CN106077703A - 利用含有酰腙键的共价型动态超支化聚胺作为分子纳米反应器制备金属纳米晶体的方法 - Google Patents
利用含有酰腙键的共价型动态超支化聚胺作为分子纳米反应器制备金属纳米晶体的方法 Download PDFInfo
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Abstract
本发明是一种化工领域的利用含有酰腙键的共价型动态超支化聚胺作为纳米反应器制备金属纳米晶体的方法。本发明的方法是利用含有酰腙键的共价型动态超支化聚胺在水相体系中制备金属纳米晶体。含有酰腙键的共价型动态超支化聚胺具有环境敏感特性,因此可赋予制备的金属纳米晶体以环境敏感特性。此外,所制备的金属纳米晶体具有较高的催化活性,能够用于催化对硝基苯酚加氢等反应。
Description
技术领域
本发明涉及一种化学合成技术领域,具体涉及一种利用含有酰腙键的共价型动态超支化聚胺作为分子纳米反应器制备金属纳米晶体的方法。
背景技术
共价型动态超支化聚合物是一类含有可逆共价键的超支化聚合物,它不仅具有超支化聚合物分子的三维准球形结构,还具有可逆的共价键,对环境(如pH、温度等)具有响应特性。
经对现有技术的文献检索发现,目前利用超支化聚合物制备纳米晶体已有诸多报道[Sooklal, K.; Hanus, L. H.; Ploehn, H. J.; Murphy, C. J. Adv. Mater. 1998,10, 1083–1087.; Lemon, B.; Crooks, R. M. J. Am. Chem. Soc. 2000, 122, 12886–12887.; Wu, X. C.; Bittner, A. M.; Kern, K. J. Phys. Chem. B 2005, 109, 230–239.; Aymonier, C.; Schlotterbeck, U.; Antonietti, L.; Zacharias, P.;Thomann, R.; Tiller, J. C.; Mecking, S. Chem. Commun. 2002, 3018–3019.; Shi,Y. F.; Tu, C. L.; Wang, R. B.; Wu, J. Y.; Zhu, X. Y. and Yan, D. Y. Langmuir 2008, 24, 11955.]。在这些报道中所采用的超支化聚合物只含有不可逆共价键或可逆非共价键。还有报道利用含有可逆共价键的共价型动态超支化聚胺制备了CdS量子点[Zhu,L. J,; Shi, Y. F.; Tu, C. L.; Wang, R. B.; Pang, Y.; Qiu, F.; Zhu, X. Y.;Yan, D. Y.; He, L.; Jin, C. Y.; Zhu, B. S. Langmuir 2010, 26, 8875.],但是目前尚未有利用共价型动态超支化聚合物制备金属纳米晶体的报道。利用共价型动态超支化聚合物制备金属纳米晶体,能够赋予金属纳米晶体以环境响应特性。
发明内容
本发明的目的是提供一种利用含有酰腙键的共价型动态超支化聚胺作为分子纳米反应器制备金属纳米晶体的方法。
为实现上述目的,本发明采用的技术方案是,一种利用含有酰腙键的共价型动态超支化聚胺作为分子纳米反应器制备金属纳米晶体的方法,包括以下步骤:
(1)将含有酰腙键的共价型动态超支化聚胺溶解在超纯水中,制成含有酰腙键的共价型动态超支化聚胺的浓度为0.1-200g/L的超支化聚胺溶液;
(2)向步骤(1)得到的超支化聚胺溶液溶液中加入金属前体水溶液,搅拌1-24h,静置,过滤。
优选的,所述步骤(2)中超支化聚胺溶液溶液和金属前体水溶液的体积比为1-25:1。
优选的,所述金属前体水溶液为0.057-11.42 g/L的氯金酸水溶液(pH值调至大于5.5)、0.059-11.89 g/L的氯铂酸水溶液(pH值调至大于5.5)、0.023-4.64 g/L的硫酸铜水溶液或0.047-9.47 g/L的四氯钯酸钾水溶液。
所述含有酰腙键的共价型动态超支化聚胺的结构式如下:
;
n取 8-455,该结构式中的七个结构的n值可以取相同,也可以取不相同;该结构的含有酰腙键的共价型动态超支化聚胺可以采用现有技术合成,如“Construction and Application of a pH-Sensitive Nanoreactor viaa Double-Hydrophilic Multiarm Hyperbranched Polymer”(Zhu, L. J,; Shi, Y. F.; Tu, C.L.; Wang, R. B.; Pang, Y.; Qiu, F.; Zhu, X. Y.; Yan, D. Y.; He, L.; Jin, C.Y.; Zhu, B. S. Langmuir 2010, 26, 8875.)中公开的方法合成。
本发明产生的有益效果是:本发明利用含有酰腙键的共价型动态超支化聚胺作为纳米反应器,封装金属离子,继而通过内部的胺基还原金属离子,从而得到金属纳米晶体。含有酰腙键的共价型动态超支化聚胺在此既作为纳米反应器合成金属纳米晶体,又作为稳定剂对合成的金属纳米晶体起稳定作用。使用本发明的方法合成的金属纳米晶体具有尺寸分布窄和稳定性较好等特点。
附图说明
图1为实施例1-4制备的Au (a)、Cu (b)、Pd (c)和Pt(d)金属纳米晶体的紫外可见光光谱图;
图2为实施例1制备的Au金属纳米晶体透射电镜图;
图3为实施例2制备的Cu金属纳米晶体透射电镜图;
图4为实施例3制备的Pd金属纳米晶体透射电镜图;
图5为实施例4制备的Pt金属纳米晶体透射电镜图。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述,但是本领域技术人员将会理解,下列实施例仅用于说明本发明,而不应视为限制本发明的范围。以下实施例中所用的含有酰腙键的共价型动态超支化聚胺的结构式如下:
;
n取 8-455,该结构式中的七个结构的n值可以取相同,也可以取不相同;该结构的含有酰腙键的共价型动态超支化聚胺采用现有技术“Construction and Application of a pH-Sensitive Nanoreactor viaa Double-Hydrophilic Multiarm Hyperbranched Polymer”(Zhu, L. J,; Shi, Y. F.; Tu, C.L.; Wang, R. B.; Pang, Y.; Qiu, F.; Zhu, X. Y.; Yan, D. Y.; He, L.; Jin, C.Y.; Zhu, B. S. Langmuir 2010, 26, 8875.)中公开的方法合成。
实施例1
(1)在25毫升反应瓶中加入含有酰腙键的共价型动态超支化聚胺5毫克,溶解于5毫升超纯水中;
(2)取2毫升浓度为0.57g/L的氯金酸水溶液,调pH至6.5,然后加入到步骤(1)制备的超支化聚胺溶液中,磁力搅拌24小时后静置存放1h,采用220 nm水相过滤头过滤。
本实施例中制备的Au纳米晶体的紫外可见光光谱如图1中所示, Au纳米晶体的吸收峰位于529纳米。Au纳米晶体的透射电镜图如图2所示,由图2可知Au纳米晶体尺寸分布较为均一。
实施例2
(1)在25毫升反应瓶中加入含有酰腙键的共价型动态超支化聚胺5毫克,溶解于5毫升超纯水中;
(2)取2毫升浓度为0.23 g/L的硫酸铜水溶液,加入到步骤(1)制备的超支化聚胺溶液中,磁力搅拌24小时后静置存放1h,采用220 nm水相过滤头过滤。
本实施例中制备的Cu纳米晶体的透射电镜图如图3所示,由图3可知Cu纳米晶体尺寸分布较为均一。
实施例3
(1)在25毫升反应瓶中加入含有酰腙键的共价型动态超支化聚胺5毫克,溶解于5毫升超纯水中;
(2)取2毫升浓度为0.47g/L的四氯钯酸钾水溶液,加入到步骤(1)制备的超支化聚胺溶液中,磁力搅拌24小时后静置存放1h,采用220 nm水相过滤头过滤。
本实施例中制备的Pd纳米晶体的透射电镜图如图4所示,由图4可知Pd纳米晶体尺寸分布较为均一。
实施例4
(1)在25毫升反应瓶中加入含有酰腙键的共价型动态超支化聚胺5毫克,溶解于5毫升超纯水中;
(2)取2毫升浓度为0.57毫克/毫升的氯铂酸水溶液,调pH至6.5,然后加入到步骤(1)制备的超支化聚胺溶液中,磁力搅拌24小时后静置存放1h,采用220 nm水相过滤头过滤。
本实施例中制备的Pt纳米晶体的透射电镜图如图5所示,由图5可知Pt纳米晶体尺寸分布较为均一。
尽管已用具体实施例来说明和描述了本发明,然而应意识到,在不背离本发明的精神和范围的情况下可以作出许多其它的更改和修改。因此,这意味着在所附权利要求中包括属于本发明范围内的所有这些变化和修改。
Claims (4)
1.一种利用含有酰腙键的共价型动态超支化聚胺作为分子纳米反应器制备金属纳米晶体的方法,其特征在于,包括以下步骤:
(1)将含有酰腙键的共价型动态超支化聚胺溶解在超纯水中,制成含有酰腙键的共价型动态超支化聚胺的浓度为0.1-200g/L的超支化聚胺溶液;
(2)向步骤(1)得到的超支化聚胺溶液溶液中加入金属前体水溶液,搅拌1-24h,静置,过滤。
2.如权利要求1所述的利用含有酰腙键的共价型动态超支化聚胺作为分子纳米反应器制备金属纳米晶体的方法,其特征在于:所述步骤(2)中超支化聚胺溶液溶液和金属前体水溶液的体积比为1-25:1。
3.如权利要求1所述的利用含有酰腙键的共价型动态超支化聚胺作为分子纳米反应器制备金属纳米晶体的方法,其特征在于:所述金属前体水溶液为0.057-11.42 g/L的氯金酸水溶液、0.059-11.89 g/L的氯铂酸水溶液、0.023-4.64 g/L的硫酸铜水溶液或0.047-9.47g/L的四氯钯酸钾水溶液。
4.如权利要求1所述的利用含有酰腙键的共价型动态超支化聚胺作为分子纳米反应器制备金属纳米晶体的方法,其特征在于:所述含有酰腙键的共价型动态超支化聚胺的结构式如下:
。
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