CN110898854B - 一种负载金粒子的磁性纳米空心材料及其制备方法与应用 - Google Patents
一种负载金粒子的磁性纳米空心材料及其制备方法与应用 Download PDFInfo
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- 239000010931 gold Substances 0.000 title claims abstract description 51
- 239000011796 hollow space material Substances 0.000 title claims abstract description 37
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 35
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002245 particle Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002105 nanoparticle Substances 0.000 claims abstract description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 43
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 43
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 43
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 43
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 43
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 34
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229960003638 dopamine Drugs 0.000 claims abstract description 17
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 9
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000007853 buffer solution Substances 0.000 claims description 8
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 5
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- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
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- 229920001690 polydopamine Polymers 0.000 description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 13
- 239000012467 final product Substances 0.000 description 9
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- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 5
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种负载金粒子的磁性纳米空心材料及其制备方法与应用,该磁性纳米空心材料为Au‑Fe3O4/PDA磁性纳米空心材料,壳层为PDA层,所述PDA层上附着Au纳米粒子和Fe3O4纳米粒子。制备方法具体为:利用多巴胺在SiO2纳米材料表面形成PDA层,之后在PDA层上负载Fe3O4纳米粒子并刻蚀掉SiO2纳米材料,形成磁性纳米空心材料,再在磁性纳米空心材料的PDA层上原位还原生成Au纳米粒子,即得到Au‑Fe3O4/PDA磁性纳米空心材料。与现有技术相比,本发明制备的磁性纳米金空心球具有易磁性回收、可催化降解有机染料的特性,在催化、载药释药、癌症化疗放疗等领域具有良好的应用价值,且制备合成方法简单易行,原料均可工业化生产,具有很好的推广应用价值。
Description
技术领域
本发明涉及一种高分子材料和生物医学工程领域,具体涉及一种负载金粒子的磁性纳米空心材料及其制备方法与应用。
背景技术
近年来,有关负载型纳米金催化剂(简称金催化剂)的研究和开发日益活跃,为了获得高催化活性的金催化剂,纳米金可负载在Fe3O4,Fe2O3,TiO2,Mn2O3,SiO2等多种金属氧化物、分子筛、及碳纳米管等载体上。而近年来的研究表明,不论在何种载体上,金催化剂的催化性能主要取决于它们的大小、分布、结晶度和形态。然而,由于金纳米粒子具有高活性表面能和强范德华吸引力,导致金纳米粒子具有较强的聚集成大的团簇的倾向,尺寸和形状的变化严重影响了催化降解的活性。良好的金催化剂应具有高催化活性、良好的稳定性,同时应该易于分离,但是常规的分离,例如过滤和离心,通常需要复杂的操作和大量的产物损失。为解决以上问题,科研工作者将金纳米粒子与磁性纳米粒子结合在一起。裸露的金纳米粒子和磁性纳米粒子由于范德华力的存在容易团聚,目前研究比较多的组合方式主要为:磁纳米粒子在复合材料外表面上或作为中心。在实际应用过程中,外表面上的磁性纳米粒子易从衬底掉落,导致磁性损失;磁性纳米粒子作为核心易导致磁性降低。因此,找到合适的方法来将金纳米粒子和磁性纳米粒子有机结合,提高金催化剂的催化活性及可回收利用性,是具有实际意义的课题。
聚多巴胺(PDA)可通过多巴胺(DA)在轻度碱性环境中的自聚合得到,由于其生物相容性、粘附性和生物降解特性引起广泛关注。由于在DA中存在儿茶酚和氨基,PDA可以在各种基底上的聚合过程中形成,并且可原位还原Au3+和Ag+的金属离子而不需要额外的还原剂。近年来,空心复合材料因其表面与体积比、表面渗透率优异、承载能力强、密度低、形貌可控而引起了极大的兴趣。目前已经开发了用于制备中空复合材料的多种策略,传统的模板辅助方法是制备中空PDA纳米粒子的最常用的方法,但是大多需要复杂的操作,如需要使用一些特殊试剂(例如,HF)刻蚀或需要特殊的处理方法(例如,高温)。
发明内容
本发明的目的就是为了解决上述问题而提供一种负载金粒子的磁性纳米空心材料及其制备方法与应用,获得了金纳米粒子和磁性纳米粒子同时存在的“一体化”催化剂,由于其结构及成分的特殊性,在催化、生物医学等领域将具有良好的发展前景。
本发明的目的通过以下技术方案实现:
一种负载金粒子的磁性纳米空心材料,该磁性纳米空心材料为Au-Fe3O4/PDA磁性纳米空心材料,壳层为PDA层,所述PDA层上附着Au纳米粒子和Fe3O4纳米粒子。
优选地,所述磁性纳米空心材料可包括空心球或空心棒,所述磁性纳米空心球的范围为150~1000nm,所述PDA层的厚度范围为30~150nm,所述Au纳米粒子的直径范围为3~30nm,所述Fe3O4纳米粒子的直径范围为3~20nm。其中磁性纳米空心球的尺寸可以通过调节SiO2的大小调节,SiO2越大,空心球的空心直径越大。磁性纳米空心球的饱和磁化强度随着Fe3+、Fe2+添加量的增加而升高。
一种如负载金粒子的磁性纳米空心材料的制备方法,该制备方法具体为:该制备方法具体为:利用多巴胺在SiO2纳米材料表面形成PDA层,之后在PDA层上负载Fe3O4纳米粒子并刻蚀掉SiO2纳米材料,形成磁性纳米空心材料,再在磁性纳米空心材料的PDA层上原位还原生成Au纳米粒子,即得到Au-Fe3O4/PDA磁性纳米空心材料。
优选地,所述制备方法具体包括以下步骤:
(a)将SiO2纳米材料分散在缓冲溶液中,并加入多巴胺,使SiO2纳米材料表面形成PDA层,得到PDA/SiO2纳米材料;
(b)将步骤(a)得到的PDA/SiO2纳米材料分散在溶剂A中,并加入Fe2+和Fe3+形成反应溶液,搅拌加热后利用碱性物质调节反应溶液的pH>9,之后反应生成中间产物,将中间产物洗涤干燥后得到Fe3O4/PDA纳米空心材料;
(c)将步骤(b)得到的Fe3O4/PDA纳米空心材料分散在溶剂B中,再加入Au3+进行反应,得到粗产物,将粗产物洗涤干燥后得到Au-Fe3O4/PDA纳米空心材料。
优选地,步骤(a)中的SiO2纳米材料采用以下制备方法得到:将正硅酸乙酯溶液加入到氨水溶液中,搅拌反应后,得到SiO2粗产品,将该SiO2粗产品洗涤后干燥,得到SiO2纳米材料,所述正硅酸乙酯混合液的浓度:氨水混合液的浓度=(0.75~1.8):1。
优选地,步骤(b)中所述的Fe2+来自FeCl2·H2O、FeCl2·4H2O、FeSO4、FeSO4·7H2O或FeSO4·H2O中的一种或多种,Fe3+来自FeCl3、FeCl3·6H2O、Fe2(SO4)3或Fe2(SO4)3·xH2O中的一种或多种;步骤(c)中所述的Au3+来自HAuCl4·3H2O水溶液,所述HAuCl4·3H2O水溶液的浓度范围为2~15mg/mL。
优选地,步骤(a)中所述的SiO2纳米材料、缓冲溶液和多巴胺的添加比例为(1~1.2)mg:(1~1.5)mL:(1~2)mg;步骤(b)中所述的Fe2+和Fe3+的摩尔添加比(0.5~0.7):1,所述Fe3+的摩尔量为0.2~0.6mmol。考虑到Fe2+容易氧化成Fe3+,为了保证能够形成足够的Fe3O4,Fe2+需要多添加一些。
优选地,所述缓冲溶液为Tris-HCl溶液,pH范围为8.0~9.0,所述溶剂A为去离子水或乙二醇,所述碱性物质为KOH、NaOH或氨水中的一种或多种,所述溶剂B为去离子水。
优选地,步骤(b)所述的洗涤干燥操作具体为:采用磁铁分离出中间产物后,用去离子水洗涤中间产物3~5遍,再将洗涤后的中间产物分散在去离子水中或在真空干燥箱中50~70℃干燥10~48h;
步骤(c)中所述的洗涤干燥操作具体为:采用磁铁分离出粗产物后,用去离子水洗涤粗产物3~5遍,再将洗涤后的粗产物分散在去离子水中或在真空干燥箱中50~70℃干燥10~48h。
优选地,步骤(b)中的反应在惰性气体保护下进行,搅拌时间为0~2h,加热温度为60~120℃,反应时间为1~3h。
优选地,步骤(c)中的反应温度为20~100℃,反应时间为5~120min,搅拌方式采用超声搅拌或机械搅拌进行。
一种负载金粒子的磁性纳米空心材料在催化降解有机染料方面的应用。
以制备磁性纳米空心球为例,本发明采用法制备SiO2纳米球,并用多巴胺在SiO2纳米球表面形成聚多巴胺(PDA)层,随后利用共沉淀法在碱液的作用下在PDA层负载Fe3O4纳米粒子,并刻蚀掉SiO2纳米球形成磁性纳米空心球,然后利用PDA层原位还原生成Au纳米粒子,最终得到磁性纳米金空心球,在负载Fe3O4纳米粒子的同时将SiO2刻蚀掉,形成空心结构,避免了二次刻蚀或二次热处理的复杂工艺,由于空心结构的存在提高了材料的比表面积,可实现药物负载及释放。
其中,PDA层表面能够吸附阳离子Fe2+和Fe3+,并在热碱性条件下利用共沉淀法生成Fe3O4纳米粒子,SiO2在热碱性条件下也会被刻蚀掉。但反应过程中碱液一旦加入Fe3O4纳米粒子,该Fe3O4纳米粒子便会瞬间成核并长大,而SiO2刻蚀是一个缓慢的反应过程,因此先生成了Fe3O4/PDA/SiO2纳米球,后在热碱性条件下,SiO2被刻蚀掉,形成Fe3O4/PDA空心球。由于Fe3O4纳米粒子和SiO2的生成不是同步完成的,所以不会造成PDA层的坍塌,Fe3O4纳米粒子会很好的附着在PDA层上。
该负载金粒子的磁性纳米空心球的饱和磁化强度10~45emu/g,Au纳米粒子不仅可以催化降解有机染料,还在放疗增敏等生物应用领域具有重要的应用,而超顺磁Fe3O4纳米粒子不仅可用磁铁进行回收,也可用于MRI造影。
与现有技术相比,本发明具有以下有益效果:
(1)制备得到的负载金粒子的磁性纳米空心材料具有易磁性回收、可催化降解有机染料的特性,在催化、载药释药、癌症化疗放疗等领域具有良好的应用价值。
(2)制备方法简单易行,均为常见的操作,具有很好的推广应用价值。
(3)原料来源广泛,所用的正硅酸乙酯、多巴胺、FeCl3·6H2O、FeCl2·4H2O、Fe2(SO4)3、HAuCl4·3H2O及各种溶剂等均可以工业化生产。
附图说明
图1为实施例1制备的金纳米粒子负载的磁性纳米空心球的透射电镜图;
图2为实施例1制备的金纳米粒子负载的磁性纳米空心球的磁学性能图;
图3为实施例6中有机染料的吸光度随催化降解时间的变化图。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1
将6mL正硅酸乙酯溶解在30mL乙醇中,将10mL氨水(28wt%)分散在30mL乙醇和30mL水的混合液中,将正硅酸乙酯的混合液滴加到氨水的混合液中,室温下,磁力搅拌1h。得到最终产物SiO2用乙醇和水各洗3遍,80℃的条件下干燥2h。
将以上步骤得到的100mg SiO2超声分散在100mL Tris-HCl(pH=8.0)的溶液中。将100mg的多巴胺加入到上述溶液中,在室温下磁力搅拌24h,得到PDA/SiO2纳米粒子。所得产物用去离子水水洗3~5遍,最终产物分散在去离子水中或在真空干燥箱中60℃干燥过夜,得到PDA/SiO2纳米粒子。
将得到的PDA/SiO2纳米粒子、FeCl3·6H2O(216mg)和FeCl2·4H2O(80mg)超声分散在装有300mL去离子水的三口烧瓶中。在N2保护下,在室温下剧烈搅拌30min后,将反应混合物加热到90℃,然后迅速加入20mL浓氨水(25%),混合物中立即出现黑色沉淀,反应持续1h。随后冷却至室温,产物用磁铁分离沉淀,用去离子水洗三次,然后在去离子水中再分散以供进一步使用或在真空干燥箱中60℃干燥过夜,得到Fe3O4/PDA纳米空心球。
将上述步骤得到的Fe3O4@PDA纳米空心球超声10min分散在300mL去离子水水中,后加入HAuCl4.3H2O水溶液(15mL,10mg/mL),继续超声并搅拌20min,用磁铁收集所得的Au-Fe3O4@PDA空心球,用去离子水冲洗3次以上,产物在去离子水中再分散以供进一步使用或在真空干燥箱中60℃干燥过夜,得到Au-Fe3O4/PDA纳米空心球,并对该Au-Fe3O4/PDA纳米空心球分别进行透射电镜测试和磁学性能测试,如图1所示,为Au-Fe3O4/PDA纳米空心球的投射电镜图,其中,A表示Au纳米粒子,B表示Fe3O4纳米粒子,可看到Au纳米粒子的直径范围为20-100nm,Fe3O4纳米粒子的直径范围为3-20nm,如图2所示,为磁学性能图,可看到Au-Fe3O4/PDA空心磁性纳米球的饱和磁化强度为43emu/g。
实施例2
将4mL正硅酸乙酯溶解在20mL乙醇中,将8mL氨水(28wt%)分散在20mL乙醇和20mL水的混合液中,将正硅酸乙酯的混合液滴加到氨水的混合液中,室温下,磁力搅拌2h。得到最终产物SiO2用乙醇和水各洗3遍,80℃的条件下干燥2h。
将以上步骤得到的100mg SiO2超声分散在100mL Tris-HCl(pH=8.5)的溶液中。将100mg的多巴胺加入到上述溶液中,在室温下磁力搅拌36h,得到PDA/SiO2纳米粒子。所得产物用去离子水水洗3~5遍,最终产物分散在去离子水中或在真空干燥箱中60℃干燥过夜,得到PDA/SiO2纳米粒子。
将得到的PDA/SiO2纳米粒子、FeCl3·6H2O(216mg)和FeSO4·7H2O(55.6mg)超声分散在装有100mL去离子水的三口烧瓶中。在N2保护下,在室温下剧烈搅拌30min后,将反应混合物加热到90℃,然后迅速加入15mL浓氨水(25%),混合物中立即出现黑色沉淀,反应持续1.5h。随后冷却至室温,产物用磁铁分离沉淀,用去离子水洗三次,然后在去离子水中再分散以供进一步使用或在真空干燥箱中60℃干燥过夜,得到Fe3O4/PDA纳米空心球。
将上述步骤得到的Fe3O4@PDA纳米空心球超声10min分散在200mL去离子水水中,后加入HAuCl4.3H2O水溶液(10mL,10mg/mL)),继续超声5min,用磁铁收集所得的Au-Fe3O4@PDA空心球,用去离子水冲洗3次以上,产物在去离子水中再分散以供进一步使用或在真空干燥箱中60℃干燥过夜,得到Au-Fe3O4/PDA纳米空心球。
实施例3
将5mL正硅酸乙酯溶解在25mL乙醇中,将10mL氨水(28wt%)分散在20mL乙醇和30mL水的混合液中,将正硅酸乙酯的混合液滴加到氨水的混合液中,室温下,磁力搅拌2h。得到最终产物SiO2用乙醇和水各洗3遍,80℃的条件下干燥2h。
将以上步骤得到的120mg SiO2超声分散在100mL Tris-HCl(pH=8.5)的溶液中。将120mg的多巴胺加入到上述溶液中,在室温下磁力搅拌24h,得到PDA/SiO2纳米粒子。所得产物用去离子水水洗3~5遍,最终产物分散在去离子水中或在真空干燥箱中60℃干燥过夜,得到PDA/SiO2纳米粒子。
将得到的PDA/SiO2纳米粒子、FeCl3·6H2O(108mg)和FeCl2·4H2O(39.8mg)超声分散在装有150mL去离子水的三口烧瓶中。在N2保护下,在室温下剧烈搅拌30min后,将反应混合物加热到90℃,然后迅速加入3mL NaOH(0.2M),混合物中立即出现黑色沉淀,反应持续2h。随后冷却至室温,产物用磁铁分离沉淀,用去离子水洗三次,然后在去离子水中再分散以供进一步使用或在真空干燥箱中60℃干燥过夜,得到Fe3O4/PDA纳米空心球。
将上述步骤得到的Fe3O4@PDA纳米空心球超声20min分散在100mL去离子水水中,后加入HAuCl4.3H2O水溶液(8mL,10mg/mL),继续搅拌10min,用磁铁收集所得的Au-Fe3O4@PDA空心球,用去离子水冲洗3次以上,产物在去离子水中再分散以供进一步使用或在真空干燥箱中60℃干燥过夜,得到Au-Fe3O4/PDA纳米空心球。
实施例4
将6mL正硅酸乙酯溶解在20mL乙醇中,将8mL氨水(28wt%)分散在20mL乙醇和20mL水的混合液中,将正硅酸乙酯的混合液滴加到氨水的混合液中,室温下,磁力搅拌2h。得到最终产物SiO2用乙醇和水各洗3遍,80℃的条件下干燥2h。
将以上步骤得到的100mg SiO2超声分散在100mL Tris-HCl(pH=8.5)的溶液中。将100mg的多巴胺加入到上述溶液中,在室温下磁力搅拌16h,得到PDA/SiO2纳米粒子。所得产物用去离子水水洗3~5遍,最终产物分散在去离子水中或在真空干燥箱中60℃干燥过夜,得到PDA/SiO2纳米粒子。
将得到的PDA/SiO2纳米粒子、FeCl3·6H2O(54mg)和FeCl2·4H2O(20mg)超声分散在装有100mL去离子水的三口烧瓶中。在N2保护下,在室温下剧烈搅拌30min后,将反应混合物加热到90℃,然后迅速加入10mL浓氨水(25%),混合物中立即出现黑色沉淀,反应持续1h。随后冷却至室温,产物用磁铁分离沉淀,用去离子水洗三次,然后在去离子水中再分散以供进一步使用或在真空干燥箱中60℃干燥过夜,得到Fe3O4/PDA纳米空心球。
将上述步骤得到的Fe3O4@PDA纳米空心球超声10min分散在120mL去离子水水中,10min后加入HAuCl4.3H2O水溶液(6mL,10mg/mL),继续搅拌30min,用磁铁收集所得的Au-Fe3O4@PDA空心球,用去离子水冲洗3次以上,产物在去离子水中再分散以供进一步使用或在真空干燥箱中60℃干燥过夜,得到Au-Fe3O4/PDA纳米空心球。
实施例5
将6mL正硅酸乙酯溶解在30mL乙醇中,将20mL氨水(28wt%)分散在30mL乙醇和40mL水的混合液中,将正硅酸乙酯的混合液滴加到氨水的混合液中,室温下,磁力搅拌2h。得到最终产物SiO2用乙醇和水各洗3遍,80℃的条件下干燥2h。
将以上步骤得到的100mg SiO2超声分散在150mL Tris-HCl(pH=9)的溶液中。将200mg的多巴胺加入到上述溶液中,在室温下磁力搅拌36h,得到PDA/SiO2纳米粒子。所得产物用去离子水水洗3~5遍,最终产物分散在去离子水中或在真空干燥箱中60℃干燥过夜,得到PDA/SiO2纳米粒子。
将得到的PDA/SiO2纳米粒子、FeCl3·6H2O(108mg)和FeCl2·4H2O(56mg)超声分散在装有150mL去离子水的三口烧瓶中。在N2保护下,在室温下剧烈搅拌30min后,将反应混合物加热到90℃,然后迅速加入20mL浓氨水(25%),混合物中立即出现黑色沉淀,反应持续2h。随后冷却至室温,产物用磁铁分离沉淀,用去离子水洗三次,然后在去离子水中再分散以供进一步使用或在真空干燥箱中60℃干燥过夜,得到Fe3O4/PDA纳米空心球。
将上述步骤得到的Fe3O4@PDA纳米空心球超声10min分散在150mL去离子水水中,10min后加入HAuCl4.3H2O水溶液(2mL,10mg/mL),继续超声15min,用磁铁收集所得的Au-Fe3O4@PDA空心球,用去离子水冲洗3次以上,产物在去离子水中再分散以供进一步使用或在真空干燥箱中60℃干燥过夜,得到Au-Fe3O4/PDA纳米空心球。
实施例6
一种负载金粒子的磁性纳米空心材料在催化还原4-硝基苯酚中的应用:为了催化还原4-硝基苯酚(4-NP),将新鲜制备的NaBH4水溶液(0.25mL,0.1M)、4-硝基酚水溶液(0.25mL,0.1mm)和去离子水(2.5mL)混合在石英小方格中,再加入30uL的实施例1制备的Au-Fe3O4/PDA空心纳米粒子水溶液(2.5mg mL-1)。随着反应的进行,溶液的颜色逐渐由亮黄色变为无色。每2min用紫外可见光谱(V-Vis)对反应过程进行监测,并根据紫外-可见光谱中400nm处的吸收峰强度的变化来测定催化活性。如图3所示,可看到随着时间的进行,该溶液的吸收峰强度越来越低,表明4-硝基苯酚逐渐转化。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (7)
1.一种负载金粒子的磁性纳米空心材料的制备方法,其特征在于,磁性纳米空心材料为Au-Fe3O4/PDA磁性纳米空心材料,壳层为PDA层,所述PDA层上附着Au纳米粒子和Fe3O4纳米粒子,
所述PDA层的厚度范围为30~150nm,所述Au纳米粒子的直径范围为3~30nm,所述Fe3O4纳米粒子的直径范围为3~20nm,
该制备方法具体为:利用多巴胺在SiO2纳米材料表面形成PDA层,之后在PDA层上负载Fe3O4纳米粒子并刻蚀掉SiO2纳米材料,形成磁性纳米空心材料,再在磁性纳米空心材料的PDA层上原位还原生成Au纳米粒子,即得到Au-Fe3O4/PDA磁性纳米空心材料,
所述制备方法具体包括以下步骤:
(a)将SiO2纳米材料分散在缓冲溶液中,并加入多巴胺,使SiO2纳米材料表面形成PDA层,得到PDA/SiO2纳米材料;
(b)将步骤(a)得到的PDA/SiO2纳米材料分散在溶剂A中,并加入Fe2+和Fe3+形成反应溶液,搅拌加热后利用碱性物质调节反应溶液的pH>9,之后反应生成中间产物,将中间产物洗涤干燥后得到Fe3O4/PDA纳米空心材料;
(c)将步骤(b)得到的Fe3O4/PDA纳米空心材料分散在溶剂B中,再加入Au3+进行反应,得到粗产物,将粗产物洗涤干燥后得到Au-Fe3O4/PDA纳米空心材料。
2.根据权利要求1所述的一种负载金粒子的磁性纳米空心材料的制备方法,其特征在于,步骤(b)中所述的Fe2+来自FeCl2·H2O、FeCl2·4H2O、FeSO4、FeSO4·7H2O或FeSO4·H2O中的一种或多种,Fe3+来自FeCl3、FeCl3·6H2O、Fe2(SO4)3或Fe2(SO4)3·xH2O中的一种或多种;
步骤(c)中所述的Au3+来自HAuCl4·3H2O水溶液,所述HAuCl4·3H2O水溶液的浓度范围为2~15mg/mL。
3.根据权利要求1所述的一种负载金粒子的磁性纳米空心材料的制备方法,其特征在于,步骤(a)中所述的SiO2纳米材料、缓冲溶液和多巴胺的添加比例为(1~1.2)mg:(1~1.5)mL:(1~2)mg;
步骤(b)中所述的Fe2+和Fe3+的摩尔添加比(0.5~0.7):1,所述Fe3+的摩尔量为0.2~0.6mmol。
4.根据权利要求1所述的一种负载金粒子的磁性纳米空心材料的制备方法,其特征在于,所述缓冲溶液为Tris-HCl溶液,pH范围为8.0~9.0,所述溶剂A为去离子水或乙二醇,所述碱性物质为KOH、NaOH或氨水中的一种或多种,所述溶剂B为去离子水。
5.根据权利要求1所述的一种负载金粒子的磁性纳米空心材料的制备方法,其特征在于,步骤(b)所述的洗涤干燥操作具体为:采用磁铁分离出中间产物后,用去离子水洗涤中间产物3~5遍,再将洗涤后的中间产物分散在去离子水中或在真空干燥箱中50~70℃干燥10~48h;
步骤(c)中所述的洗涤干燥操作具体为:采用磁铁分离出粗产物后,用去离子水洗涤粗产物3~5遍,再将洗涤后的粗产物分散在去离子水中或在真空干燥箱中50~70℃干燥10~48h。
6.根据权利要求1所述的一种负载金粒子的磁性纳米空心材料的制备方法,其特征在于,步骤(b)中的反应在惰性气体保护下进行,搅拌时间为0~2h,加热温度为60~120℃,反应时间为1~3h。
7.根据权利要求1所述的一种负载金粒子的磁性纳米空心材料的制备方法,其特征在于,步骤(c)中反应的反应温度为20~100℃,反应时间为5~120min。
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