CN106986320B - 一种金属氧化物嵌入的磁性有序介孔碳复合材料及其制备方法与应用 - Google Patents
一种金属氧化物嵌入的磁性有序介孔碳复合材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种金属氧化物嵌入的磁性有序介孔碳复合材料及应用。该材料以碱催化的酚醛缩合反应合成可溶性的酚醛树脂预聚体,并以此为碳源,以两性三嵌段共聚物F127为模板,乙酰丙酮为偶合试剂,通过软模板法采用溶剂挥发自组装方式,得到有序介孔碳;利用乙二醇与柠檬酸钠的还原性,采用热溶剂法,将四氧化三铁和银纳米颗粒负载在有序介孔碳上,得到金属氧化物嵌入的磁性有序介孔碳复合材料。本发明的磁性金属氧化物嵌入有序介孔碳复合材料可以实现对硫醇化合物的选择性富集,而且可以利用材料的超顺磁性在5min内进行快速的分离。同时,利用拉曼光谱可以得到高灵敏检测且具有相当好的稳定性。
Description
技术领域
本发明涉及磁性材料领域,表面增强拉曼光谱的分析检测领域,具体地是利用软模板法通过溶剂挥发自组装形成有序介孔碳复合材料,通过热溶剂法对有序介孔碳进行磁功能化修饰,利用银纳米颗粒的表面增强拉曼特性实现对硫醇化合物的富集检测方法。
背景技术
介孔材料是指孔径介于2-50nm之间的一类多孔材料,它的孔道结构高度有序,具有很高的比表面积。有序介孔炭作为介孔材料的一种,除具有比表面积大(可达到2500m2g-1)、孔径可调、化学稳定性好、热稳定性好、良好的导电性和机械强度高等优点外,还具有孔径均一、孔道排列有序等特点,因此其在诸多方面具有很好的应用前景。有研究者将有序介孔碳材料进一步发展,将金属及金属氧化物负载在有序介孔碳上,进一步扩展介孔碳材料在催化剂载体、吸附分离、药物载体和电化学电极材料中的应用。
表面增强拉曼散射(SERS)是指当一些分子或者官能团被吸附到某些金属或半导体的特殊表面(如纳米颗粒、纳米线的表面以及具有纳米级粗糙度的表面)上时,在激发区域内它的拉曼散射信号强度会大幅增加的一种光谱现象。SERS由于具有高灵敏度、快速、丰富的光谱信息,被广泛用于研究表面、吸附界面表面状态、生物大小分子的界面取向及构型构象、结构分析等,可以有效地分析化合物在界面的吸附取向、吸附态的变化、界面信息等。
发明内容
本发明的目的在于提供一种以磁性四氧化三铁为磁性介质,同时在有序介孔碳上修饰的银纳米颗粒,利用银纳米颗粒的表面增强拉曼特性,实现对硫醇化合物的富集检测。
本发明的金属氧化物嵌入的磁性有序介孔碳复合材料的制备方法,包括下述步骤:
(1)将苯酚加热熔融,加入氢氧化钠溶液均匀混合,再滴加甲醛溶液,后升温至60~80℃反应50~70min得可溶性酚醛树脂预聚体;
(2)将可溶性酚醛树脂预聚体以酸调pH=4~6,并于40~70℃下真空干燥10~14h,离心去除氯化钠,用无水乙醇配制酚醛树脂溶液;
(3)取酚醛树脂溶液与三嵌段共聚物F127混合搅拌10~30min,得到液体待用;
(4)将步骤(3)所得液体与乙酰丙酮混合搅拌30~60min,得无色透明液体,并于表面皿中自然蒸发20~24h得液膜;
(5)将步骤(4)液膜进行固化,于100~150℃下烘干至无色透明固体;
(6)将步骤(5)无色透明固体,转移至管式炉,氮气保护下煅烧得黑色固体。
(7)将步骤(6)黑色固体、三氯化铁、无水乙酸钠、聚乙二醇和柠檬酸钠于乙二醇中混合均匀形成混合溶液;
(8)将步骤(7)中混合溶液中加入硝酸银,于聚四氟乙烯反应釜中100~250℃,下反应6~12h,即得。
优选的,上述所述金属氧化物嵌入的磁性有序介孔碳复合材料的制备方法,步骤(1)中,苯酚、氢氧化钠溶液与甲醛溶液的质量比为8~12:2~4:15~19;其中氢氧化钠溶液浓度15~25wt%,甲醛溶液浓度30~40wt%。
优选的,上述所述金属氧化物嵌入的磁性有序介孔碳复合材料的制备方法,步骤(3)中,酚醛树脂溶液与三嵌段共聚物F127的质量比为1.0~3.0:0.3~0.5,其中,酚醛树脂溶液浓度10~30wt%,三嵌段共聚物F127以无水乙醇配制,三嵌段共聚物F127与无水乙醇质量比为0.3~0.5:5.0~9.0;步骤(4)中,所述乙酰丙酮与三嵌段共聚物F127的质量比为0.01~0.03:0.3~0.5。
优选的,上述所述金属氧化物嵌入的磁性有序介孔碳复合材料的制备方法,步骤(6)中,以1~2℃·min-1升温速率将材料煅烧至600~800℃,并于该温度煅烧3~5h。
优选的,上述所述金属氧化物嵌入的磁性有序介孔碳复合材料的制备方法,步骤(7)和步骤(8)中,黑色固体、三氯化铁、无水乙酸钠、聚乙二醇、柠檬酸钠、硝酸银质量比为0.05~0.20:0.05~0.20:0.50~0.60:0.20~0.60:0.05~0.10:0.03~0.06。所述聚乙二醇分子量5000-20000。
本发明所述金属氧化物嵌入的磁性有序介孔碳复合材料在利用表面增强拉曼方面对硫醇化合物富集检测中进行应用。
上述所述应用,包括步骤:将5mg~10mg金属氧化物嵌入的磁性有序介孔碳复合材料加入含有硫醇化合物的乙醇溶液中,室温吸附2min~5min,利用磁铁将富集硫醇化合物的复合材料进行分离。利用拉曼光谱仪进行检测。
本发明以碱催化的酚醛缩合反应合成可溶性的酚醛树脂预聚体,并以此为碳源,以两性三嵌段共聚物F127为模板,乙酰丙酮为偶合试剂,通过软模板法采用溶剂挥发自组装方式,得到有序介孔碳,利用乙二醇与柠檬酸钠的还原性,采用热溶剂法,将四氧化三铁和银纳米颗粒负载在有序介孔碳上,得到金属氧化物嵌入的磁性有序介孔碳复合材料。
巯基化合物对银纳米颗粒具有很强的相互作用,其相互作用强度远高于氨基、羧基等其它基团。磁性有序介孔碳材对硫醇化合物的富集检测主要是通过巯基与银纳米颗粒的特异性结合,利用银纳米颗粒的表面增强特性,实现对硫醇化合物的分析检测。
本方法以磁性无机物四氧化三铁为磁性介质,同时以具有表面增强拉曼特性的银纳米嵌入有序介孔碳复合材料,其具有高比表面积(440-450m2·g-1),合适的孔径(4.8-5.0nm),大的孔体积(0.35-0.37cm3·g-1),同时具有良好的亲水性和超顺磁性(3.0emu·g-1),能够利用其与硫醇化合物进行特性结合,实现对硫醇化合物的选择性富集。
利用本发明制备的磁性金属氧化物嵌入有序介孔碳复合材料可以对硫醇化合物进行选择性富集,而且可以利用材料的超顺磁性在5min内进行快速的分离。同时,利用拉曼光谱可以得到高灵敏检测且具有相当好的稳定性。
附图说明
图1是磁性金属氧化物嵌入有序介孔碳复合材料的高分辨率透射电镜图。从图中可以看出该材料为有序介孔结构。
图2是磁性金属氧化物嵌入有序介孔碳复合材料的氮气吸附脱附等温曲线(A)和孔径分布曲线(B)。从图中可以看出该材料的比表面积和孔径分布。
图3是磁性金属氧化物嵌入有序介孔碳复合材料的磁滞回线图。从图中可以看出材料超顺磁性。
图4(a)是直接分析4-硝基苯硫酚固体的拉曼光谱图,图4(b)是富集4-硝基苯硫酚的磁性金属氧化物嵌入有序介孔碳复合材料的表面增强拉曼光谱图。图4(c)是4-硝基苯硫酚的饱和乙醇溶液拉曼光谱图。由图可以看出,磁性金属氧化物嵌入有序介孔碳复合材料能够富集吸附4-硝基苯硫酚,其拉曼信号得到显著增强。
图5(a)是富集4-硝基苯硫酚的磁性金属氧化物嵌入有序介孔碳复合材料的表面增强拉曼光谱图,图5(b)是放置15天后的表面增强拉曼光谱图。由图可知,4-硝基苯硫酚被富集到磁性金属氧化物嵌入有序介孔碳复合材料,放置15天后拉曼信号仍较强,吸附稳定。
具体实施方式
下述实施例是对于本发明内容的进一步说明以作为对本发明技术内容的阐释,但本发明的实质内容并不仅限于下述实施例所述,本领域的普通技术人员可以且应当知晓任何基于本发明实质精神的简单变化或替换均应属于本发明所要求的保护范围。
实施例1
(1)取10g苯酚加热至42℃至熔融,然后加入2.13g氢氧化钠溶液(20wt%)缓慢搅拌,之后,逐滴加入17.7g甲醛溶液(37wt%),继续升温,稳定加热至75℃后,继续搅拌反应60min。反应结束冷却至室温。
(2)用盐酸溶液将pH调节至6,之后,将溶液放入50℃真空干燥箱中烘12h,蒸发除去水,然后,离心除去氯化钠固体,再加入无水乙醇配置成为20wt%酚醛树脂溶液待用。
(3)将0.5g三嵌段共聚物F127溶于7.0g无水乙醇中,然后加入2.5g酚醛树脂溶液搅拌10min。
(4)向所得溶液中加入0.025g乙酰丙酮,混合溶液室温搅拌30min后,将溶液转移至表面皿,在室温下,使溶剂无水乙醇自然蒸发12h。
(5)将表面皿于烘箱中加入至100℃烘干24h,得到无色透明模块状固体。
(6)将表面皿上膜块用刮刀刮下,转移至管式炉中,在氮气保护条件下,以1℃min-1升温速率将材料煅烧至600℃,煅烧3h。在煅烧过程中,模板剂去除,形成黑色固体状的有序介孔碳材料。
(7)将0.05g有序介孔碳,0.05g三氯化铁,0.60g无水乙酸钠,0.33g聚乙二醇10000,0.06g柠檬酸钠与15mL乙二醇混合均匀。
(8)将混合溶液中加入0.05g硝酸银,于聚四氟乙烯反应釜中200℃下反应8h,即得到磁性金属氧化物嵌入有序介孔碳复合材料。
实施例2
将5mg金属氧化物嵌入的磁性有序介孔碳复合材料加入4-硝基苯硫酚的饱和乙醇溶液中,室温吸附2min,实现对硫醇化合物的选择性富集;利用磁铁可将富集4-硝基苯硫酚后的金属氧化物嵌入的磁性有序介孔碳复合材料与基质溶液进行分离。利用拉曼光谱仪进行检测结果如图4。
实施例3
将5mg金属氧化物嵌入的磁性有序介孔碳复合材料加入0.01mol/L 4-硝基苯硫酚的乙醇溶液中,室温吸附5min,实现对硫醇化合物的选择性富集;利用磁铁可将富集4-硝基苯硫酚后的金属氧化物嵌入的磁性有序介孔碳复合材料与基质溶液进行分离。利用拉曼光谱仪进行检测结果如图5所示。
Claims (8)
1.一种金属氧化物嵌入的磁性有序介孔碳复合材料的制备方法,包括下述步骤:
(1)将苯酚加热熔融,加入氢氧化钠溶液均匀混合,再滴加甲醛溶液,后升温至60~80℃反应50~70min得可溶性酚醛树脂预聚体;
(2)将可溶性酚醛树脂预聚体以酸调pH=4~6,并于40~70℃下真空干燥10~14h,离心去除氯化钠,用无水乙醇配制酚醛树脂溶液;
(3)取酚醛树脂溶液与三嵌段共聚物F127混合搅拌10~30min,得到液体待用;
(4)将步骤(3)所得液体与乙酰丙酮进行均匀混合搅拌30~60min,得无色透明液体,并于表面皿中自然蒸发12~24h得液膜;
(5)将步骤(4)液膜进行固化,于100~150℃下烘干至无色透明固体;
(6)将步骤(5)无色透明固体,转移至管式炉,氮气保护下煅烧得黑色固体;
(7)将步骤(6)黑色固体、三氯化铁、无水乙酸钠、聚乙二醇和柠檬酸钠于乙二醇中混合均匀形成混合溶液;
(8)向步骤(7)混合溶液中加入硝酸银,于聚四氟乙烯反应釜中100~250℃下反应6~12h,即得。
2.如权利要求1所述金属氧化物嵌入的磁性有序介孔碳复合材料的制备方法,其特征在于,步骤(1)中,苯酚、氢氧化钠溶液与甲醛溶液的质量比为8~12:2~4:15~19,其中氢氧化钠溶液浓度15~25wt%,甲醛溶液浓度30~40wt%。
3.如权利要求1所述金属氧化物嵌入的磁性有序介孔碳复合材料的制备方法,其特征在于,步骤(3)中,酚醛树脂溶液与三嵌段共聚物F127的质量比为1.0~3.0:0.3~0.5,酚醛树脂溶液浓度10~30wt%。
4.如权利要求1所述金属氧化物嵌入的磁性有序介孔碳复合材料的制备方法,其特征在于,步骤(6)中,以1~2℃·min-1升温速率将材料煅烧至600~800℃,并于该温度继续煅烧3~5h。
5.如权利要求1所述金属氧化物嵌入的磁性有序介孔碳复合材料的制备方法,其特征在于,步骤(7)和步骤(8)中,黑色固体、三氯化铁、无水乙酸钠、聚乙二醇、柠檬酸钠、硝酸银质量比为0.05~0.20:0.05~0.20:0.50~0.60:0.20~0.60:0.05~0.10:0.03~0.06。
6.由权利要求1-5任一项所述制备方法得到的金属氧化物嵌入的磁性有序介孔碳复合材料。
7.由权利要求1-5任一项所述制备方法得到的金属氧化物嵌入的磁性有序介孔碳复合材料在作为表面增强拉曼光谱基底对硫醇化合物富集和检测中的应用。
8.如权利要求7所述应用,其特征在于,包括步骤:将5~10mg金属氧化物嵌入的磁性有序介孔碳复合材料加入硫醇化合物的乙醇溶液中,室温吸附2~5min利用磁铁将富集硫醇化合物的复合材料进行分离。
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