CN105597714A - 一种苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的制备及作为固相萃取剂的应用 - Google Patents
一种苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的制备及作为固相萃取剂的应用 Download PDFInfo
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Abstract
本发明提供了一种本发明苯基修饰的磁性石墨烯/介孔二氧化硅（MG-MS-Ph）复合材料，主要作为固相萃取剂用于复杂的农药废水处理中，属于复合材料领域和废水处理领域。本发明先通过溶剂热反应一步合成磁性石墨烯，再通过一锅法完成苯基官能化的介孔二氧化硅对磁性石墨烯的表面修饰，从而得到具有分层的桥洞结构，大表面积，高度有序的中孔结构和更高的饱和磁化强度的苯基修饰的磁性石墨烯/介孔二氧化硅（MG-MS-Ph）复合材料。吸附试验表明，该材料对常见的农药具有较高的去除效率和平衡吸附量，而且吸附速度快、吸附效率高，因此可用于有效除去复杂废水中的农药。
Description
技术领域
本发明涉及一种新型苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的制备；本发明同时还涉及该复合材料作为固相萃取剂应用于复杂农药废水的处理，属于复合材料领域和废水处理领域。
背景技术
农药是指在农业生产中，为保障、促进植物和农作物的成长，所施用的杀虫、杀菌、杀灭有害动物（或杂草）的一类药物统称，包括有机磷酸酯（有机磷农药），氨基甲酸酯类，氯乙酰苯胺，和拟除虫菊酯类，在农业上用于防治病虫以及调节植物生长、除草等药剂。即使在很低的浓度，广泛而长期使用和处置不当都会造成严重的空气，水，土壤和农产品的污染，最终危害生态系统，包括人类。杀虫剂的高毒性归因于它们不可逆地抑制乙酰胆碱酯酶在中枢和周围神经系统的活性，从而导致乙酰胆碱递质在体内的积累，这可导致对神经系统，呼吸道，和心血管系统的损害，多器官功能衰竭和致命的后果。因此，必须开发一种简单，高灵敏度和快速的分析方法用于检测和定量测定残留农药保护环境和公众安全。然而，即使现代已有强大技术应用到农药检测，由于在复杂的环境中杀虫剂是痕量级的，杀虫剂的直接分析很困难。因此，仪器分析之前，分析物的富集和浓缩预处理是必要的。
目前，已经有许多样品预处理技术用于提取农药，如固相萃取，液液萃取，固相微萃取等。其中，固相萃取是最有效的方法之一，其操作简便，萃取时间短，良好的富集效率和有机溶剂用量少等特点。磁性固相萃取（MSPE）技术作为一种新型的萃取分离技术，使用磁性纳米材料作为吸附剂，磁性纳米颗粒分散到样品溶液中显著的增加了与分析物之间的接触界面。而且，吸附剂可以很容易地通过外部磁场分离无需繁琐的离心分离或过滤，使样品的预处理过程省时省力，更方便，且经济。相较常规固相萃取填料（活性炭（AC），多壁碳纳米管（MWNTs），单壁碳纳米管（SWNTs））相比，纳米颗粒的比表面积大，扩散距离短，只需要使用少量的吸附剂和较短的平衡时间就能实现低浓度的微量萃取，具有非常高的萃取能力和萃取效率。因此，磁性固相萃取技术在细胞分离，药物转运，酶的固定化，目标有机物的吸附-分离，环境科学，食品科学，基因组学，蛋白组学等诸多领域中都展示了极高的应用前景。然而，由于单纯的磁性纳米颗粒表面积小和容易团聚，使其吸附容量和去除效率较低。因此，对磁性纳米颗粒的表面进行适当的修饰已引起相当大的关注。
发明内容
本发明的目的是提供一种苯基修饰的磁性石墨烯/介孔二氧化硅复合材料（MG-MS-Ph）的制备方法。
本发明的另一目的是提供上述苯基修饰的磁性石墨烯/介孔二氧化硅复合材料（MG-MS-Ph）作为固相萃取剂在农药废水处理中的应用。
一、复合材料（MG-MS-Ph）的制备
本发明苯基修饰的磁性石墨烯/介孔二氧化硅复合材料（MG-MS-Ph）的制备，是先通过溶剂热反应合成磁性石墨烯，再通过一锅法完成苯基官能化的介孔二氧化硅对磁性石墨烯的表面修饰。其具体制备工艺如下：
（1）溶剂热还原反应合成磁性石墨烯：将氧化石墨烯分散于乙二醇中超声剥离0.5~1h，加入FeCl3﹒6H2O超声分散均匀后，于30~40℃搅拌反应2~3h；再加入乙酸钠和聚乙二醇，继续搅拌0.5~1h；然后转入反应釜，于180~200℃反应20~24h，乙醇洗涤，真空干燥，得磁性石墨烯（MG）。
氧化石墨烯与FeCl3·6H2O的质量比为1:3~1:5;氧化石墨烯与乙酸钠的质量比为1:10~1:30；氧化石墨烯与聚乙二醇的质量比为1:5~1:10。
（2）苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的制备：将磁性石墨烯、十六烷基三甲基溴化铵超声分散于去离子，加入氢氧化钠超声分散均匀后加热至50~60℃搅拌30~60min；然后加入乙醇、正硅酸四乙酯、苯基三乙氧基硅烷的混合物，继续搅拌10~12h；磁分离收集产物，去离子洗涤，丙酮回流去除模版剂，干燥。
十六烷基三甲基溴化铵为模板剂。磁性石墨烯与十六烷基三甲基溴化铵的质量比为1:5~1:10。
氢氧化钠的作用是提供碱性条件。氢氧化钠与十六烷基三甲基溴化铵的质量比为1:5~1:10。
正硅酸四乙酯作为硅源，正硅酸四乙酯与十六烷基三甲基溴化铵的摩尔比为60:1~62:1。
苯基三乙氧基硅烷的作用是作为硅烷偶联剂提供苯基。正硅酸四乙酯与苯基三乙氧基硅烷的摩尔比为2:1~3:1。
正硅酸四乙酯、苯基三乙氧基硅烷的加入分别采取分步加入和一步法同时加入。
所述搅拌的条件为：转速300转/分。
所述丙酮回流条件为：温度60~70℃，时间为12~24h。
干燥条件：-55~-50℃真空冷冻干燥。
本发明复合材料MG-MS-Ph的合成原理示意图见图1。首先将氧化石墨烯分散在乙二醇里加入FeCl3·6H2O，乙二醇，乙酸钠和聚乙二醇搅拌均匀后移入反应釜，一步完成GO的还原和Fe3+向Fe3O4晶体的转化；再以十六烷基三甲基溴化铵作为模板剂一锅法反应制备复合材料MG-MS-Ph。因此，具有快速、高效、便捷、成本低、环境友好及可大量制备等优点。
二、复合材料（MG-MS-Ph）的结构和性能测试
1、SEM分析
图2分别为两个实施例制备苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的扫描电镜图。从图2a可以看出出现了严重的团聚现象。从图2b可以看出，磁性复合材料具有的层状结构，Fe3O4磁性颗粒均匀分布在整个石墨烯片层的表面。
2、TEM分析
图3为苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的透射电镜图。从图3可以看出，单分散的Fe3O4微球不仅复合在石墨烯片层上而且混合了多孔二氧化硅层。虽然有一些有序孔结构被磁性石墨烯覆盖，但是几乎没有聚集或磁性石墨烯的多片层堆积，这表明介孔硅插在磁性石墨烯片层之间，有效地扩大了层间距和增强了复合材料的去除效率。
3、FT-IR分析
图4为苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的FT-IR谱图。在582cm-1处是Fe3O4的Fe-O-Fe的伸缩振动峰，说明Fe3O4纳米粒子成功的符合在石墨烯上。Si-O-Si的对称和不对称振动峰均出现在1056、791和451cm-1附近，表明在磁性石墨烯片层上有介孔二氧化硅的形成。苯基的骨架振动峰出现在1644、1489cm-1处。3439cm-1是-OH的弯曲和伸缩振动。这些数据表明，苯基基团已成功被嫁接到磁性材料上。
4、XRD分析
利用粉末X-射线衍射仪（XRD）对制备的磁性材料进行表征，其XRD谱图如图5所示。在约2θ=25°表现出强烈的衍射峰，表明在复合材料中大量的石墨烯层。2θ＝35°出现了Fe3O4的(311)晶面的吸收峰，与此同时，一些山峰约30°，43°，57°，63°均为磁性微球的特征峰。说明该方法成功制备了磁性复合材料。
6、磁性分析
采用振动样品磁强计(VSM)对四氧化三铁，磁性石墨烯（MG）和本发明制备的苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的磁性进行表征，其磁滞回线如图6所示。曲线中未见滞后环的出现，呈现S形，矫顽力为0，这说明即使经过多次修饰后的磁性材料具有超顺磁性。这对于该材料在污水吸附应用中十分有利，具有超顺磁性可以快速响应外磁场作用而聚集，在外磁场消失后，剩磁为零，从而又分散于水体中，便于吸附剂的回收再利用。苯基修饰的磁性石墨烯/介孔二氧化硅材料的磁力饱和度为25emu/g。Fe3O4的磁力饱和度为82emu/g，磁性石墨烯的磁力饱和度为43emu/g，磁力饱和度的减小进一步说明成功的制备了磁性复合材料。
7、N2吸附-脱附分析
苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的N2吸附-脱附等温线如图7所示。本发明制备的材料的N2吸附-脱附等温线属于第IV类型等温线，在约0.4P/P0时有H1型滞后环和一个明显的毛细管冷凝过程，这介孔具有非常均匀孔径的特性。从图7可以看出四氧化三铁颗粒没有堵塞介孔硅的孔隙。插图为该材料的孔径分布曲线。使用BJH方法分析表明材料孔径小于10纳米，比表面积和孔体积分别为446.5m2/g和0.32cm3/g，表明此材料具有高的比表面积和大的孔体积。
8、吸附性能测试
选择8种农药分别为阿维菌素，辛硫磷，水胺硫磷，哒螨灵，毒死蜱，敌敌畏，吡虫啉，啶虫脒作为常见农药污染物的代表，对本发明制备的磁性纳米复合材料作为固体萃取剂对农药的吸附性能进行了测试。测试的操作步骤如下：
取0.1g干燥的MG-MS-Ph分散于水中（100mg/L)，形成MG-MS-Ph悬浮液；置于振荡器中，振荡2h后，磁分离，紫外-可见分光光度计检测。分别研究了吸附平衡时间，吸附最佳温度。
吸附等温线是用来确定吸附剂的吸附行为。分别拟合了MG-MS-Ph对八种农药的Langmuir和Freundlich吸附模型如图8，9所示。Langmuir模型通常用于评价在稀溶液中在界面处固相和液相之间单分子层吸附。Freundlich模型是同时适用于单层和多层吸附。吸附等温线的结果表明MG-MS-Ph对杀虫剂吸附是单层和多层吸附，即Freundlich等温为更适于表达农药的吸附在MG-MS-Ph的表面上。
MG-MS-Ph在不同的温度时对上述八种农药吸附动力学曲线如图10所示：所有曲线随时间呈上升趋势。大部分农药大约在140分钟后达到平衡。25℃、30℃和35℃，平衡吸附量变化不大，这表明温度对吸附的影响不大。为了进一步研究MG-MS-Ph吸附过程中内在的控速步骤，分别拟合了准一级，准二级动力学模型。图11为苯基改性磁性石墨烯/介孔二氧化硅固相萃取剂对8种农药不同温度的吸附动力学模型图。其结果表明，MG-MS-Ph对农药的吸附属于准一级动力学模型。
对环境实际水样进行吸附分析见图12（为MG-MS-Ph固相萃取剂与AC，MWNTs，SWNTs在四个实际废水样品（（a）东江上游；（b）东江下游；（c）西江上游；（d）西江下游）中对8种农药去除效率（%）的对比图）。图12显示，MG-MS-Ph较固相萃取剂AC、MWNTs、SWNTs，对8种农药有更高的去除效率和平衡吸附量，而且吸附速度快、吸附效率高。原因在于：由于MG-MS-Ph的物理化学特性的改进，如比表面积大，高孔容和层次“桥梁孔径”结构，苯基官能团为吸附含苯环的农药提供充足的吸附位点。
综上所述，本发明制备的复合材料MG-MS-Ph具有分层的桥洞结构，大表面积，高度有序的中孔结构和更高的饱和磁化强度。对常见的农药具有较高的去除效率和平衡吸附量，因此可用于有效除去复杂废水中的农药。
附图说明
图1为苯基改性磁性石墨烯/介孔二氧化硅固相萃取剂的合成路线示意图。
图2为苯基改性磁性石墨烯/介孔二氧化硅固相萃取剂的扫描电镜图。
图3为苯基改性磁性石墨烯/介孔二氧化硅固相萃取剂的透射电镜图。
图4为苯基改性磁性石墨烯/介孔二氧化硅固相萃取剂的FT-IR谱图。
图5为苯基改性磁性石墨烯/介孔二氧化硅固相萃取剂的XRD谱图。
图6为四氧化三铁，磁性石墨烯和苯基改性磁性石墨烯/介孔二氧化硅的磁滞回线。
图7为苯基改性磁性石墨烯/介孔二氧化硅固相萃取剂的N2吸附-脱附等温线。
图8为苯基改性磁性石墨烯/介孔二氧化硅固相萃取剂对8种农药的Langmuir吸附等温线图。
图9为苯基改性磁性石墨烯/介孔二氧化硅固相萃取剂对8种农药的Freundlich吸附等温线图。
图10为苯基改性磁性石墨烯/介孔二氧化硅固相萃取剂对8种农药的吸附动力学图。
图11为苯基改性磁性石墨烯/介孔二氧化硅固相萃取剂对8种农药不同温度的吸附动力学模型图。
图12为苯基改性磁性石墨烯/介孔二氧化硅固相萃取剂与活性炭，多壁碳纳米管，单壁碳纳米管在四个实际废水样品（（a）东江上游；（b）东江下游；（c）西江上游；（d）西江下游）中对8种农药去除效率（%）的对比图。
具体实施方式
下面通过具体实施例对本发明苯基修饰的磁性石墨烯/介孔二氧化硅得制备及性能作进一步说明。
实施例1
磁性石墨烯（MG）的制备：称取200mg氧化石墨烯于250mL圆底烧瓶中，加入100mL乙二醇溶液超声剥离1h，加入0.6gFeCl3·6H2O超声分散均匀，40℃搅拌3h，加入7.2g乙酸钠，2g聚乙二醇，继续搅拌1h混合均匀后转入反应釜，200℃加热24h，乙醇洗涤，50℃干燥。
复合材料MG-MS-Ph的制备：称取50mg磁性石墨烯于250mL圆底烧瓶中，加入50mL去离子水超声分散，加入500mg十六烷基三甲基溴化铵（CTAB）超声分散后，加入35mg氢氧化钠超声30min，加入4mL乙醇，加热至50℃搅拌30min后，逐滴加入2.5mL正硅酸四乙酯（TEOS）/乙醇（v/v=1/4），继续搅拌30min后，加入150μLTEOS/苯基三乙氧基硅烷（PTES），（v/v=2/1）。60℃搅拌12h，磁分离收集，去离子水洗涤，70℃丙酮回流24h去除模版剂，50℃干燥。
制备的复合材料MG-MS-Ph经扫描电镜确定形貌出现严重团聚现象，如图2a所示。
实施例2
磁性石墨烯（MG）制备：同实施例1；
复合材料MG-MS-Ph的制备：称取50mg磁性石墨烯于250mL圆底烧瓶中，加入50mL去离子水超声分散，加入500mg十六烷基三甲基溴化铵（CTAB）超声分散后，加入35mg氢氧化钠超声30min，加入4mL乙醇，加热至50℃搅拌6h；加入500μL正硅酸四乙酯（TEOS），162μL苯基三乙氧基硅烷（PTES），（摩尔比2.3/1），50℃搅拌12h，磁分离收集产物，去离子水洗涤，70℃丙酮回流24h去除模版剂，冷冻干燥。
复合材料MG-MS-Ph对农药的吸附性能：对于农药阿维菌素，辛硫磷，水胺硫磷，哒螨灵，毒死蜱，敌敌畏，吡虫啉，啶虫脒的去除率可以从图12所示。
Claims (10)
1.一种苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的制备，包括以下工艺步骤：（1）溶剂热还原反应合成磁性石墨烯：将氧化石墨烯分散于乙二醇中超声剥离0.5~1h，加入FeCl3﹒6H2O超声分散均匀后，于30~40℃搅拌反应2~3h；再加入乙酸钠和聚乙二醇，继续搅拌0.5~1h；然后转入反应釜，于180~200℃反应20~24h，乙醇洗涤，真空干燥，得磁性石墨烯;
（2）苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的制备：将磁性石墨烯、十六烷基三甲基溴化铵超声分散于去离子，加入氢氧化钠超声分散均匀后加热至50~60℃搅拌30~60min；然后加入乙醇、正硅酸四乙酯、苯基三乙氧基硅烷的混合物，继续搅拌10~12h；磁分离收集产物，去离子洗涤，丙酮回流去除模版剂，-55~-50℃真空冷冻干燥即得。
2.如权利要求1所述苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的制备，其特征在于：步骤（1）中，氧化石墨烯与FeCl3·6H2O的质量比为1:3~1:5。
3.如权利要求1所述苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的制备，其特征在于：步骤（1）中，氧化石墨烯与乙酸钠的质量比为1:10~1:30；氧化石墨烯与聚乙二醇的质量比为1:5~1:10。
4.如权利要求1所述苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的制备，其特征在于：步骤（2）中，磁性石墨烯与十六烷基三甲基溴化铵的质量比为1:5~1:10。
5.如权利要求1所述苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的制备，其特征在于：步骤（2）中，氢氧化钠与十六烷基三甲基溴化铵的质量比为1:5~1:10。
6.如权利要求1所述苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的制备，其特征在于：步骤（2）中，正硅酸四乙酯与十六烷基三甲基溴化铵的摩尔比为60:1~62:1。
7.如权利要求1所述苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的制备，其特征在于：步骤（2）中，乙醇和水的体积比为1:5~1:10。
8.如权利要求1所述苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的制备，其特征在于：步骤（2）中，正硅酸四乙酯与苯基三乙氧基硅烷的摩尔比为2:1~5:1。
9.如权利要求1所述苯基修饰的磁性石墨烯/介孔二氧化硅复合材料的制备，其特征在于：步骤（2）中，所述丙酮回流条件为：温度60~70℃，时间为12~24h。
10.如权利要求1所述方法制备的苯基修饰的磁性石墨烯/介孔二氧化硅复合材料作为固相萃取剂应用于农药废水的处理中。
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