中毒,它可与人体的血红蛋白结合,削弱血红蛋白输氧能力,从而出现缺氧,轻者可出现头痛、头晕、恶心、呕吐、全身乏力,重者可因呼吸麻痹而死亡。CO主要来自于机动车尾气、工厂废气、民用炉灶、固体废弃物焚烧排出的废气等。目前 CO的低温氧化已成为催化研究的热点之一,其在许多方面都有重要的应用价值,如空气净化、CO防毒面罩、CO传感器等。其中催化氧化是消除CO最有效的方法。
目前CO催化燃烧催化剂主要分为两大类一类是在低温条件下催化性能较好的负载型贵金属催化剂如钯、铂等,另一类是在高温条件下催化性能好的金属氧化物催化剂如钙钛矿型氧化物、过渡金属氧化物固溶体和六铝酸盐等。负载型贵金属催化剂活性高,但是热稳定性差,高温下易烧结和中毒并导致活性下降。如何提高贵金属的利用效率和抗烧结性能是CO催化燃烧亟待解决的关键问题。
SnO2属于四方金红石型结构,是一种典型的n型半导体,由于其高温热稳定性,在气敏材料、气体传感器和检测器、半导体及电池等方面有广泛的应用。由于SnO2表面具有活泼的缺位氧,其在催化方面的应用日益引起人们的广泛关注。如1977年,Fuller等在Nature上发表的结果表明,SnO2负载Pd催化剂对CO氧化具有高的活性,比常规催化剂Pd/SiO2活性高的多,并且在有水的情况表现出更加优异的性能,不仅不会抑制CO的氧化活性,反而使得CO的氧化活性有所提高;反观传统载体负载型催化剂Pd/SiO2活性受到水的影响大幅降低,他们得出结论指明这是由于Pd和SnO2之间存在强烈的金属与载体间相互作用。传统的负载法制备的负载型贵金属催化剂活性高,但是热稳定性差,贵金属因烧结聚集而失活。核壳结构材料能有效的解决该问题。目前研究较多的是以SiO2做外包覆物,因其具有较好的高温热稳定性,在一氧化碳催化燃烧也可以保持很好的结构稳定性,进而能够有效抑制活性组分聚集,提高其活性和抗烧结性能。
发明内容
本发明的目的是提出一种核壳结构Pd-Sn@SiO2催化剂及制备方法。该催化剂中Pd-Sn纳米簇,且很好的包裹在耐高温SiO2壳层内,在高温反应下能够有效的抑制颗粒的迁移和聚集。采用该方法制备的Pd的质量分数为0.5%~2%,Sn的质量分数为1%~10%的Pd-Sn@SiO2催化剂,在常压下、反应气组成为1% CO,21% O2,N2平衡气,空速为3,6000ml.gcat-1.h-1。
本发明所述的一种核壳结构Pd-Sn@SiO2催化剂,其特征是钯的质量分数为0.5%~2%,锡的质量分数为1%~10%。
本发明所述的一种核壳结构Pd-Sn@SiO2催化剂的制备方法,其特征是用聚乙二醇单-4-壬苯醚(n≈5)为表面活性剂,环己烷为溶剂,四氨硝酸钯水溶液为钯源,六水硝酸铈为铈源,正硅酸四乙酯为硅源,浓氨水为沉淀剂,经过室温搅拌反应、离心、真空干燥、高温焙烧制得Pd-Sn@SiO2核壳催化剂。
更具体地说,本发明所述的一种核壳结构Pd-Sn@SiO2催化剂的制备方法,其特征在于包含以下步骤。
称取四氨硝酸钯和五水四氯化锡前驱体盐,将其溶于蒸馏水配成Pd2+浓度为0.0145mol/L~0.0583mol/L,Sn4+浓度为0.0261mol/L~0.2612mol/L的水溶液。将聚乙二醇单-4-壬苯醚(n≈5)溶于环己烷中,加入2.16ml上述四氨硝酸钯和五水四氯化锡水溶液,在30℃下搅拌15h;然后加入2.16ml质量分数28%的浓氨水,在30℃继续搅拌2h,再往其中加入2.5ml正硅酸四乙酯,在30℃继续搅拌48h。往所得溶液中加入16ml乙醇,随后在10000rp/min转速下离心15min收集,用环己烷洗涤;之后在40℃下真空干燥12h,研磨后在空气气氛下以1~2℃/min升温速率,在600℃焙烧4h,得Pd-Sn@SiO2核壳催化剂。
本发明以四氨硝酸钯和五水四氯化锡为钯和锡的前驱体直接制得核壳结构Pd-Sn@SiO2,避免了先制备Pd-Sn纳米簇,再包裹SiO2壳层这种分步法的复杂制备过程。
本发明制备的催化剂钯的质量分数2%,锡的质量分数为10%的Pd-Sn@SiO2,平均Pd-Sn纳米簇截面尺寸小于5nm,催化剂在一氧化碳催化燃烧中表现出优良的活性和稳定性。
本发明所制备的核壳结构催化剂的外包覆物为SiO2。
本发明所制得的Pd-Sn@SiO2核壳材料中每个硅球中包含多个Pd-Sn纳米线。
与现有技术相比,本发明制备的催化剂具有如下优点。
(1)本发明制备过程简单易行,设备要求低、溶剂可回收、对环境无二次污染。
(2)本发明以四氨硝酸钯和五水四氯化锡为钯和锡的前驱体采用反相微乳液法直接制得核壳结构Pd-Sn@SiO2,避免了先制备Pd-Sn纳米簇,再包裹SiO2壳层这种分步法的复杂制备过程。
(3)本发明制备的采用该方法制备的钯的质量分数为2%,锡的质量分数为10%的Pd-Sn@SiO2纳米线核壳催化剂,Pd-Sn纳米簇截面尺寸小于2nm,加上核壳结构的物理限域效应,催化剂在一氧化碳催化燃烧中表现出优良的活性和抗烧结能力。具有低温高活性、高温抗烧结等优点。
附图说明
图1为本发明制备Pd的质量分数为2%,Sn的质量分数为10%的Pd-Sn@SiO2催化剂透射电镜图。
图2为本发明制备的钯的质量分数为2%,锡的质量分数为10%的Pd-Sn@SiO2催化剂的CO催化燃烧活性测试。
图3为发明制备的钯的质量分数为2%,锡的质量分数为10%的Pd-Sn@SiO2催化剂在150℃下有5%水蒸气存在下的寿命测试。
图4 为本发明制备的钯的质量分数为2%,锡的质量分数为10%的Pd-Sn@SiO2催化剂在150℃下使用30h后的透射电镜照片。
具体实施方式
为了更清楚的说明本发明,列举以下实施例,但其对本发明的范围无任何限制。
实施例1。
称取四氨硝酸钯和五水四氯化锡,共同溶于蒸馏水,配成Pd2+溶度为0.0583mol/L,Sn4+溶度为0.2612mol/L 的水溶液。称取20.16g聚乙二醇单-4-壬苯醚(n≈5)溶于环己烷中,往该溶液中加入2.16ml上述配置的硝酸镍水溶液,在30℃下搅拌15h。然后加入2.16ml质量分数28%的浓氨水,在30℃继续搅拌2h,再往其中加入2.5ml正硅酸四乙酯,30℃下继续搅拌48h。往所得溶液中加入16ml乙醇,随后在10000rp/min转速下离心15min收集,用环己烷洗涤三次。在40℃下真空干燥12h,适当研磨后在空气气氛下以2℃/min升温速率,在600℃焙烧4h,得Pd-Sn@SiO2催化剂,其中钯的质量分数为2%,锡的质量分数为10%。
催化剂活性测试:取0.05g上述制备的Pd-Sn@SiO2催化剂核壳材料用流速为30ml/min,在常压下、反应气组成为1% CO,22% O2, N2平衡气。
实施例2。
称取四氨硝酸钯和五水四氯化锡,共同溶于蒸馏水,配成Pd2+溶度为0.0291mol/L,Sn4+溶度为0.2612mol/L 的水溶液。称取20.16g聚乙二醇单-4-壬苯醚(n≈5)溶于环己烷中,往该溶液中加入2.16ml上述配置的硝酸镍水溶液,在30℃下搅拌15h。然后加入2.16ml质量分数28%的浓氨水,在30℃继续搅拌2h,再往其中加入2.5ml正硅酸四乙酯,30℃下继续搅拌48h。往所得溶液中加入16ml乙醇,随后在10000rp/min转速下离心15min收集,用环己烷洗涤三次。在40℃下真空干燥12h,适当研磨后在空气气氛下以2℃/min升温速率,在600℃焙烧4h,得Pd-Sn@SiO2催化剂,其中钯的质量分数为1%,锡的质量分数为10%。
实施例3。
称取四氨硝酸钯和五水四氯化锡,共同溶于蒸馏水,配成Pd2+溶度为0.0583mol/L,Sn4+溶度为0.1306mol/L 的水溶液。称取20.16g聚乙二醇单-4-壬苯醚(n≈5)溶于环己烷中,往该溶液中加入2.16ml上述配置的硝酸镍水溶液,在30℃下搅拌15h。然后加入2.16ml质量分数28%的浓氨水,在30℃继续搅拌2h,再往其中加入2.5ml正硅酸四乙酯,30℃下继续搅拌48h。往所得溶液中加入16ml乙醇,随后在10000rp/min转速下离心15min收集,用环己烷洗涤三次。在40℃下真空干燥12h,适当研磨后在空气气氛下以2℃/min升温速率,在600℃焙烧4h,得Pd-Sn@SiO2催化剂,其中钯的质量分数为2%,锡的质量分数为5%。
Claims (3)
1.一种核壳结构Pd-Sn@SiO2催化剂,其特征是钯的质量分数为0.5%~2%,锡的质量分数为1%~10%。
2.权利要求1所述的核壳结构Pd-Sn@SiO2催化剂的制备方法,其特征是用聚乙二醇单-4-壬苯醚为表面活性剂,环己烷为溶剂,四氨硝酸钯水溶液为钯源,六水硝酸铈为铈源,正硅酸四乙酯为硅源,浓氨水为沉淀剂,经过室温搅拌反应、离心、真空干燥、高温焙烧。
3.根据权利要求2所述的核壳结构Pd-Sn@SiO2催化剂的制备方法,其特征是包含以下步骤:
称取四氨硝酸钯和五水四氯化锡前驱体盐,将其溶于蒸馏水配成Pd2+浓度为0.0145mol/L~0.0583mol/L,Sn4+浓度为0.0261mol/L~0.2612mol/L的水溶液;将聚乙二醇单-4-壬苯醚溶于环己烷中,加入2.16ml上述四氨硝酸钯和五水四氯化锡水溶液,在30℃下搅拌15h;然后加入2.16ml质量分数28%的浓氨水,在30℃继续搅拌2h,再往其中加入2.5ml正硅酸四乙酯,在30℃继续搅拌48h;往所得溶液中加入16ml乙醇,随后在10000rp/min转速下离心15min收集,用环己烷洗涤;之后在40℃下真空干燥12h,研磨后在空气气氛下以1~2℃/min升温速率,在600℃焙烧4h。
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