CN108452808A - 一种海胆状银壳磁性纳米催化剂的制备及应用 - Google Patents
一种海胆状银壳磁性纳米催化剂的制备及应用 Download PDFInfo
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Abstract
本发明涉及了一种海胆状银壳磁性纳米催化剂的制备方法及其应用,该结构是以磁性纳米颗粒(Fe3O4)为核心,在Fe3O4颗粒表面包裹一层SiO2壳,并在SiO2壳表面生长出海胆状银外壳。制备方法包括如下步骤:首先制备Fe3O4颗粒作为磁性内核;在Fe3O4磁性颗粒表面包覆一层SiO2壳;通过正丁胺还原法在Fe3O4@SiO2磁性颗粒表面生长出一层密集的银粒子作为种子;最后在氨水提供的碱性环境中,以甲醛为还原剂,在超声条件下快速还原出海胆状银壳磁性纳米颗粒。本发明还涉及了由上述方法制备的海胆状银壳磁性纳米颗粒作为催化剂的应用,由于其分散性好、结构稳定、催化活性强,并具有强磁响应性及超顺磁性,便于循环利用,可用于催化降解水体中的多种有机污染物,例如对硝基苯酚(4‑NP)、亚甲基蓝(MB)等。
Description
技术领域
本发明属于纳米材料及催化领域,具体涉及一种海胆状银壳磁性纳米催化剂的制备方法及其应用。
背景技术
随着我国经济的快速发展,环境保护问题日益突出,工业及农业污水排放量呈现逐年增加的趋势,这些有机污染物的排放使得水资源环境严重恶化。目前,针对水体中有机污染物的处理手段主要包括吸附处理、微生物降解、凝集/絮凝/沉降、化学氧化还原、催化降解及电化学处理等。大量研究表明,金属纳米颗粒(金、银、钯、铂、镍等)在催化反应中显示出较强的催化性能。这些纳米金属催化剂具有巨大的比表面积及表面催化活性,催化降解有机污染物的效率远远优于传统金属催化剂。但这些小尺寸的金属纳米颗粒易团聚并且很难回收,在实际应用中受到很大的限制。
近年来,研究人员发现将金属纳米催化剂固定在固相载体上可以保持金属纳米颗粒的催化活性,并保护纳米颗粒在溶液中不团聚。特别是采用磁性纳米颗粒或亚微米颗粒为载体时,由于这些磁性颗粒具有超顺磁性,可以利用外加磁场进行分离和回收,撤去外加磁场后,又可恢复纳米催化剂的高度分散性,因此可以回收重复使用,使成本极大的降低。
纳米银具有强大的催化性能,且价格便宜,是一种理想的纳米催化剂。将纳米银与磁性纳米粒子结合在一起可以制备出高性能的纳米催化剂。目前,一些银壳磁核颗粒或银颗粒修饰的磁复合纳米催化剂已经被报道。但上述结构存在比表面积小、结构不稳定或者磁性弱等问题,不能完全满足实际使用的需求。因此,目前存在的问题是急需开发一种比表面积大、结构稳定、催化效能高、磁响应能力强的银壳磁性纳米催化剂。
发明内容
本发明所要解决的技术问题是针对上述现有纳米催化剂的不足,提供一种高性能的海胆状银壳磁性纳米催化剂及其制备与应用。本发明以超顺磁性的Fe3O4粒子作为核心提供了很强的磁响应能力,并在磁核表面还原出海胆状的银壳,提供了较大的比表面积和催化活性。这种海胆状银壳磁性纳米颗粒还具有结构稳定、成本低廉、可重复使用的优点,可作为一种性能优异的催化剂。
为实现上述目的,本发明采用的技术方案是:以Fe3O4颗粒为核心提供磁性能,并通过正硅酸乙酯水解在Fe3O4颗粒表面包覆上一层SiO2壳作为保护层,然后通过正丁胺还原法在Fe3O4@SiO2磁性颗粒表面生长出一层密集的银粒子作为种子,最后在氨水提供的碱性环境中,以甲醛为还原剂,在超声条件下快速还原出海胆状银壳磁性纳米颗粒。
一种海胆状银壳磁性纳米催化剂的制备,其特征在于,包括以下步骤:
1)通过改进的溶剂热法合成不同粒径的Fe3O4颗粒作为海胆状银壳磁性纳米颗粒的核心,Fe3O4颗粒的粒径范围为100纳米-500纳米;
2)在步骤1)合成的Fe3O4颗粒表面通过正硅酸乙酯水解包覆上一层SiO2壳,制备出Fe3O4@SiO2颗粒。SiO2壳的厚度范围在10纳米到100纳米。
3)在步骤2)合成的Fe3O4@SiO2颗粒表面通过正丁胺还原法生长出一层密集的银粒子作为种子,制备出种子化的Fe3O4@SiO2-Ag seed磁性颗粒。
4)将步骤3)合成的种子化的Fe3O4@SiO2-Ag seed磁性颗粒通过种子生长法合成出比表面积大、结构稳定、催化效能高、磁响应能力强的海胆状银壳磁性纳米催化剂。
其中,步骤(2)所述Fe3O4颗粒粒径范围从100纳米-500纳米,正硅酸乙酯水解的条件为超声或搅拌。
其中,步骤(3)所述中正丁胺还原法生长银种子是在无水乙醇中进行的,加入的正丁胺浓度为0.1-2毫摩尔/升。
其中,步骤(4)中所用的Fe3O4@SiO2-Ag seed磁性颗粒的浓度范围0.005-10毫克/毫升,还原剂为甲醛,催化剂为浓氨水,分散剂为聚乙烯吡咯烷酮,通过超声或搅拌快速还原出海胆状的银壳。
有益效果
本发明的方法可以简单高效地制备比表面积大、结构稳定、催化效能高、磁响应能力强的海胆状银壳磁性纳米催化剂。在该海胆状银壳磁性纳米颗粒的组成部件中,Fe3O4磁性纳米粒子作为核心提供了足够的磁性,可快速从溶液富集回收纳米催化剂,保证了纳米催化剂可以多次重复使用。而在Fe3O4磁性颗粒外包裹一层较厚的SiO2壳,避免了后续合成过程中发生磁性粒子团聚,使其具有良好的分散性。使用正丁胺还原法在Fe3O4@SiO2的表面形成均一、密集的纳米银种子,后续的海胆状银壳优先在这些细小银种子上生长。最终获得的海胆状银壳是高度分枝化的纳米银结构,具有较大的比表面积及催化活性。
本发明可以通过改变硝酸银的加入量控制海胆状银壳的形貌。在一定范围内加入硝酸银量越多,海胆状银壳的银分枝长度越长,实验证明海胆状银壳磁性纳米颗粒的形貌对催化效果有影响,较长的分枝更有利于反应的快速进行。
本发明所述的海胆状银壳磁性纳米颗粒的合成方法简便可控,所需材料皆为实验室常见的药品、试剂,价格便宜易获取;所需仪器皆为常用实验仪器,成本较低易操作。
本发明制备海胆状银壳磁性纳米颗粒可作为一种有效的催化剂,在对有机污染物的催化还原中表现出很强的催化性能,且方便回收,经过清洗后可循环使用,不会对水体造成二次污染,在水污染的处理方面具有很大的应用潜力,尤其对于环境保护领域有广阔的应用前景。
附图说明
图1为实施例1制备海胆状银壳磁性纳米颗粒的实验流程图。
图2为实施例1制备的海胆状银壳磁性纳米颗粒的透射电子显微镜(TEM)照片。
图3为实施例1制备的海胆状银壳磁性纳米颗粒的场发射扫描电子显微镜(SEM)照片。
图4为实施例1制备的海胆状银壳磁性纳米颗粒的X射线衍射(XRD)结果。
图5为实施例1制备的海胆状银壳磁性纳米颗粒的磁滞曲线结果。
图6为海胆状银壳磁性纳米颗粒催化环境中常见的有机污染物4-NP还原的UV监测图。
图7为海胆状银壳磁性纳米颗粒催化环境中常见的有机污染物MB还原的UV监测图。
具体实施方式
以下实施将结合附图对本发明做进一步说明。
实施例1
一种海胆状银壳磁性纳米催化剂的制备:
图1给出海胆状银壳磁性纳米催化剂的制备流程示意图。其具体的制备方法分为以下四步:第一步,采用改进的溶剂热法合成Fe3O4磁性颗粒。取1.35克六水合三氯化铁溶解在50毫升乙二醇中,磁力搅拌30分钟。然后加入2.7克无水醋酸钠和1克聚乙烯吡咯烷酮到该溶液中并搅拌直至反应物完全溶解。然后,将混合物转移至聚四氟乙烯内胆的高压釜(100毫升容量)中并加热到200℃反应10小时。反应结束后磁回收产物,用纯水洗涤3次,最后将产物60℃真空干燥6小时,得到Fe3O4磁性颗粒粉末备用。
第二步,合成的Fe3O4磁性颗粒表面以改进的Stober法包覆一层较厚的SiO2壳,形成单分散的Fe3O4@SiO2磁性纳米颗粒。改进的Stober法的反应体系为400毫升乙醇,20毫升纯水,15毫升浓氨水混合溶液体系,Fe3O4磁性质量为20毫克,正硅酸乙酯用量为200微升,超声反应一小时。反应完成后磁富集产物,用去离子水洗三遍,溶于10毫升无水乙醇。
第三步,将1毫升Fe3O4@SiO2磁性纳米颗粒溶于10毫升无水乙醇,加入一定量1毫摩尔/升的正丁胺,超声反应半小时,然后加入硝酸银溶液超声半小时,获得稳定的Fe3O4@SiO2-Ag seed磁性颗粒。
第四步,采用快速生长法将Fe3O4@SiO2-Ag颗粒还原成具有高度分枝化外壳的海胆状银壳磁性纳米颗粒。将上述制备的Fe3O4@SiO2-Ag颗粒投入到100毫升水溶液中,,依次加入一定量的硝酸银、80微升甲醛溶液及160微升浓氨水,继续超声5分钟后加入100毫克聚乙烯吡咯烷酮,最终获得海胆状银壳磁性纳米颗粒。
图2a、2b、2c、2d依次为Fe3O4球、Fe3O4@SiO2,Fe3O4@SiO2-Ag seed、海胆状银壳磁性纳米颗粒的透射电镜图。
图3显示的是海胆状银壳磁性纳米颗粒的扫描电镜图。
图4显示的是Fe3O4@SiO2-Ag seed颗粒和海胆状银壳磁性纳米颗粒的X射线晶型衍射结果,证明了海胆状银壳的形成。
图5显示的是Fe3O4@SiO2-Ag seed颗粒和海胆状银壳磁性纳米颗粒的磁滞曲线结果,采用本发明方法制备海胆状银壳磁性纳米颗粒的饱和磁化强度为24.2emu/g,表明海胆状银壳磁性纳米催化剂具有较好的磁响应能力及超顺磁性。
实施例2
利用环境中常见的有机污染物对硝基苯酚(4-NP)验证海胆状银壳磁性纳米催化剂的催化性能:
4-NP是常见的有机污染物,4-NP水溶液是浅黄色,在溶液中加入还原剂NaBH4后变为亮黄色,在海胆状银壳磁性纳米催化剂的作用下溶液渐渐变为无色,肉眼即可观察到反应过程的进行,也可以通过紫外分光光度计精确监测这一过程。2微克海胆状银壳磁性纳米催化剂加入到1毫升的4-NP水溶液(0.2毫摩尔/升)中,再加入1毫升新制的硼氢化钠(NaBH4)水溶液(0.1摩尔/升),测混合溶液每分钟的紫外吸收。待溶液变为无色,反应结束,4-NP被还原为对氨基苯酚(4-AP)。用外加磁铁吸附溶液中的海胆状银壳磁性纳米催化剂,水洗两次,乙醇洗两次,回收待下次使用。
催化4-NP还原的紫外吸收图谱如图6所示,400纳米处是4-NP加入NaBH4后的峰,300纳米处是4-AP的峰,随着反应的进行,400纳米处的峰逐渐降低,300纳米处的峰逐渐升高。该结果表明催化反应快速进行,海胆状银壳磁性纳米催化剂完全催化了溶液中的4-NP。
实施例3
利用环境中常见的有机污染物亚甲基蓝(MB)验证海胆状银壳磁性纳米催化剂的催化性能:
MB是常见的有机污染物,MB水溶液呈蓝色,在溶液中加入还原剂NaBH4后,在海胆状银壳磁性纳米催化剂的作用下溶液渐渐变为无色,在这个过程中,NaBH4先吸附在海胆状银壳磁性纳米催化剂表面形成金属氢化物,MB也吸附到纳米催化剂表面,被还原后解吸附。该反应的进行可以通过溶液颜色的变化进行观察,也可以通过紫外分光光度计精确监测这一过程。10微克海胆状银壳磁性纳米催化剂加入到1毫升的MB水溶液(40毫克/升)中,再加入1毫升新制的NaBH4水溶液(0.1摩尔/升),测混合溶液每分钟的紫外吸收。待溶液变为无色,反应结束,MB被还原为还原态MB。用外加磁铁吸附溶液中的海胆状银壳磁性纳米催化剂,水洗两次,乙醇洗两次,回收待下次使用。
催化MB还原的紫外吸收图谱如图所7示,664纳米处的峰即MB,随着反应的进行,664纳米处的峰逐渐降低,趋于平缓。该结果表明催化反应快速进行,海胆状银壳磁性纳米催化剂完全催化了溶液中的有机污染物MB。
上述实施例只为说明本发明的技术构思和特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能依此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (7)
1.一种海胆状银壳磁性纳米催化剂的制备及应用,其特征在于:所述海胆状银壳磁性纳米催化剂以磁性Fe3O4颗粒为核心,通过正硅酸乙酯水解在Fe3O4颗粒表面包覆上二氧化硅外壳,并通过正丁胺在二氧化硅壳表面生长出密集的银种子,最终加入高浓度的硝酸银制备出海胆状的银壳磁性纳米颗粒。所述结构中磁性纳米颗粒为Fe3O4,磁性纳米颗粒的尺寸范围从100纳米到500纳米均适用于该方法。所述海胆状银壳磁性纳米催化剂具有均一的结构,海胆状的粗糙银壳,强的磁响应性及超顺磁性,并表现出高催化活性及稳定性,可用于溶液中多种污染物的高效催化还原及循环催化使用。
2.根据权利要求1所述海胆状银壳磁性纳米催化剂的制备方法,其特征在于:具体包括如下步骤:
1)在100-500纳米的磁性Fe3O4纳米颗粒表面用正硅酸乙酯水解的方法,在超声条件下快速包覆一层二氧化硅(SiO2)壳,形成Fe3O4@SiO2磁性纳米颗粒。
2)利用正丁胺还原的方法在Fe3O4@SiO2磁性纳米粒子的表面生长出密集的微小银种子,形成Fe3O4@SiO2-Ag seed磁性颗粒。
3)将制备的Fe3O4@SiO2-Ag seed磁性颗粒分散在水溶液中,在超声条件下,按顺序加入硝酸银,甲醛,然后加入氨水。室温超声分散,待海胆状磁性银纳米颗粒生长完成后往溶液中加入聚乙烯基吡咯烷酮,继续超声5分钟以上。磁富集后用去离子水清洗3遍,得到单分散的海胆状银壳磁性颗粒。
3.根据权利要求2所述的海胆状银壳磁性纳米催化剂的制备方法,其特征在于:步骤(1)所述磁性Fe3O4纳米颗粒粒径范围从100纳米到500纳米,SiO2壳的包覆厚度在10纳米到100纳米。
4.根据权利要求2所述的海胆状银壳磁性纳米催化剂的制备方法,其特征在于:步骤(2)中所用的正丁胺还原银种子是在无水乙醇中进行的,加入的正丁胺浓度为0.1-2毫摩尔/升。
5.根据权利要求2所述的海胆状银壳磁性纳米催化剂的制备方法,其特征在于:步骤(3)中所用的Fe3O4@SiO2-Ag seed磁性粒子的浓度范围0.005-10毫克/毫升,还原剂为甲醛,催化剂为浓氨水,分散剂为聚乙烯吡咯烷酮,通过超声或搅拌快速还原出海胆状的银壳。
6.一种海胆状银壳磁性纳米颗粒,其特征在于,其是由权利要求1至5任一项的方法得到。
7.权利要求6的海胆状银壳磁性纳米颗粒作为高效、可循环利用的纳米催化剂的用途。
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