CN106541148B - 一种金铂合金纳米双锥框架、制备方法及其应用 - Google Patents
一种金铂合金纳米双锥框架、制备方法及其应用 Download PDFInfo
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Abstract
本发明提供了一种金铂合金纳米双锥框架、制备方法及其应用;与现有技术相比,本发明提供的一步法合成空心框架结构,无需繁琐的步骤,反应时间较短,且反应条件温和,所需设备简单。而且,合成的纳米双锥框架结构比较稳定;所合成的样品常温放置两个月之后没有发生变化。产物具有双功能结构,能够实现对催化反应的指导。
Description
技术领域
本发明属于无机纳米材料领域和催化材料研究领域,具体涉及一种金铂合金纳米双锥框架、制备方法及其应用。
背景技术
贵金属纳米材料由于其独特的表面等离子体性能而吸引了众多关注,在催化、表面增强拉曼散射、荧光增强、传感以及光热治疗等方面有着广泛应用。目前,在贵金属材料的表面增强拉曼效应已用来指导不同种类的催化反应,这要求材料具有催化和表面等离子体双功能结构。金纳米颗粒尺寸小于10nm时具有很好的催化性能,但是不具有表面增强拉曼散射性能,只有金纳米颗粒尺寸大于20nm时才具有等离子体活性,但大颗粒的材料不具有催化活性;金属铂具有很好的催化性能,但铂的等离子体性能很弱。因此,可以利用金的等离子体性能与铂的催化性能合成金铂合金材料。
但目前合成金铂合金材料具有以下几个问题:第一,合成步骤繁琐,反应条件比较苛刻;第二,合成的材料稳定性差;第三,合成的材料比表面积比较小。因此,为了增加表面增强拉曼效应在指导催化反应方面的应用就必须发展一种简单且合成比表面较大的金铂合金纳米材料。
发明内容
本发明的目的在于提供一种金铂合金纳米双锥框架及其制备方法,制备方法操作简单、反应条件温和,所得金铂合金纳米双锥框架结构比表面积大,催化活性高且表面增强拉曼效应比较显著。
本发明提供的一种金铂合金纳米双锥框架的制备方法,包括以下步骤:
A、种子溶液的制备:将HAuCl4水溶液和H2PtCl6水溶液加入到十六烷基三甲基溴化铵水溶液中,搅拌均匀后,向其中加入新配制的NaBH4冰水溶液,在25~35℃恒温条件中静置2-5h得到种子溶液;
B、金铂合金纳米双锥框架的制备:
将HAuCl4水溶液、H2PtCl6水溶液、AgNO3水溶液和稀HCl溶液依次加入到十六烷基三甲基溴化铵水溶液中,混匀后,在搅拌条件下加入抗坏血酸水溶液,待溶液被还原为无色后立即加入步骤A制备的种子溶液,在70℃恒温反应7-24小时,离心分离,即可得到金铂合金纳米双锥框架结构;
步骤A中,所述HAuCl4水溶液、十六烷基三甲基溴化铵水溶液、NaBH4冰水溶液的体积之比为(50~200):10000:(500~1200);HAuCl4水溶液与H2PtCl6水溶液的体积之比为(0.2~2):1。选择NaBH4冰水溶液的原因在于:NaBH4非常活泼,在水中容易水解放出H2,用冰水可抑制其水解。
进一步的,步骤A中,所述HAuCl4水溶液、H2PtCl6水溶液、十六烷基三甲基溴化铵水溶液和NaBH4冰水溶液的摩尔浓度之比为(0.005~0.015):(0.005~0.015):(0.08~0.15):(0.005~0.015)。
步骤B中,所述十六烷基三甲基溴化铵水溶液、HAuCl4水溶液、AgNO3水溶液、HCl溶液、抗坏血酸水溶液和种子溶液的体积之比为(30000~50000):(300~1500):(300~1200):(700~1200):(280~600):(50~800);HAuCl4水溶液与H2PtCl6水溶液的体积之比为(0.2~1.5):1。
进一步的,步骤B中,所述HAuCl4水溶液、H2PtCl6水溶液、AgNO3水溶液、HCl溶液、十六烷基三甲基溴化铵水溶液和抗坏血酸水溶液的摩尔浓度之比为(0.005~0.015):(0.005~0.015):(0.005~0.015):(0.5~1.5):(0.08~0.15):0.1。
具体的,所述金铂合金纳米双锥框架的制备方法,包括以下步骤:
A.种子溶液的制备:把0.005~0.015M的HAuCl4水溶液50~200μL和0.005~0.015M的H2PtCl6水溶液依次加入到10ml浓度为0.08~0.15M的十六烷基三甲基溴化铵水溶液中,HAuCl4水溶液与H2PtCl6水溶液的体积之比为(0.2~2):1,搅拌均匀后,向其中加入新配制的0.005~0.015M的NaBH4冰水溶液500~1200μL,25~35℃恒温条件中静置2-5h,得到种子溶液;
B.金铂合金纳米双锥框架结构的制备:把浓度为0.005~0.015M的HAuCl4水溶液300~1500μL、0.005~0.015M的H2PtCl6水溶液、0.005~0.015M的AgNO3水溶液300~1200μL和0.5~1.5M的HCl溶液700~1200μL依次加入到30~50mL浓度为0.08~0.15M的十六烷基三甲基溴化铵水溶液中,并在搅拌条件下加入0.1M的抗坏血酸水溶液280~600μL,待溶液被还原为无色后立即加入步骤A制备的种子溶液50~800μL,70℃恒温反应7-24小时,离心分离,即可得到金铂合金纳米双锥框架。
本发明提供的一种金铂合金纳米双锥框架,采用以上方法制备得到,金铂合金纳米双锥框架为空心框架结构,双锥框架的长轴尺寸100~200nm、短轴尺寸30~60nm、棱的厚度为8~16nm。
本发明还提供了一种金铂合金纳米双锥框架催化对硝基苯硫酚还原的应用。
本发明的制备的金铂合金纳米双锥框架性能的评价方法:
1、对硝基苯硫酚吸附
取2ml样离心分离,稀释到1ml的水中,然后向其中加入200μL的1m对硝基苯硫酚丙酮溶液,静置2h后离心,用水洗一次分散在100μL水中。
2、拉曼信号峰的测试
取40μL样加入PDMS小槽中,然后加入15μL的0.02M新配制的硼氢化钠冰水溶液,用RENISHAW拉曼光谱仪进行谱图收集。
本发明调控了原料氯金酸与氯铂酸溶液的配比,由于金离子比铂离子更容易得电子,在铂离子的诱导下被还原出来长成双锥结构,此方法中增加的氯铂酸慢慢被抗坏血酸及零价的金还原在锥的尖端和棱表面能较大的地方生长,而新形成的金离子又会被抗坏血酸还原,如此不断反应,便会形成金铂合金纳米框架结构。而氯铂酸量少时则不会形成这种结构。框架架构具有比表面积大且为金铂合金,可以用拉曼信号指导催化反应的进行。而金纳米双锥结构由于只有单一的金催化性能很差。
与现有技术相比,本发明提供的一步法合成空心框架结构,无需繁琐的步骤,反应时间较短,且反应条件温和,所需设备简单。而且,合成的纳米双锥框架结构比较稳定;所合成的样品常温放置两个月之后没有发生变化。产物具有双功能结构,能够实现对催化反应的指导。
附图说明
图1a为实施例1所得的金铂合金纳米双锥框架结构在水溶液中的消光光谱图;
图1b为实施例1所得的金铂合金纳米双锥框架结构在水溶液中对应的透射电镜图;
图2为实施例7所得的金铂合金纳米双锥框架结构的TEM图;
图3为实施例2所得的金铂合金纳米双锥框架结构的XRD图;
图4为实施例2所得金铂合金纳米双锥框架结构催化还原对硝基苯硫酚的拉曼信号随时间的变化图;从下到上依次为1、100s、200s、300s、10min、15min、20min、25min。
具体实施方式
实施例1
一种金铂合金纳米双锥框架的制备方法,所述制备方法包括以下步骤:
A、取10mL的0.1M的CTAB水溶液于一试管中,然后加入125μL的0.01M的HAuCl4水溶液和125μL的0.01M的H2PtCl6水溶液,最后加入1000μL的新配置0.01M的NaBH4冰水溶液,摇匀后将溶液放置在35℃的烘箱中2h。
B、取40mL的0.1M的CTAB水溶液于一烧杯中,依次加入1.0mL的0.01M的HAuCl4水溶液、0.8mL的0.01M的H2PtCl6水溶液、400μL的0.01M的AgNO3水溶液、800μL的1M的HCl溶液,搅拌条件下加入320μL的0.1M的抗坏血酸水溶液,变无色后立即加入步骤A制备的种子溶液100μL,放入70℃的烘箱中放置7小时;离心分离即可得到金铂合金纳米双锥框架。
测其在水溶液中的消光光谱图和透射电镜图,如图1a和图1b所示,从图中可以看到,产物为纳米双锥框架结构。长轴尺寸为95~120nm,短轴尺寸为40~50nm,棱的宽度为10~12nm。
实施例2
一种金铂合金纳米双锥框架的制备方法,所述制备方法包括以下步骤:
A、取10mL的0.1M的CTAB水溶液于一试管中,然后加入125μL的0.01M的HAuCl4水溶液和125μL的0.01M的H2PtCl6水溶液,最后加入1000μL的新配置0.01M的NaBH4冰水溶液,摇匀后将溶液放置在35℃的烘箱中2h。
B、取40mL的0.1M的CTAB水溶液于一烧杯中,依次加入1.0mL的0.01M的HAuCl4水溶液、1.0mL的0.01M的H2PtCl6水溶液、400μL的0.01M的AgNO3水溶液、800μL的1M的HCl溶液,搅拌条件下加入320μL的0.1M的抗坏血酸水溶液,待溶液变无色后立即加入步骤A制备的种子溶液100μL,放入70℃的烘箱中放置7小时,离心分离即可得到金铂合金纳米双锥框架。长轴尺寸为110~134nm,短轴尺寸为45~53nm,棱的宽度为9.2~14.5nm。
测其XRD图,如图3所示,从图中可以看到,所得产物为金铂合金纳米双锥框架结构。
实施例3
一种金铂合金纳米双锥框架的制备方法,所述制备方法包括以下步骤:
A、取10mL的0.1M的CTAB水溶液于一试管中,然后加入125μL的0.01M的HAuCl4水溶液和125μL的0.01M的H2PtCl6水溶液,最后加入1000μL的新配置0.01M的NaBH4冰水溶液,摇匀后将溶液放置在35℃的烘箱中2h。
B、取40ml的0.1M的CTAB水溶液于一烧杯中,依次加入1.0mL的0.01M的HAuCl4水溶液、1.2mL的0.01M的H2PtCl6水溶液、600μL的0.01M的AgNO3水溶液、800μL的1M的HCl溶液,搅拌条件下加入320μL的0.1M的抗坏血酸水溶液,变无色后立即加入步骤A制备的种子溶液100μL,放入70℃的烘箱中放置7小时;离心分离即可得到金铂合金纳米双锥框架。
实施例4
一种金铂合金纳米双锥框架的制备方法,所述制备方法包括以下步骤:
A、取10mL的0.12M的CTAB水溶液于一试管中,然后加入150μL的0.01M的HAuCl4水溶液和100μL的0.01M的H2PtCl6水溶液,最后加入1000μL的新配置0.008M的NaBH4冰水溶液,摇匀后将溶液放置在35℃的烘箱中2h。
B、取40mL的0.1M的CTAB水溶液于一烧杯中,依次加入1.0mL的0.01M的HAuCl4水溶液、1.0mL的0.01M的H2PtCl6水溶液、400μL的0.01M的AgNO3水溶液、800μL的1M的HCl溶液,搅拌条件下加入320μL的0.1M的抗坏血酸水溶液,变无色后立即加入步骤A制备的种子溶液200μL,放入70℃的烘箱中放置7小时;离心分离即可得到金铂合金纳米双锥框架。
实施例5
一种金铂合金纳米双锥框架的制备方法,所述制备方法包括以下步骤:
A、取10mL的0.1M的CTAB水溶液于一试管中,然后加入100μL的0.01M的HAuCl4水溶液和150μL的0.01M的H2PtCl6水溶液,最后加入1000μL的新配置0.01M的NaBH4冰水溶液,摇匀后将溶液放置在35℃的烘箱中2h。
B、取40mL的0.1M的CTAB水溶液于一烧杯中,依次加入1.0mL的0.01M的HAuCl4水溶液、1.2mL的0.01M的H2PtCl6水溶液、400μL的0.01M的AgNO3水溶液、1.0mL的1M的HCl溶液,搅拌条件下加入320μL的0.1M的抗坏血酸水溶液,变无色后立即加入步骤A制备的种子溶液200μL,放入70℃的烘箱中放置20小时;离心分离即可得到金铂合金纳米双锥框架。
实施例6
一种金铂合金纳米双锥框架的制备方法,所述制备方法包括以下步骤:
A、取10mL的0.15M的CTAB水溶液于一试管中,然后加入125μL的0.015M的HAuCl4水溶液和125μL的0.015M的H2PtCl6水溶液,最后加入900μL的新配置0.015M的NaBH4冰水溶液,摇匀后将溶液放置在35℃的烘箱中4h。
B、取50mL的0.15M的CTAB水溶液于一烧杯中,依次加入0.5mL的0.015M的HAuCl4水溶液、1.0mL的0.015M的H2PtCl6水溶液、500μL的0.015M的AgNO3水溶液、1000μL的1.5M的HCl溶液,搅拌条件下加入600μL的0.1M的抗坏血酸水溶液,变无色后立即加入步骤A制备的种子溶液500μL,放入70℃的烘箱中放置24小时;离心分离即可得到金铂合金纳米双锥框架。
实施例7
一种金铂合金纳米双锥框架的制备方法,所述制备方法包括以下步骤:
A、取10mL的0.08M的CTAB水溶液于一试管中,然后加入50μL的0.005M的HAuCl4水溶液和200μL的0.005M的H2PtCl6水溶液,最后加入500μL的新配置0.005M的NaBH4冰水溶液,摇匀后将溶液放置在35℃的烘箱中3h。
B、取30mL的0.08M的CTAB水溶液于一烧杯中,依次加入0.3mL的0.01M的HAuCl4水溶液、1.0mL的0.01M的H2PtCl6水溶液、400μL的0.01M的AgNO3水溶液、800μL的1M的HCl溶液,搅拌条件下加入320μL的0.1M的抗坏血酸水溶液,变无色后立即加入步骤A制备的种子溶液100μL,放入70℃的烘箱中放置10小时;;离心分离即可得到金铂合金纳米双锥框架。长轴尺寸为80~98.5nm,短轴尺寸为39.5~46.5nm,棱的宽度为11~16nm。
Claims (7)
1.一种金铂合金纳米双锥框架的制备方法,其特征在于,所述制备方法包括以下步骤:
A、种子溶液的制备:将HAuCl4水溶液和H2PtCl6水溶液加入到十六烷基三甲基溴化铵水溶液中,搅拌均匀后,向其中加入新配制的NaBH4冰水溶液,在25~35℃恒温条件中静置2−5h得到种子溶液;
B、金铂合金纳米双锥框架的制备:
将HAuCl4水溶液、H2PtCl6水溶液、AgNO3水溶液和稀HCl溶液依次加入到十六烷基三甲基溴化铵水溶液中,混匀后,在搅拌条件下加入抗坏血酸水溶液,待溶液被还原为无色后立即加入步骤A制备的种子溶液,在70℃恒温反应7−24小时,离心分离,即可得到金铂合金纳米双锥框架结构;
步骤A中,所述HAuCl4水溶液、十六烷基三甲基溴化铵水溶液、NaBH4冰水溶液的体积之比为(50~200):10000:(500~1200);HAuCl4水溶液与H2PtCl6水溶液的体积之比为(0.2~2):1;
步骤B中,所述十六烷基三甲基溴化铵水溶液、HAuCl4水溶液、AgNO3水溶液、HCl溶液、抗坏血酸水溶液和种子溶液的体积之比为(30000~50000):(300~1500):(300~1200):(700~1200):(280~600):(50~800);HAuCl4水溶液与H2PtCl6水溶液的体积之比为(0.2~1.5):1。
2.根据权利要求1所述的金铂合金纳米双锥框架的制备方法,其特征在于,步骤A中,所述HAuCl4水溶液、H2PtCl6水溶液、十六烷基三甲基溴化铵水溶液和NaBH4冰水溶液的摩尔浓度之比为(0.005~0.015):(0.005~0.015):(0.08~0.15):(0.005~0.015)。
3.根据权利要求1或2所述的金铂合金纳米双锥框架的制备方法,其特征在于,步骤B中,所述HAuCl4水溶液、H2PtCl6水溶液、AgNO3水溶液、HCl溶液、十六烷基三甲基溴化铵水溶液和抗坏血酸水溶液的摩尔浓度之比为(0.005~0.015):(0.005~0.015):(0.005~0.015):(0.5~1.5):(0.08~0.15):0.1。
4.根据权利要求1或2所述的金铂合金纳米双锥框架的制备方法,其特征在于,所述金铂合金纳米双锥框架的制备方法,包括以下步骤:
A.种子溶液的制备:把0.005~0.015M的HAuCl4水溶液50~200 µL和0.005~0.015M的H2PtCl6水溶液依次加入到10 ml浓度为0.08~0.15M的十六烷基三甲基溴化铵水溶液中,HAuCl4水溶液与H2PtCl6水溶液的体积之比为(0.2~2):1,搅拌均匀后,向其中加入新配制的0.005~0.015M的NaBH4冰水溶液500~1200 µL,25~35℃恒温条件中静置2−5h,得到种子溶液;
B.金铂合金纳米双锥框架结构的制备:把浓度为0.005~0.015M的HAuCl4水溶液300~1500µL、0.005~0.015M的H2PtCl6水溶液、0.005~0.015M的AgNO3水溶液300~1200 µL和0.5~1.5M的HCl溶液700~1200 µL依次加入到30~50mL浓度为0.08~0.15M的十六烷基三甲基溴化铵水溶液中,并在搅拌条件下加入0.1M的抗坏血酸水溶液280~600 µL,待溶液被还原为无色后立即加入步骤A制备的种子溶液50~800µL,70℃恒温反应7−24小时,离心分离,即可得到金铂合金纳米双锥框架。
5.根据权利要求3所述的金铂合金纳米双锥框架的制备方法,其特征在于,所述金铂合金纳米双锥框架的制备方法,包括以下步骤:
A.种子溶液的制备:把0.005~0.015M的HAuCl4水溶液50~200 µL和0.005~0.015M的H2PtCl6水溶液依次加入到10 ml浓度为0.08~0.15M的十六烷基三甲基溴化铵水溶液中,HAuCl4水溶液与H2PtCl6水溶液的体积之比为(0.2~2):1,搅拌均匀后,向其中加入新配制的0.005~0.015M的NaBH4冰水溶液500~1200 µL,25~35℃恒温条件中静置2−5h,得到种子溶液;
B.金铂合金纳米双锥框架结构的制备:把浓度为0.005~0.015M的HAuCl4水溶液300~1500µL、0.005~0.015M的H2PtCl6水溶液、0.005~0.015M的AgNO3水溶液300~1200 µL和0.5~1.5M的HCl溶液700~1200 µL依次加入到30~50mL浓度为0.08~0.15M的十六烷基三甲基溴化铵水溶液中,并在搅拌条件下加入0.1M的抗坏血酸水溶液280~600 µL,待溶液被还原为无色后立即加入步骤A制备的种子溶液50~800µL,70℃恒温反应7−24小时,离心分离,即可得到金铂合金纳米双锥框架。
6.一种金铂合金纳米双锥框架,其特征在于,采用权利要求1-5任一项所述方法制备得到,所述金铂合金纳米双锥框架为空心框架结构,双锥框架的长轴尺寸100~200nm、短轴尺寸30~60nm、棱的厚度为8~16nm。
7.一种权利要求6所述的金铂合金纳米双锥框架催化对硝基苯硫酚还原的应用。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003226901A (ja) * | 2002-02-05 | 2003-08-15 | Hitachi Maxell Ltd | 二元系合金微粒子及びその製造方法 |
CN101406832A (zh) * | 2008-11-24 | 2009-04-15 | 中国科学院长春应用化学研究所 | 不同粒径单分散的花状金/铂杂化纳米粒子制备方法 |
CN103240420A (zh) * | 2013-05-24 | 2013-08-14 | 苏州大学 | 一种金双锥结构纳米粒子的提纯方法 |
CN103394704A (zh) * | 2013-08-20 | 2013-11-20 | 纳米籽有限公司 | 高纯度金纳米双锥及其复合纳米材料的制备方法 |
KR20140119393A (ko) * | 2013-03-29 | 2014-10-10 | 인텔렉추얼디스커버리 주식회사 | 백금 팔면체 나노 프레임, 계층형 조립 백금 나노 구조체, 및 그 제조 방법 |
CN105458293A (zh) * | 2016-01-08 | 2016-04-06 | 苏州大学 | 一种双锥结构金纳米粒子及其制备方法 |
CN105665744A (zh) * | 2016-03-22 | 2016-06-15 | 安徽师范大学 | 一种金纳米双锥的制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5285054B2 (ja) * | 2010-12-08 | 2013-09-11 | 本田技研工業株式会社 | 酸化還元反応用合金触媒の製造方法 |
-
2016
- 2016-11-25 CN CN201611051753.0A patent/CN106541148B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003226901A (ja) * | 2002-02-05 | 2003-08-15 | Hitachi Maxell Ltd | 二元系合金微粒子及びその製造方法 |
CN101406832A (zh) * | 2008-11-24 | 2009-04-15 | 中国科学院长春应用化学研究所 | 不同粒径单分散的花状金/铂杂化纳米粒子制备方法 |
KR20140119393A (ko) * | 2013-03-29 | 2014-10-10 | 인텔렉추얼디스커버리 주식회사 | 백금 팔면체 나노 프레임, 계층형 조립 백금 나노 구조체, 및 그 제조 방법 |
CN103240420A (zh) * | 2013-05-24 | 2013-08-14 | 苏州大学 | 一种金双锥结构纳米粒子的提纯方法 |
CN103394704A (zh) * | 2013-08-20 | 2013-11-20 | 纳米籽有限公司 | 高纯度金纳米双锥及其复合纳米材料的制备方法 |
CN105458293A (zh) * | 2016-01-08 | 2016-04-06 | 苏州大学 | 一种双锥结构金纳米粒子及其制备方法 |
CN105665744A (zh) * | 2016-03-22 | 2016-06-15 | 安徽师范大学 | 一种金纳米双锥的制备方法 |
Non-Patent Citations (1)
Title |
---|
金属表面对硝基苯硫酚等离激元催化反应的SERS研究;翁华怡;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20160215(第2期);B014-210页 * |
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