CN109603848A - 一种多层核壳结构磁性纳米光催化剂的制备和应用 - Google Patents
一种多层核壳结构磁性纳米光催化剂的制备和应用 Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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Abstract
本发明公开了一种多层核壳结构磁性纳米光催化剂的制备和应用;包括如下步骤:1)水热法一步合成磁性‑银核壳结构纳米颗粒;2)用修正史托伯法在磁性‑银核壳结构纳米颗粒外包覆二氧化硅得到二氧化硅包覆的磁性‑银核壳结构纳米颗粒;3)用共沉淀法合成磁性‑银‑氧化锌核壳结构纳米光催化剂;所得多层核壳结构磁性纳米光催化剂光催化效果好,颗粒均匀,分散性好,并可通过磁力分离,具有广阔的应用前景。
Description
技术领域
本发明具体属于纳米复合材料和光催化领域。具体涉及一种多层核壳结构磁性纳米光催化剂,还涉及该多层核壳结构磁性纳米光催化剂的制备方法,还涉及该多层核壳结构磁性纳米光催化剂在染料降解方面的应用。
背景技术
偶氮染料是染料中品种和数量最多的一类,占有机染料产品总量一半以上,是染料废水的主要污染物之一,其通常拥有一个或多个偶氮键(–N=N–),并且关联芳族体系和助色团(–OH,–SO3等)特征,其生物降解性差,具有高毒性和潜在的致突变和致癌危害,因此偶氮染料的处理引起人们极大的关注。
70年代末开始利用光催化降解处理各类污染物废水的研究已有大量的报导。光催化降解法可以有效地降解多种有机污染物,并将有机物全部矿化为二氧化碳、水或毒性较小的有机物,能彻底破坏有机物,达到无害处理的要求。目前,在光催化反应所使用的半导体催化剂中,ZnO以其无毒、催化活性高、氧化能力强、稳定性好最为常用。但由于ZnO的带隙较宽(约3.2eV),只能被波长较短的紫外线激发,故它对太阳光的利用率很低。而且,由于光激发产生的电子和空穴的复合率高而导致光量子效率降低。因此,如何提高光催化剂的光谱响应、光催化量子效率及光催化反应速率等一直是半导体光催化技术研究的焦点。为克服以上缺点,人们进行了大量的研究,(1)通过改进工艺制备具有量子尺寸效应的纳米颗粒,提高其在可见光区的光活性;(2)通过改性半导体,如:表面螯合与衍生、金属离子掺杂、非金属元素掺杂改性、半导体偶合和染料敏化等,可以延长光生电子和空穴复合的时间,提高光生电子和空穴存在的寿命,进而提高光量子效率。
但光催化技术在水处理与废水处理上尚未工业化,在工程应用上存在的主要问题是悬浮体系光催化剂粉末需要分离回收,而且相当一部分催化剂流失,回收的催化剂活性也有所降低。将光催化剂固定在玻璃等材料上可以解央光催化剂的分离回收问题,但其光催化效率却明显低于悬浮体系。因此,在保证较高的光催化效率的前提下解决光催化剂的回收问题成了光催化废水处理工业化应用的关键。
发明内容
本发明的目的是克服现有技术的不足,提供一种多层核壳结构磁性纳米光催化剂的制备和应用。
磁性-银-氧化锌核壳结构纳米光催化剂中,各组分发挥了不同的作用。
一方面,本发明所述核壳结构光催化剂的核为磁性-银纳米颗粒,半导体与银表面等离子体共振产生的电磁场在等离子性纳米结构附近产生的相互作用,使得产生电子/空穴的速率上升,提高催化效率;该催化剂具有磁性,便于分离回收。
另一方面,本发明对磁性-银纳米颗粒进行二氧化硅包覆,使得其在水溶液中具有良好的分散性,并可避免纳米颗粒在极端条件下被腐蚀、降解或氧化。
另一方面,本发明的目的在于提供上述光催化剂在环境工程领域的应用。
本发明提供一种制备多层核壳结构磁性纳米光催化剂的方法,该方法包括以下步骤:
1)磁性-银核壳结构纳米颗粒的合成:在乙二醇中加入硝酸铁和硝酸银,搅拌至完全溶解后转移到高压反应釜中,160-300℃温度范围内焙烧,利用永久磁铁将带磁性物质与水相分离,用蒸馏水和醇溶液洗涤数次,烘干所得带磁性的物质为磁性-银核壳结构纳米颗粒;
2)二氧化硅包覆的磁性-银核壳结构纳米颗粒的合成:将磁性-银核壳结构纳米颗粒加入醇溶液中搅拌以分散,调节pH值至9-12,加入硅源,搅拌时间为2-4小时,搅拌方法为机械搅拌,搅拌速度500-1000r/min的条件下进行包埋反应,利用永久磁铁将带磁性物质与水相分离,用蒸馏水和醇溶液洗涤数次,烘干所得带磁性的物质为二氧化硅包覆的磁性-银核壳结构纳米颗粒;
3)磁性-银-氧化锌核壳结构纳米光催化剂的合成:二氧化硅包覆的磁性-银核壳结构纳米颗粒超声溶解于二甲基甲酰胺溶剂中,并在超声作用下,缓慢加入锌源溶液,并持续超声,再加入氢氧化钠溶液,并持续超声,将所得混合液在室温下老化,利用永久磁铁将带磁性物质与水相分离,用蒸馏水和醇溶液洗涤数次,烘干所得带磁性的物质为磁性-银-氧化锌核壳结构纳米光催化剂。
在一些具体的方式中,步骤(1)中,焙烧时间6-10小时;醇水溶液为甲醇、乙醇、异丙醇中的一种或几种,醇和水的比例为5:1-10:1。
在一些具体的方式中,步骤(2)中,pH调节剂为氢氧化钠、氨水、氢氧化钾中的一种或几种;所述的硅源为硅酸钠、正硅酸乙酯、正硅酸甲酯中的一种或几种。
在一些具体的方式中,步骤(3)中,所述的超声功率为50-100W,加入硝酸锌溶液后持续超声时间为20-40min,加入氢氧化钠溶液后持续超声时间为40-60min;所述的锌源为硝酸锌,硫酸锌,盐酸锌在的一种或几种。
在光照下,将所述光催化剂与含有偶氮染料的水溶液相接触,催化剂用量为每100g溶液加催化剂0.01-0.5g,pH值为2-8,光照强度100-3000W氙灯或者紫外灯。
所述的降解反应后的光催化剂可以被再生,其再生方法如下:将反应后的磁性光催化剂使用溶液在超声中清洗,所用溶剂为甲醇、乙腈、甲苯、二甲基甲酰胺中的一种或几种,pH在9-12,之后再氮气、氩气或氦气保护下、30-50℃下分散5-30min,得到再生的磁性光催化剂。
本发明有如下优点:
1)所获得多层核壳结构磁性纳米光催化剂具有统一尺寸、结构上有序包覆的核壳结构,该核壳结构光催化材料的单分散性良好,粒径可控。
2)所获得多层核壳结构磁性纳米光催化剂中银可发挥近场电磁作用,使得半导体与表面等离子体共振产生的电磁场在等离子性纳米结构附近产生的相互作用,使得产生电子/空穴的速率上升,提高光催化效率
3)所获得多层核壳结构磁性纳米光催化剂磁性-银纳米颗粒外包覆二氧化硅,使得其在水溶液中具有良好的分散性,并可避免纳米颗粒在极端条件下被腐蚀、降解或氧化。
4)所获得多层核壳结构磁性纳米光催化剂具有磁性,克服了传统光催化剂在光催化反应中分离步骤较多,回收过程存在质量损失的缺点。采用磁性材料载体后,在外加磁场的作用下吸附剂可方便地回收,操作简便,回收率与再生率高,极大方便了光催化反应中光催化剂回收。
附图说明
图1为本发现制备多层核壳结构磁性纳米光催化剂的反应流程图与实例1中所制备得到的磁性-银纳米颗粒、二氧化硅包覆的磁性-银核壳结构纳米颗粒、磁性-银-氧化锌核壳结构纳米光催化剂的投射电镜图。
具体实施方式
下面结合具体实施例对本发明作进一步详细描述,但是本发明不限于所给的例子。所述方法如无特别说明均为常规方法。所述原材料如无特别说明均能从公开商业途径而得。
实施例1:
①Ag@Fe3O4纳米颗粒的合成:在乙二醇(40mL)中加入Fe(NO3)·9H2O(4mmol),NaAc(35mmol)和AgNO3(0.59mmol),磁力搅拌至完全溶解后转移到聚四氟乙烯内里不锈钢高压反应釜中,200℃下反应8小时。反应结束后用乙醇洗涤数次并磁力收集,60℃真空烘箱中过夜干燥。
②Ag@Fe3O4@SiO2纳米颗粒的合成:将38mL乙醇和6mL去离子水混合,加入0.1gAg@Fe3O4纳米颗粒,机械搅拌,加入2mL氨水,再向该混合液中滴加0.38mL TEOS,搅拌3小时,将所得产物用乙醇洗涤数次并磁力收集,50℃真空烘箱中过夜干燥。
③Ag@Fe3O4@SiO2@ZnO纳米颗粒的合成:将ZnNO3×6H2O(0.3g)溶解于DMF(50mL)中,NaOH(0.04g)溶解于去离子水(2mL)中,Ag@Fe3O4@SiO2(0.5g)超声溶解于DMF(50mL)中。在超声下,将ZnNO3×6H2O溶液缓慢加入Ag@Fe3O4@SiO2溶液中,并持续超声30min,再加入NaOH溶液,并持续超声1h。将所得混合液在室温下老化1天。所得产物用乙醇洗涤数次并磁力收集,60℃真空烘箱中干燥6h。
④催化剂的性能评价:在100W紫外灯光照下,将所述光催化剂与10mg/L橙黄G的水溶液相接触,催化剂用量为每100g溶液加催化剂0.01g,pH值为7。反应一段时间后,取上清液,采用紫外分光光度计测定反应前后橙黄G溶液的浓度。
实施例2:
同实施例1,与实施例1不同之处在于步骤1)中高压釜反应温度为160℃。
实施例3:
同实施例1,与实施例1不同之处在于步骤1)中高压釜反应温度为240℃。
实施例4:
同实施例1,与实施例1不同之处在于步骤4)中pH值为3。
上述实施例用来解释说明本发明,而不是对本发明进行限制,在本发明的精神和权利要求的保护范围内,对本发明做出的任何修改和改变,都归入本发明的保护范围。
Claims (8)
1.一种多层核壳结构磁性纳米光催化剂的制备和应用,其特征在于包括如下步骤:
①磁性-银核壳结构纳米颗粒的合成:在乙二醇中加入硝酸铁和硝酸银,搅拌至完全溶解后转移到高压反应釜中,160-300℃温度范围内焙烧,利用永久磁铁将带磁性物质与水相分离,用蒸馏水和醇溶液洗涤数次,烘干所得带磁性的物质为磁性-银核壳结构纳米颗粒;
②二氧化硅包覆的磁性-银核壳结构纳米颗粒的合成:将磁性-银核壳结构纳米颗粒加入醇溶液中搅拌以分散,调节pH值至9-12,加入硅源,搅拌时间为2-4小时,搅拌方法为机械搅拌,搅拌速度500-1000r/min的条件下进行包埋反应,利用永久磁铁将带磁性物质与水相分离,用蒸馏水和醇溶液洗涤数次,烘干所得带磁性的物质为二氧化硅包覆的磁性-银核壳结构纳米颗粒;
③磁性-银-氧化锌核壳结构纳米光催化剂的合成:二氧化硅包覆的磁性-银核壳结构纳米颗粒超声溶解于二甲基甲酰胺溶剂中,并在超声作用下,缓慢加入锌源溶液,并持续超声,再加入氢氧化钠溶液,并持续超声,将所得混合液在室温下老化,利用永久磁铁将带磁性物质与水相分离,用蒸馏水和醇溶液洗涤数次,烘干所得带磁性的物质为磁性-银-氧化锌核壳结构纳米光催化剂。
2.根据权利要求1所述的多层核壳结构磁性纳米光催化剂的制备和应用,其特征在于:步骤(1)中,焙烧时间6-10小时;醇水溶液为甲醇、乙醇、异丙醇中的一种或几种,醇和水的比例为5:1-10:1。
3.根据权利要求1所述的多层核壳结构磁性纳米光催化剂的制备和应用,其特征在于:步骤(2)中,pH调节剂为氢氧化钠、氨水、氢氧化钾中的一种或几种;所述的硅源为硅酸钠、正硅酸乙酯、正硅酸甲酯中的一种或几种。
4.根据权利要求1所述的多层核壳结构磁性纳米光催化剂的制备和应用,其特征在于:步骤(3)中,所述的超声功率为50-100W,加入硝酸锌溶液后持续超声时间为20-40min,加入氢氧化钠溶液后持续超声时间为40-60min;所述的锌源为硝酸锌,硫酸锌,盐酸锌在的一种或几种。
5.一种权利要求1-4任一所述的多层核壳结构磁性纳米光催化剂的制备和应用,其特征在于:该多层核壳结构磁性纳米高效光催化剂用于光催化降解染料。
6.根据权利要求5所述的多层核壳结构磁性纳米光催化剂的制备和应用,其中所述的染料包括:偶氮基两端连接芳基的偶氮染料。
7.根据权利要求5所述的多层核壳结构磁性纳米光催化剂的制备和应用,其特征在于:在光照下,将所述光催化剂与含有偶氮染料的水溶液相接触,催化剂用量为每100g溶液加催化剂0.01-0.5g,pH值为2-8,光照强度100-3000W氙灯或者紫外灯。
8.根据权利要求5所述的多层核壳结构磁性纳米光催化剂的制备和应用,其特征在于:所述的降解反应后的光催化剂可以被再生,其再生方法如下:将反应后的磁性光催化剂使用溶液在超声中清洗,所用溶剂为甲醇、乙腈、甲苯、二甲基甲酰胺中的一种或几种,pH在9-12,之后再氮气、氩气或氦气保护下、30-50℃下分散5-30min,得到再生的磁性光催化剂。
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