CN106732774B - 一种维生素b12功能化石墨烯复合材料及其制备方法和应用 - Google Patents
一种维生素b12功能化石墨烯复合材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种维生素B12功能化石墨烯复合材料及其制备方法和应用。采用的技术方案是：将氧化石墨烯超声分散在水中，将一定量的共聚物poly(B12‑IL)和水合肼加入到氧化石墨烯水分散液中，回流，反应结束后离心，固体用蒸馏水反复洗涤至洗涤液无色且呈中性，真空干燥得目标产物。本发明制备的poly(B12‑IL)/rGO可在光催化下高效降解有机卤代物。
Description
技术领域
本发明属于催化剂材料领域，尤其涉及一种具有光催化活性的石墨烯复合材料及其制备方法和应用。
背景技术
光催化脱卤反应由于其在治理卤代有机溶剂废料及残留在土壤中的有机卤代农药而得到催化领域的广泛关注。维生素B12及其衍生物被广泛用于催化脱卤反应中，选择合适的载体以提高催化效率是目前的研究重点之一。
发明内容
本发明的目的是，将一种维生素B12的衍生物与离子液体共聚得到相应的共聚物，然后通过静电自组装，将共聚物固载于还原氧化石墨烯片层表面，从而得到一种新型的维生素 B12功能化石墨烯复合材料，该材料可在光催化下高效降解有机卤代物。
本发明采用的技术方案是：一种维生素B12功能化石墨烯复合材料(poly(B12-IL)/rGO)，制备方法如下：将氧化石墨烯超声分散在水中，将一定量的共聚物poly(B12-IL)和水合肼加入到氧化石墨烯水分散液中，回流，反应结束后离心，固体用蒸馏水反复洗涤至洗涤液无色且呈中性，真空干燥得目标产物。
优选的，按质量比，共聚物poly(B12-IL):氧化石墨烯:水合肼＝1:1:0.5。
优选的，所述的共聚物poly(B12-IL)的制备方法包括如下步骤：将维生素B12衍生物、离子液体和偶氮二异丁腈(AIBN)溶于氯仿中，氮气保护下，回流，反应结束后减压下旋除溶剂，将固体用乙醚洗涤除去未反应的B12-styrene，然后将固体溶于少量蒸馏水，在截留分子量≥1000的半透膜中透析24h后，减压下旋除溶剂，真空干燥，得到共聚物poly(B12-IL)。
优选的，所述的维生素B12衍生物是B12-styrene。更优选的，所述的B12-styrene的制备方法包括如下步骤：取[(CN)(H2O)Cob(Ⅲ)6CesterCOOH]Cl、DMAP、EDC·HCl和4-乙烯基苄胺，溶于二氯甲烷中，0℃下搅拌混合均匀后，常温搅拌3小时，反应结束后，向反应液中加入蒸馏水，用四氯化碳萃取，有机相依次用盐酸和蒸馏水洗涤，减压下旋除溶剂，得目标产物。
优选的，所述的离子液体是N-乙基-N-乙烯基咪唑溴盐(ViEtIm+Br-)。
上述的一种维生素B12功能化石墨烯复合材料作为催化剂在光催化降解有机卤代物中的应用。方法如下：常温下，称取上述的维生素B12功能化石墨烯复合材料，超声分散于含有有机卤代物的甲醇溶液中，再加入三乙醇胺水溶液，搅拌，反应液通入氮气除氧，氮气保护下紫外光照射。优选的，所述的有机卤代物是DDT。
本发明的有益效果是：本发明将一种维生素B12衍生物与离子液体共聚得到共聚物poly(B12-IL)，然后通过静电自组装，使共聚物固载于还原氧化石墨烯片层表面，从而得到一种新型的维生素B12功能化石墨烯复合材料(poly(B12-IL)/rGO)。通过将催化剂分子固载到还原氧化石墨烯片层表面，利用石墨烯优异的电子传输性能及其大π平面对芳香族底物的吸附作用，提高对有机卤代污染物的光催化降解效率，并且可以实现催化剂高效回收再利用，该材料在光催化脱卤领域具有很好的应用前景。
附图说明
图1是poly(B12-IL)/rGO的合成路线图。
图2是poly(B12-IL)和poly(B12-IL)/rGO的紫外-可见吸收光谱。
图3是poly(B12-IL)/rGO的TEM图。
图4是光催化降解DDT的反应式。
图5是poly(B12-IL)/rGO光催化降解DDT的产物核磁图。
具体实施方式
实施例1 一种维生素B12功能化石墨烯复合材料(poly(B12-IL)/rGO)
(一)制备方法如下：
1、B12-styrene的合成
取[(CN)(H2O)Cob(Ⅲ)6CesterCOOH]Cl(200mg，0.186mmol)、DMAP(117mg，0.959mmol)、EDC·HCl(176mg，0.919mmol)、4-乙烯基苄胺(133mg，1.0mmol)溶于5ml二氯甲烷中，0℃下搅拌，混合均匀后，常温搅拌3小时。反应结束后，向反应液中加入50ml 蒸馏水，用四氯化碳萃取三次(3×20ml)，有机相用1％的盐酸(2×50ml)、蒸馏水(2×50ml) 各洗涤两次，减压下旋除溶剂，得紫色粉末状固体B12-styrene 197mg，产率为60％。
2、poly(B12-IL)的合成
取B12-styrene(71mg，0.06mmol)、ViEtIm+Br-(635mg，2.88mmol)、偶氮二异丁腈(16 mg，0.1mmol)溶于8ml CHCl3，氮气保护下回流12h，减压下旋除溶剂，向混合物中滴加30mL乙醚，搅拌，过滤，固体用10ml乙醚洗涤2次。固体溶于20mL蒸馏水中，用截留分子量≥1000的半透膜透析24h，减压下旋除溶剂，得共聚物poly(B12-IL)353mg。
3、复合物poly(B12-IL)/rGO的制备
取GO(50mg)超声分散于50ml蒸馏水中，加入25mg水合肼、50mg poly(B12-IL)，反应回流10h，离心，固体用蒸馏水反复洗涤至洗涤液无色且呈中性，真空干燥得产物65 mg。
(二)检测结果
图2是poly(B12-IL)和poly(B12-IL)/rGO的紫外-可见吸收光谱。通过对比可以确定， poly(B12-IL)在353nm和530nm处出现了化合物B12衍生物的特征吸收峰，而poly(B12-IL)/rGO在相应位置也出现了这两个特征吸收峰，由此证明poly(B12-IL)成功的固载到还原氧化石墨烯(rGO)的表面。
图3是poly(B12-IL)/rGO的TEM图。由图可以看出，修饰后，poly(B12-IL)/rGO复合物呈现良好的片层结构。
实施例2 一种维生素B12功能化石墨烯复合材料的应用
将poly(B12-IL)/rGO(5mg)、DDT(2.4×10-3M)、和三乙醇胺(0.2M)加入到5ml甲醇中，通入氮气除氧30min后，氮气保护下，100W紫外灯照射6h。利用核磁氢谱确定DDT转化率为100％。
图4是光催化降解DDT的反应式，图5是poly(B12-IL)/rGO催化降解DDT的产物核磁图。从图中可以看出归属为DDT结构中次甲基上的质子峰(5.1ppm)完全消失，同时在 4.55和6.3ppm的双重峰对应于DDD结构中两个次甲基中质子的特征峰。通过计算得知 DDT转化率为100％，并且完全转化为DDD。
Claims (5)
1.一种维生素B12功能化石墨烯复合材料，其特征在于：制备方法如下：将氧化石墨烯超声分散在水中，将一定量的共聚物poly(B12-IL)和水合肼加入到氧化石墨烯水分散液中，回流，反应结束后离心，固体用蒸馏水反复洗涤至洗涤液无色且呈中性，真空干燥得目标产物；
所述的共聚物poly(B12-IL)的制备方法包括如下步骤：将维生素B12衍生物、离子液体和偶氮二异丁腈(AIBN)溶于氯仿中，氮气保护下回流，反应结束后减压下旋除溶剂，将固体用乙醚洗涤后溶于水中，透析，减压蒸馏除去水，真空干燥，得到共聚物poly(B12-IL)；
所述的维生素B12衍生物是B12-styrene，结构式如下所示：
所述的离子液体是N-乙基-N-乙烯基咪唑溴盐。
2.根据权利要求1所述的一种维生素B12功能化石墨烯复合材料，其特征在于：按质量比，共聚物poly(B12-IL):氧化石墨烯:水合肼＝1:1:0.5。
3.权利要求1所述的一种维生素B12功能化石墨烯复合材料作为催化剂在光催化降解有机卤代物中的应用。
4.根据权利要求3所述的应用，其特征在于方法如下：常温下，称取权利要求1所述的维生素B12功能化石墨烯复合材料，超声分散于含有有机卤代物的甲醇溶液中，再加入三乙醇胺水溶液，搅拌，反应液通入氮气除氧，氮气保护下紫外光照射。
5.根据权利要求3或4所述的应用，其特征在于：所述的有机卤代物是2,2-双(4-氯苯基)-1,1,1-三氯乙烷(DDT)。
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