CN111250727A - 一种银纳米簇的同分异构体及其制备方法与应用 - Google Patents

一种银纳米簇的同分异构体及其制备方法与应用 Download PDF

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CN111250727A
CN111250727A CN201811459032.2A CN201811459032A CN111250727A CN 111250727 A CN111250727 A CN 111250727A CN 201811459032 A CN201811459032 A CN 201811459032A CN 111250727 A CN111250727 A CN 111250727A
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林欣章
黄家辉
刘超
付雪梅
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Dalian Institute of Chemical Physics of CAS
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Abstract

本发明涉及银纳米簇同分异构体的合成技术。本发明的目的是提供一种银纳米簇的同分异构体的制备方法。其方法如下:在采用典型的尺寸刻蚀方法合成金属纳米簇的过程中,在被硼氢化钠还原之前或之后,向反应溶液中加入二价铜离子金属盐,反应5‑9小时后,获得单一尺寸银纳米簇的同分异构体。通过紫外可见吸收光谱表征同分异构体的光学性质的变化。通过培养单晶,解析纳米簇的晶体结构。此发明涉及的方法具有可行性,操作简单,易于控制。本发明合成的银纳米簇的同分异构体具有不同光学性质,可以应用于铜离子检测,也可以应用于纳米簇的结构和性质的构效关系的构建。

Description

一种银纳米簇的同分异构体及其制备方法与应用
技术领域
本发明属于银纳米簇的合成技术领域,具体涉及一种银纳米簇的同分异构体的制备方法。
背景技术
近年来,金属纳米簇作为一种新型的纳米材料备受关注并得到了广泛的研究。纳米簇一般是指尺寸小于2nm,有配体保护的、具有精确原子个数的、具有量子尺寸效应的纳米粒子。由于金属纳米簇具有独特的化学和物理性质,在催化、能源、环保、医学成像、化学传感等领域具有十分广阔的应用前景。
在金属纳米簇的研究中,获得纳米簇的晶体结构是十分重要。结构决定性质,通过获得晶体结构和性质,可以构建金属纳米簇的结构和性质的构效关系。金纳米簇的合成和应用得到最广泛的研究,而银纳米簇的合成和晶体结构的获得相对有限,包括Ag14(Chem.Commun.2013,49,300-302)、Ag16(Nanoscale.2013,5,2674-2677)、Ag21(Angew.Chem.Int.Ed.2015,54,3702-3706)、Ag23(Nat.Commun.2018,9,744)、Ag25(J.Am.Chem.Soc.2015,137,11578-11581)、Ag29(J.Am.Chem.Soc.2015,137,11970-11975)、Ag44(Nature.2013,501,399-402)、Ag67(J.Am.Chem.Soc.2016,138,14727-14732)、Ag141(J.Am.Chem.Soc.2017)、Ag136和Ag374(Nat.Commun.2016,7,12809)。银纳米簇的合成方法包括尺寸刻蚀归一化法、配体交换法等。
同分异构体,对于研究金属纳米簇的构效关系十分重要。尽管分子式相同,结构的细微差别,会导致性质的不同。但在金属纳米簇中,同分异构体并不常见,尤其在银纳米簇中。
发明内容
本发明的目的是提供一种银纳米簇的同分异构体的制备方法。
制备方法如下:在采用典型的尺寸刻蚀方法合成金属纳米簇的过程中,在被硼氢化钠还原之前或之后,向反应溶液中加入二价铜离子金属盐,反应5-9小时后,获得单一尺寸银纳米簇的同分异构体。通过紫外可见吸收光谱表征同分异构体的光学性质的变化。通过培养单晶,解析纳米簇的晶体结构。
所述制备方法,其特征在于:金属纳米簇是由配体保护的银纳米簇;金属纳米簇是银纳米簇;使用的金属盐包括氯化铜、硝酸铜、硫酸铜等所有二价铜离子金属盐;在合成金属纳米簇的过程中,二价铜离子金属盐既可以在被硼氢化钠还原之前加入,也可以在被硼氢化钠还原之后加入;反应时间为5-9小时。
本发明一方面提供一种银纳米簇的同分异构体的制备方法,所述方法包括如下步骤:
(1)将银前驱体溶于有机溶剂A中得到溶液a,将配体A溶于有机溶剂A中得到溶液b,将配体B溶于有机溶剂B中得到溶液c;所述溶液a的浓度为10mg/mL.;所述溶液b的浓度为30mg/mL.;所述溶液c的浓度为15mg/mL。
(2)将铜前驱体加入溶液a中,搅拌10-15min后,加入所述溶液b,然后搅拌25-40min后,加入溶液c,搅拌10-20min后加入平衡离子,最后加入还原剂搅拌5-9h后,经过洗涤提纯得到所述银纳米簇同分异构体。
基于以上技术方案,优选的,所述Ag前驱体为硝酸银、四氟硼化银.;所述铜前驱体为二价铜离子盐。
基于以上技术方案,优选的,所述有机溶剂A为甲醇、乙醇、正己烷等;所述有机溶剂B为二氯甲烷、四氢呋喃、甲苯等。
基于以上技术方案,优选的,在所述合成Ag纳米簇的同分异构体的过程中,铜前驱体加入的顺序为在加入还原剂之前或之后加入均可。
基于以上技术方案,优选的,所述配体A为乙硫醇;所述配体B为三苯基膦。
基于以上技术方案,优选的,所述平衡离子为四苯基溴化磷、六氟锑化钠。
基于以上技术方案,优选的,所述还原剂为硼氢化钠、六氟硼化钠、氢气。
基于以上技术方案,优选的,反应时间为5-6小时。
基于以上技术方案,优选的,所述二价铜离子盐为氯化铜、硝酸铜、硫酸铜。
本发明另一方面提供一种上述制备方法制备的银纳米簇同分异构体。
本发明再一方面提供一种上述银纳米簇同分异构体的应用,其特征在于,所述银同分异构体在铜离子检测和在纳米簇的结构和性质的构效关系的构建中的应用
有益效果
a)本发明为合成银纳米簇的同分异构体提供新的方法,此发明涉及的方法具有可行性,操作简单,易于控制。
b)本发明合成的银纳米簇的同分异构体具有不同光学性质,可以应用于铜离子检测,也可以应用于纳米簇的结构和性质的构效关系的构建。
附图说明
图1为对比例1制备的Ag23纳米簇和实施例1制备的Ag23纳米簇的同分异构体的紫外可见吸收光谱图。
图2为对比例1制备的中Ag23纳米簇和实施例1制备Ag23纳米簇的同分异构体的结构图。
具体实施方式
以下结合实例对本发明做具体的说明
对比例1
Ag23纳米簇的合成
称取24mg硝酸银于50mL圆底烧瓶中,加1mL甲醇,超声溶解;10分钟后,加入38微升苯乙硫醇溶于1mL甲醇;20分钟后,加入214mg三苯基膦溶于12mL二氯甲烷;10分钟后,加入5mg四苯基溴化磷,最后加入13mg硼氢化钠溶于1mL冰水,搅拌6小时。通过紫外可见吸收光谱表征光学性质。如图1所示,NC1对应Ag23纳米簇的紫外可见吸收光谱。旋蒸浓缩,在浓缩液和乙醇的混合液中培养单晶。通过X射线衍射测得晶体结构。如图2所示,NC1对应Ag23纳米簇的结构简图。
实施例1
Ag23纳米簇的同分异构体的合成
称取24mg硝酸银于50mL圆底烧瓶中,加1mL甲醇,超声溶解,再加入7mg二水氯化铜;10分钟后,加入38微升苯乙硫醇溶于1mL甲醇;20分钟后,加入214mg三苯基膦溶于12mL二氯甲烷;10分钟后,加入5mg四苯基溴化磷,最后加入13mg硼氢化钠溶于1mL冰水,搅拌6小时。通过紫外可见吸收光谱表征光学性质。如图1所示,NC2对应Ag23纳米簇同分异构体的紫外可见吸收光谱。旋蒸浓缩,在浓缩液和乙醇的混合液中培养单晶。通过X射线衍射测得晶体结构。如图2所示,NC2对应Ag23纳米簇的结构简图。
实施例2
Ag23纳米簇的同分异构体的合成
称取22mg硝酸银于50mL圆底烧瓶中,加1mL甲醇,超声溶解,;10分钟后,加入36微升苯乙硫醇溶于1mL甲醇;20分钟后,加入198mg三苯基膦溶于12mL二氯甲烷;10分钟后,加入4mg四苯基溴化磷,最后加入12mg硼氢化钠溶于1mL冰水,搅拌3小时。再加入9mg三水硝酸铜,搅拌5小时。通过紫外可见吸收光谱表征光学性质。旋蒸浓缩,在浓缩液和乙醇的混合液中培养单晶。通过X射线衍射测得晶体结构。

Claims (10)

1.一种银纳米簇的同分异构体的制备方法,其特征在于,所述方法包括如下步骤:
(1)将银前驱体溶于有机溶剂A中得到溶液a,将配体A溶于有机溶剂A中得到溶液b,将配体B溶于有机溶剂B中得到溶液c;所述溶液a的浓度为10mg/mL.;所述溶液b的浓度为30mg/mL.;所述溶液c的浓度为15mg/mL;
(2)将铜前驱体加入溶液a中,搅拌10-15min后,加入所述溶液b,然后搅拌25-40min后,加入溶液c,搅拌10-20min后加入平衡离子,最后加入还原剂搅拌5-9h后,经过洗涤提纯得到所述银纳米簇同分异构体。
2.根据权利要求1所述的制备方法,其特征在于:所述银前驱体为硝酸银、四氟硼化银;所述铜前驱体为二价铜离子盐。
3.根据权利要求1所述的制备方法,其特征在于,所述有机溶剂A为甲醇、乙醇、正己烷;所述有机溶剂B为二氯甲烷、四氢呋喃、甲苯。
4.根据权利要求1所述的制备方法,其特征在于,所述配体A为乙硫醇;所述配体B为三苯基膦。
5.根据权利要求1所述的制备方法,其特征在于,所述平衡离子为四苯基溴化磷、六氟锑化钠。
6.根据权利要求1所述的制备方法,其特征在于,所述还原剂为硼氢化钠、六氟硼化钠、氢气。
7.根据权利要求1所述的制备方法,其特征在于:反应时间为5-6小时。
8.根据权利要求2所述的制备方法,其特征在于,所述二价铜离子盐为氯化铜、硝酸铜、硫酸铜。
9.一种权利要求1所述制备方法制备的银纳米簇同分异构体。
10.一种权利要求9所述的银纳米簇同分异构体的应用,其特征在于,所述银同分异构体在铜离子检测中的应用。
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