CN107988589B - 一种纳米金属复合物及其制备方法 - Google Patents

一种纳米金属复合物及其制备方法 Download PDF

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CN107988589B
CN107988589B CN201711183376.0A CN201711183376A CN107988589B CN 107988589 B CN107988589 B CN 107988589B CN 201711183376 A CN201711183376 A CN 201711183376A CN 107988589 B CN107988589 B CN 107988589B
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周学昌
杨梦嫣
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Abstract

本发明公开了一种纳米金属复合物及其制备方法,其中,方法包括步骤:提供一基材,所述基材表面接有亲水基团;采用硅烷偶联剂对所述基材进行表面修饰,得到表面硅烷偶联剂修饰的基材;将所述表面硅烷偶联剂修饰的基材、引发剂和含乙烯基的聚合物单体混合,使所述含乙烯基的聚合物单体发生聚合反应并在表面硅烷偶联剂修饰的基材上长出聚合物刷,得到自由基聚合后的基材;通过离子交换向所述自由基聚合后的基材置换上PdCl4 2‑,然后置于金属镀液中进行金属无电沉积,即得到纳米金属复合物。本发明解决了现有技术中纳米金属在实际使用时需在表面包覆表面活性剂导致其反应活性不高,以及纳米金属无法有效回收利用的问题。

Description

一种纳米金属复合物及其制备方法
技术领域
本发明涉及纳米材料领域,尤其涉及一种纳米金属复合物及其制备方法。
背景技术
纳米金属是三维空间中至少有一维处于纳米尺度或由它们作为基本单元构成的金属材料,其具有许多其本体普通材料所没有的物理性能和化学性能,例如黑金能够特异性地吸收太阳光,纳米金、纳米银具有显著的拉曼增强性能,这些特性使得纳米金属在光、电、磁、催化剂、传感、生物医药等方面具有广泛的应用前景。以往纳米金属大都以胶体溶液的形式直接利用,以这种方式利用纳米金属时,纳米金属回收困难,无法进行重复利用,而且因为纳米金属的尺寸过小,易团聚,需要在纳米金属表面包覆表面活性剂,以稳定纳米金属,防止它们团聚,表面活性剂的存在使得纳米金属的各项活性受到严重影响。针对纳米金属无法回收利用的问题,现有研究采用吸水性良好的材料如棉花等基材直接吸取纳米金属胶体溶液的方法来固定纳米金属,此法虽然能够在一定程度上对纳米金属进行回收利用,但是仍需在纳米金属表面包覆表面活性剂,纳米金属的活性仍受影响,而且纳米金属与基材的结合不牢,纳米金属易脱落,并不能实现真正意义上的纳米金属回收利用。
因此,现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足,本发明的目的在于提供一种纳米金属复合物及其制备方法,旨在解决现有技术中纳米金属在使用时需在其表面包覆表面活性剂导致其活性不佳,以及纳米金属无法有效回收利用的问题。
本发明的技术方案如下:
一种纳米金属复合物的制备方法,其中,包括步骤:
提供一载体,所述基材表面接有亲水基团;
采用硅烷偶联剂对所述基材进行表面修饰,得到表面硅烷偶联剂修饰的基材;
将所述表面硅烷偶联剂修饰的基材、引发剂和含乙烯基的聚合物单体混合,使所述含乙烯基的聚合物单体发生聚合反应并在表面硅烷偶联剂修饰的基材上长出聚合物刷,得到自由基聚合后的基材;
通过离子交换向所述自由基聚合后的基材置换上PdCl4 2-,然后置于金属镀液中进行金属无电沉积,即得到纳米金属复合物。
所述的纳米金属复合物的制备方法,其中,还包括步骤:
先对所述基材进行预处理,以去除表面杂质。
所述的纳米金属复合物的制备方法,其中,所述硅烷偶联剂为乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、γ-胺基丙基三甲氧基硅烷或γ-胺基丙基三乙氧基硅烷。
所述的纳米金属复合物的制备方法,其中,所述含乙烯基的聚合物单体为丙烯酸酯、甲基丙烯酸酯、乙烯基醚、马来酸酐酯、丁二烯及其衍生物或丙烯酰胺。
所述的纳米金属复合物的制备方法,其中,所述引发剂为KPS。
所述的纳米金属复合物的制备方法,其中,采用等离子体处理或浓酸处理的方式在基材表面接上亲水基团。
所述的纳米金属复合物的制备方法,其中,所述步骤使含乙烯基的聚合物单体发生聚合反应并在表面硅烷偶联剂修饰的基材上长出聚合物刷的具体反应温度为50-100℃,反应时间为1-180分钟。
所述的纳米金属复合物的制备方法,其中,所述通过离子交换向所述自由基聚合后的基材置换上PdCl4 2-的具体步骤为:
将所述自由基聚合后的硅橡胶基材浸泡在离子浓度为0.001-0.01mol/L的PdCl4 2-水溶液中,进行离子交换反应1-60分钟。
所述的纳米金属复合物的制备方法,其中,所述基材为硅橡胶海绵。
一种纳米金属复合物,其中,所述纳米金属复合物由如上所述的方法制备而成。
有益效果:本发明通过预先在基材表面接上亲水基团,然后进行硅烷偶联剂修饰,再在引发剂的作用下与含乙烯基的聚合物单体聚合,得到表面带有聚合物刷的基材,再通过离子交换在基材表面沉积具有催化性的PdCl4 2-,最后通过PdCl4 2-离子的作用进行金属无电沉积,得到纳米金属复合物,制备过程简单,对设备要求低,无毒无害,对环境污染小,且所制备得到的纳米金属复合物中,纳米金属颗粒的表面没有表面活性剂的覆盖,其催化活性及其它各项特性没有损失,并且纳米金属颗粒均匀且稳定地分布在基材的内部和表面,不易脱落,使用方便,能够反复利用,解决了现有技术中纳米金属在利用时需在其表面包覆表面活性剂导致其活性不佳,以及纳米金属无法有效回收利用。
附图说明
图1为本发明所述纳米金属复合物制备方法的较佳实施例流程图。
图2为本发明实施例1中所制备的纳米金属复合物的扫描电镜图。
图3为本发明实施例1~3中所使用的硅橡胶海绵的扫描电电镜图。
图4为本发明实施例2中所制备的纳米金属复合物的扫描电镜图。
具体实施方式
本发明提供一种纳米金属复合物及其制备方法,为使本发明的目的、技术方案及效果更加清楚、明确,以下对本发明进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
本发明所述的纳米金属复合物的制备方法,如图1所示,包括步骤:
S1、提供一基材,并在所述基材表面接上亲水基团;
S2、采用硅烷偶联剂对所述基材进行表面修饰,得到表面硅烷偶联剂修饰的基材;
S3、将所述表面硅烷偶联剂修饰的基材、引发剂和含乙烯基的聚合物单体混合,使所述含乙烯基的聚合物单体发生聚合反应并在表面硅烷偶联剂修饰的基材上长出聚合物刷,得到自由基聚合后的基材;
S4、通过离子交换向所述自由基聚合后的基材置换上PdCl4 2-,然后置于金属镀液中进行金属无电沉积,即得到纳米金属复合物。
本发明所制备的纳米金属复合物也即一种负载在基材上是纳米金属催化剂,预先在基材表面接上亲水基团,通过该亲水基团能够更好地进行硅烷偶联剂修饰反应,再在引发剂的作用下与含乙烯基的聚合物单体聚合,得到表面带有聚合物刷的基材,再通过离子交换在基材表面沉积具有催化性的PdCl4 2-,最后通过PdCl4 2-离子的作用进行金属无电沉积,得到纳米金属复合物。
本发明所述基材可以为海绵、滤纸、棉花、氧化铝等,所述海绵优选为具有三维分层结构的硅橡胶海绵,具有更大比表面积,其内部和表面均能够负载纳米金属颗粒,从而提高纳米金属负载量。
较佳地,在所述步骤S1之前,还包括步骤:
预先对所述基材进行预处理,以去除表面杂质。具体是将基材用乙醇在超声清洗机里清洗1-20分钟,也可以用浓碱、浓酸或强氧化溶液如铬酸洗液等进行清洗,同样能够达到清除表面杂质的效果;然后将清洗后的海绵放入鼓风烘箱烘干。
所述步骤S1中,将烘干的基材放入等离子体清洗机里处理1-20分钟,或者用浓硝酸或铬酸洗液处理,从而在基材的表面接上羟基等亲水基团,同时可以改善基底表面的粗糙度。亲水基团的加入能够促进基材与后续硅烷偶联剂的反应,进而加强与含乙烯基的聚合物单体发生自由基反应,从而在基材表面长出能够大量沉积纳米金属粒子的聚合物刷。
所述步骤S2中,将经过亲水处理的基材浸泡在含双键的硅烷偶联剂的溶液中1-120分钟,其中,含双键的硅烷偶联剂的体积百分比为1-10%,然后用去离子水冲洗干净,即得到表面硅烷偶联剂修饰的基材。较佳地,所述硅烷偶联剂为乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、γ-胺基丙基三甲氧基硅烷或γ-胺基丙基三乙氧基硅烷。
所述步骤S3中,将表面硅烷偶联剂修饰的基材浸泡在含乙烯基的聚合物单体溶液中,其中,含乙烯基的聚合物单体的体积百分比为1~20%,同时加入KPS等引发剂,50-100℃温度作用下反应1-180分钟,所述含乙烯基的聚合物单体发生聚合反应并在表面硅烷偶联剂修饰的基材上长出聚合物刷,即得到自由基聚合后的基材。反应温度太低,反应速率太慢,耗时太长,温度太高的话,会造成含乙烯基的聚合物单体自聚,生成大量均聚物。较佳地,反应时间为60~120分钟,反应时间太短,未能充分反应生成聚合物刷,而反应时间太长的话,会增加发生副反应的机率,影响产物质量。
较佳地,所述含乙烯基的聚合物单体为丙烯酸酯、甲基丙烯酸酯、乙烯基醚、马来酸酐酯、丁二烯及其衍生物或丙烯酰胺,上述含乙烯基的聚合物单体能够快速地与表面硅烷偶联剂修饰的基材发生自由基聚合反应,并在海绵表面长出大量聚合物刷。
所述步骤S4中,通过离子交换向所述自由基聚合后的基材置换上PdCl4 2-的具体步骤为:
将所述自由基聚合后的基材浸泡在离子浓度为0.001-0.01mol/L的PdCl4 2-水溶液中,进行离子交换反应1-60分钟,即能够在基材表面附着上PdCl4 2-,再将表面附着有PdCl4 2-的基材置于金属镀液中进行金属无电沉积,金属镀液中的金属离子在PdCl4 2-的催化作用下,即得到纳米金属复合物。所制备的纳米金属复合物中,直接牢固沉积在海绵内部及间隙、孔洞等处,不易脱落,而且纳米金属表面没有表面活性剂的包裹束缚,因而其催化活性剂各项特性均没有损失,催化活性高,其中,金属无电沉积方法步骤简单,对设备要求低,无毒无害,对环境污染小。
较佳地,所述金属镀液为金镀液,所制备的黑色的纳米金颗粒除了具有一般纳米金的特性外,还有优异的光学特性,也即使得纳米金海绵具有优异的光学特性。
基于上述方法,本发明还提供了一种纳米金属复合物,其中,所述纳米金属复合物由如上所述的方法制备而成。
下面通过实施例对本发明进行详细说明。
实施例1
将尺寸为1cm×1cm×1cm的硅橡胶海绵方块用乙醇在超声清洗机里清洗10分钟,然后放入45℃鼓风烘箱中干燥;
将干燥后的硅橡胶海绵方块放入等离子体清洗机里处理10分钟,然后置于体积百分比为10%乙烯基三乙氧基硅烷溶液中,处理反应60分钟后,取出固体并用去离子水冲洗干净,得到表面硅烷偶联剂修饰的硅橡胶海绵;
将表面硅烷偶联剂修饰的硅橡胶海绵置于体积百分比为10%的丙烯酸酯溶液中,同时加入引发剂KPS,60℃反应120分钟,得到自由基聚合后的硅橡胶海绵;
将自由基聚合后的硅橡胶海绵置于离子浓度为0.001-0.01mol/L的PdCl4 2-溶液中进行离子交换30分钟后取出并用去离子水冲洗干净;
将经离子交换处理的硅橡胶海绵置于金镀液中进行金属无电沉积,即得到纳米金属复合物。
将上述制备的纳米金属复合物及硅橡胶海绵进行扫描电镜表征,其结果分布如图2和3所示,通过图2和图3对比可知,所制备的纳米金硅橡胶海绵上牢牢负载有大量纳米金。
实施例2
将尺寸为1cm×1cm×1cm的硅橡胶海绵方块用乙醇在超声清洗机里清洗20分钟,然后放入45℃鼓风烘箱中干燥;
将干燥后的硅橡胶海绵方块放入等离子体清洗机里处理20分钟,然后置于体积百分比为5%乙烯基三甲氧基硅烷溶液中,处理反应120分钟后,取出固体并用去离子水冲洗干净,得到表面硅烷偶联剂修饰的硅橡胶海绵;
将表面硅烷偶联剂修饰的硅橡胶海绵置于体积百分比为10%的丙烯酰胺溶液中,同时加入引发剂KPS,100℃反应180分钟,得到自由基聚合后的硅橡胶海绵;
将自由基聚合后的硅橡胶海绵置于离子浓度为0.001-0.01mol/L的PdCl4 2-溶液中进行离子交换60分钟后取出并用去离子水冲洗干净;
将经离子交换处理的硅橡胶海绵置于金镀液中进行金属无电沉积,即得到纳米金属复合物。
将上述制备的纳米金属复合物进行扫描电镜表征,其结果分布如图4所示,通过图3和图4对比可知,所制备的纳米金属复合物上牢牢负载有大量纳米金。
实施例3
将尺寸为1cm×1cm×1cm的硅橡胶海绵方块用乙醇在超声清洗机里清洗1分钟,然后放入45℃鼓风烘箱中干燥;
将干燥后的硅橡胶海绵方块放入等离子体清洗机里处理1分钟,然后置于体积百分比为1%γ-胺基丙基三甲氧基硅烷溶液中,处理反应30分钟后,取出固体并用去离子水冲洗干净,得到表面硅烷偶联剂修饰的硅橡胶海绵;
将表面硅烷偶联剂修饰的硅橡胶海绵置于体积百分比为10%的丁二烯溶液中,同时加入引发剂KPS,50℃反应30分钟,得到自由基聚合后的硅橡胶海绵;
将自由基聚合后的硅橡胶海绵置于离子浓度为0.001-0.01mol/L的PdCl4 2-溶液中进行离子交换10分钟后取出并用去离子水冲洗干净;
将经离子交换处理的硅橡胶海绵置于镍镀液中进行金属无电沉积,即得到纳米金属复合物。
所制备的纳米金属复合物经反复压缩和拉伸后,未见有明显的金属脱落,说明纳米镍牢固地负载在硅橡胶海绵上。
综上所述,本发明通过预先在基材表面接上亲水基团,然后进行硅烷偶联剂修饰,再在引发剂的作用下与含乙烯基的聚合物单体聚合,得到表面带有聚合物刷的基材,再通过离子交换向基材表面置换上具有催化性的PdCl4 2-,最后通过PdCl4 2-离子的作用进行金属无电沉积,得到纳米金属复合物,制备过程简单,对设备要求低,无毒无害,对环境污染小,且所制备得到的纳米金属复合物中,纳米金属颗粒的表面没有表面活性剂的覆盖,其催化活性及其它各项特性没有损失,并且纳米金属颗粒均匀且稳定地分布在基材的内部和表面,不易脱落,可以重复利用,解决了现有技术在利用纳米金属时需在其表面包覆表面活性剂导致其活性不佳,以及纳米金属无法有效回收利用的问题。
应当理解的是,本发明的应用不限于上述的举例,对本领域普通技术人员来说,可以根据上述说明加以改进或变换,所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (7)

1.一种纳米金属复合物的制备方法,其特征在于,包括步骤:
提供一基材,所述基材表面接有亲水基团;
采用硅烷偶联剂对所述基材进行表面修饰,得到表面硅烷偶联剂修饰的基材;
将所述表面硅烷偶联剂修饰的基材、引发剂和含乙烯基的聚合物单体混合,使所述含乙烯基的聚合物单体发生聚合反应并在表面硅烷偶联剂修饰的基材上长出聚合物刷,得到自由基聚合后的基材;
通过离子交换向所述自由基聚合后的基材置换上PdCl4 2-,然后置于金属镀液中进行金属无电沉积,即得到纳米金属复合物;
所述基材为硅橡胶海绵;所述金属镀液为金镀液,所述纳米金属复合物中纳米金颗粒为黑色;
所述步骤使含乙烯基的聚合物单体发生聚合反应并在表面硅烷偶联剂修饰的基材上长出聚合物刷的具体反应温度为50-100℃,反应时间为1-180分钟;
所述通过离子交换向所述自由基聚合后的海绵置换上PdCl4 2-的具体步骤为:
将所述自由基聚合后的基材浸泡在离子浓度为0.001-0.01mol/L的PdCl4 2-水溶液中,进行离子交换反应1-60分钟。
2.根据权利要求1所述的纳米金属复合物的制备方法,其特征在于,还包括步骤:
先对所述基材进行预处理,以去除表面杂质。
3.根据权利要求1所述的纳米金属复合物的制备方法,其特征在于,所述硅烷偶联剂为乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、γ-胺基丙基三甲氧基硅烷或γ-胺基丙基三乙氧基硅烷。
4.根据权利要求1所述的纳米金属复合物的制备方法,其特征在于,所述含乙烯基的聚合物单体为丙烯酸酯、甲基丙烯酸酯、乙烯基醚、马来酸酐酯、丁二烯及其衍生物或丙烯酰胺。
5.根据权利要求1所述的纳米金属复合物的制备方法,其特征在于,所述引发剂为KPS。
6.根据权利要求1所述的纳米金属复合物的制备方法,其特征在于,采用等离子体处理或浓酸处理的方式在基材表面接上亲水基团。
7.一种纳米金属复合物,其特征在于,所述纳米金属复合物由如权利要求1~6任一所述的方法制备而成。
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