CN105618015A - 一种三维介孔碳复合材料的制备及其作为固相微萃取纤维涂层材料的应用 - Google Patents
一种三维介孔碳复合材料的制备及其作为固相微萃取纤维涂层材料的应用 Download PDFInfo
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Abstract
本发明提供了一种三维介孔碳复合材料，是以介孔硅为模板，蔗糖为碳源，乙醇为介质，在加热条件下不断搅拌使介孔硅的空隙被蔗糖完全填满，冷冻干燥；然后在氮气保护下碳化，用NaOH除去模板介孔硅即得。该介孔碳复合材料具有蜂窝状的形貌和多孔结构，和很好的吸附能。以其为涂层材料制备的固相微萃取纤维具有良好的萃取性能和效率，对环境水样中的溴代阻燃剂具有很好的富集分离效率，因此可用于富集分离环境中的溴代阻燃剂。
Description
技术领域
本发明属于新材料技术领域，涉及一种三维介孔碳复合材料的制备；本发明同时还涉及以该三维介孔碳复合材料为涂层材料制备的固相微萃取纤维，主要用于富集分离环境中溴代阻燃剂。
背景技术
固相微萃取(Solid-phaseMicroextraction,SPME)作为一种新型的萃取分离技术，具有溶剂耗量少，高效，富集能力强，便于与仪器联用实现自动化在线分析等优点，使得样品前处理的时间很大程度上被缩短，故其被广泛应用于环境监测，食品安全，医药和生物等领域，成为痕量物质分离检测分析不可或缺的工具。
SPME技术的核心是SPME萃取纤维头，目前已存在的一些商品化萃取纤维，如PDMS、PA等，大都采用石英丝为载体，高聚物为涂层，这使得此种纤维存在易碎、在有机溶剂中易溶胀、涂层容易脱落和价格昂贵等一些缺陷。因此，制备一种机械强度好、萃取效率高、抗溶剂性好且廉价的新型固相微萃取纤维势在必行。
随着社会的发展，溴代阻燃剂逐渐地被用于工业生产当中，在为推动经济发展做出巨大贡献的同时，由于其在使用和废物处置的阶段会不同程度地释放到环境中，使得其在环境和生物体内的含量迅速增多。研究表明，溴代阻燃剂能够对人类健康和环境造成持久性的危害。由于目前关于检测和富集分离环境样品中溴代阻燃剂的研究报道很少，故建立一种能够有效的富集分离环境中溴代阻燃剂的固相微萃取纤维涂层材料显得尤为重要。
发明内容
本发明的目的是提供一种三维介孔碳复合材料的制备方法；
本发明的另一方法是提供一种上述制备的三维介孔碳复合材料作为固相微萃取纤维涂层材料的应用。
一、三维明介孔碳复合材料的制备
本发明三维介孔碳复合材料的制备，是以介孔硅为模板，蔗糖为碳源，乙醇为介质，在加热条件下不断搅拌使介孔硅的空隙被蔗糖完全填满，冷冻干燥；然后在氮气保护下碳化，用NaOH除去模板介孔硅，即得三维介孔碳复合材料。
具体制备工艺：将介孔硅粉末浸入浓度为35~45mg/mL蔗糖的乙醇溶液中，40~50℃下搅拌4~6h；重复上述过程至介孔硅的空隙被蔗糖完全填满，冷冻干燥后，在氮气保护下于600~700℃碳化2~3h，最后用NaOH除去模板介孔硅，得到介孔碳复合材料。
NaOH的用量为介孔硅材料质量1~2倍。
二、固相微萃取纤维的制备
本发明制备的三维介孔碳复合材料作为涂层材料制备固相微萃取纤维，是以不锈钢金属丝为纤维载体，环氧树脂胶为粘结剂，将三维介孔碳复合材料固定在不锈钢丝上而得。
具体制备工艺：将不锈钢丝分别在丙酮，超纯水中超声，干燥之后，将环氧树脂胶均匀涂覆在不锈钢丝的一端头（环氧树脂胶涂覆不锈钢丝端头的范围为1.5~1.8cm），再将其插入介孔碳材料粉末中并迅速拉出；重复该过程使介孔碳材料粉的厚度达到20~25μm；然后在60~80℃下真空干燥，得到固相微萃取纤维。
三、三维介孔碳复合材料及固相微萃取纤维的结构表征
采用X射线衍射、扫描电镜、透射电镜、氮气吸附脱附等现代仪器手段对介孔碳复合材料的结构和微结构进行了表征和分析。采用扫描电镜对新型固相微萃取纤维的形貌进行了表征。
图1为介孔碳复合材料的扫描电镜(a、b)和透射电镜(c、d)图。通过扫描电镜图和透射电镜图可以看出，本发明制备的介孔碳复合材料具有蜂窝状的形貌和多孔结构，能够作为一种很有潜力的吸附材料。
图2为介孔碳复合材料的X射线衍射图。从小角X射线衍射图可以看出，在0.8°附近有很弱的衍射峰，表明其具有有序的介孔结构。广角X射线衍射图表明，介孔碳复合材料具有无定型结构。
图3为介孔碳复合材料的氮气吸附脱附曲线。图3的结果表明，介孔碳复合材料具有较大的比表面积(728.28m2g-1)和孔容(0.96cm3g-1)，孔径约为48nm，进一步说明其具有很好的吸附性能。
图4为固相微萃取纤维的扫描电镜图。由图4可以看出，纤维具有粗糙的表面和多孔结构，涂层材料牢固的粘在不锈钢丝上，说明此纤维可以作为一种萃取性能优异的固相微萃取纤维。
五、固相微萃取纤维萃取性能测试
考察了固相微萃取纤维对加标环境水样（含有溴代阻燃剂）的萃取性能和效率，并与商业化纤维作了对比。图5为环境水样加标100μgL-1，介孔碳复合材料为涂层的固相微萃取纤维(a)，介孔硅复合材料为涂层的固相微萃取纤维(b)，商业PA纤维(c)，商业PDMS纤维(d)，和不加标水样用固相微萃取纤维(e)，直接进样(f)的液相色谱对比图。通过图5可以看出，本发明制备的固相微萃取纤维具有良好的萃取性能和效率，并远远好于商业纤维。
综上所述，本发明以蔗糖为碳源，介孔硅为模板剂，制备的三维介孔碳复合材料具有蜂窝状的形貌和多孔结构，具有很好的吸附能。以其为涂层材料制备的固相微萃取纤维具有良好的萃取性能和效率，对环境水样中的溴代阻燃剂具有很好的富集分离效率。
附图说明
图1为本发明制备的介孔碳复合材料的扫描电镜(a,b)和透射电镜(c,d)图。
图2为本发明制备的介孔碳复合材料的X射线衍射图。
图3为本发明制备的介孔碳复合材料的氮气吸附脱附曲线。
图4为本发明制备的介孔碳复合材料为涂层的固相微萃取纤维的扫描电镜图。
图5为本发明制备的固相微萃取纤维与商品化纤维的萃取性能对比图。
具体实施方式
下面通过具体实施例对本发明介孔碳复合材料的制备，固相微萃取纤维的制备以及对环境水中溴代阻燃剂的萃取性能作进一步说明。
1、介孔硅的制备
将石墨烯气凝胶10mg加入到含有480mg十六烷基三甲基溴化铵，4mL乙醇和20mg氢氧化钠的水溶液中，40℃下搅拌6h，然后，加入0.5mL正硅酸四乙酯，继续搅拌6h后，将得到的样品用热的乙醇和蒸馏水洗涤，冷冻干燥过夜，最后在管式炉中氮气保护下800℃煅烧3h，得到介孔硅复合材料。
2、三维介孔碳复合材料的制备
称取1g上述制备的介孔硅，浸入浓度为40mg/ml蔗糖的乙醇溶液中，40℃下搅拌6h，多次重复上述过程，至介孔硅的空隙被蔗糖完全填满，冷冻干燥过夜，再在氮气保护下700℃碳化3h，然后加入2mol/L的NaOH溶液中搅拌60min以除去模板介孔硅，最后在50℃干燥过夜，得三维介孔碳复合材料。
3、固相微萃取纤维的制备
取一段不锈钢丝，分别在丙酮、超纯水中超声清洗15min；干燥之后，将环氧树脂胶均匀的涂覆在不锈钢丝一头（约1.5cm）；再将其插入介孔碳复合材料材料粉末中并迅速拉出；重复该过程几次使介孔碳材料粉的厚度达到约25μm；最后将其放置在80℃的真空干燥箱中1h，得到固相微萃取纤维。
4、固相微萃取纤维的萃取性能测定
将固相微萃取与高效液相色谱联用，用于环境样品中痕量溴代阻燃剂的富集分离。取样品溶液15mL置于20mL样品瓶中，将内部放置磁子的样品瓶放置在磁力搅拌器上。将上述制备的SPME纤维浸入水样在600rpm的条件下搅拌30min。然后将完成萃取的纤维中取出，轻轻地插入到SPME-HPLC接口，让萃取纤维最大程度地进入解吸室，以流动相作解吸液静态解吸2min。解吸完毕后，取出萃取头，开始进样，此时流动相流过解吸室，把刚才解吸下来的待测物输送到色谱柱进行HPLC分析。结果见表1。
Claims (7)
1.一种三维介孔碳复合材料的制备方法，是以介孔硅为模板，蔗糖为碳源，乙醇为介质，在加热条件下不断搅拌使介孔硅的空隙被蔗糖完全填满，冷冻干燥；然后在氮气保护下碳化，用NaOH除去模板介孔硅，即得三维介孔碳复合材料。
2.如权利要求1所述三维介孔碳复合材料的制备方法，其特征在于：将介孔硅粉末浸入浓度为35~45mg/mL蔗糖的乙醇溶液中，40~50℃下搅拌4~6h；重复上述过程至介孔硅的空隙被蔗糖完全填满，冷冻干燥后，在氮气保护下于600~700℃碳化2~3h，最后用NaOH除去模板介孔硅，得到介孔碳复合材料。
3.如权利要求1所述三维介孔碳复合材料的制备方法，其特征在于：所述NaOH的用量为介孔硅材料质量1~2倍。
4.如权利要求1所述方法制备的三维介孔碳复合材料作为固相微萃取纤维涂层材料的应用。
5.如权利要求4所述三维介孔碳复合材料作为固相微萃取纤维涂层材料的应用，其特征在于：以不锈钢金属丝为纤维载体，环氧树脂胶为粘结剂，将三维介孔碳复合材料固定在不锈钢丝上而得。
6.如权利要求4或5所述三维介孔碳复合材料作为固相微萃取纤维涂层材料的应用，其特征在于：具体应用工艺：将不锈钢丝分别在丙酮，超纯水中超声，干燥之后，将环氧树脂胶均匀涂覆在不锈钢丝的一端头，再将其插入介孔碳材料粉末中，并迅速拉出；重复该过程使介孔碳材料粉的厚度为20~25μm；然后在60~80℃下真空干燥，得到固相微萃取纤维。
7.如权利要求4或5所述三维介孔碳复合材料作为固相微萃取纤维涂层材料的应用，其特征在于：环氧树脂胶均匀涂覆不锈钢丝端头的范围为1.5~1.8cm。
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