CN107913668B - 一种具有吸附和催化降解功能的纳米复合材料及其制备方法和应用 - Google Patents
一种具有吸附和催化降解功能的纳米复合材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种具有吸附和催化降解功能的纳米复合材料及其制备方法和应用,制备如下:(1)恒温水浴中,将碳纳米管、聚乙二醇分散在纯净水中,超声形成均匀的悬浮液;(2)无氧环境下向所得悬浮液中加入FeCl3和FeCl2并持续搅拌,反应4~6小时,然后调节pH至11~11.5,升高水浴温度至70~80℃继续反应2~3小时,得混合液;(3)向混合液中依次加入MnSO4和KMnO4和KOH,反应2~4小时,得混合液,经后处理即得复合材料。本发明采用两步沉淀法制备CNT/MnO2/Fe3O4纳米复合材料,在复合物的制备过程中,Fe3O4和MnO2纳米粒子在CNT上原位沉淀生长,利用CNT的管壁结构固载和分散Fe3O4和MnO2纳米粒子,同时阻止CNT的团聚。
Description
技术领域
本发明属于纳米材料及环境科学技术领域,尤其涉及一种具有吸附和催化降解功能的磁性CNT/Fe3O4/MnO2纳米复合材料及其应用。
背景技术
染料广泛应用于纺织、皮革、造纸、印刷和化妆品等行业,据统计我国染料的年产量约75万吨,居世界首位。染料在生产和使用过程中约有10~15%要释放到环境中,因染料污染导致的水体安全问题已引起广泛关注。通常染料分子具有复杂的芳香结构很稳定,在水环境中很难自然降解。目前,染料废水的处理方法主要有吸附法、膜分离法,和催化氧化降解等。吸附法是废水深度处理的重要技术,在众多的吸附剂中,活性炭已广泛应用染料废水处理中。但活性炭存在吸附量不大、活化温度高、孔分布过宽、机械性能差、不易再生和表面不容易修饰等缺点。碳纳米材料,因其具有高的比表面积和良好的化学稳定性,在废水中污染物的吸附中显示了巨大的潜力和诱人的应用前景。
碳纳米管比表面积大、表面能高,对重金属和有机污染物均有较强的吸附作用(Kuma R R,Khan M A,Haq N.Application of carbon nanotubes in heavy metalsremediation[J].CriticalReviews in Environmental Science and Technology,2014,44(9):1000-1035;Ajmani G S,Cho H H,Abbott-Chalew T E,et al.Static and dynamicremoval of aquatic natural organic matter by carbon nanotubes[J].WaterResearch,2014,59:262-270)。碳纳米管中常含有羟基、羧基、羰基、氨基等官能团,这些官能团使碳纳米管具有一定的吸附/催化作用(Chen W,Zhu D,Zheng S,et al.Catalyticeffects of functionalized carbon nanotubes on dehydrochlorination of 1,1,2,2–tetrachloroethane[J].Environmental Science&Technology,2014,48(7):3856-3863)。但微小尺寸的碳纳米管存在密度小、沉降及分离回收困难等问题。
此外,由于碳纳米管间存在范德华作用,在水体中易团聚,导致有效表面积减少,从而降低吸附能力。因此开发具有亲水性、易回收的碳纳米管复合材料,是基于碳纳米管的新型吸附功能材料的研究开发方向。
磁性吸附材料既具有良好的吸附能力,又可通过外加磁场从水体分离,已经成为近年来环境净化的新一代材料。催化氧化降解也是去除有机污染物有效方法之一。相比于吸附法,催化氧化法利用催化剂降解水体中的有机污染物,从而达到环境治理的目的。MnO2具有较高的氧化电位,能够氧化很多有机化合物,作为氧化剂被广泛应用于水处理中。但MnO2的视密度较小,在水中易形成超细颗粒,使用后难以实现固液分离。
发明内容
本发明提供了一种具有吸附和催化降解功能的磁性CNT/Fe3O4/MnO2纳米复合材料及其制备方法和应用。
一种具有吸附和催化降解功能的纳米复合材料的制备方法,包括如下步骤:
(1)20~40℃恒温水浴中,将碳纳米管、聚乙二醇分散在纯净水中,超声形成均匀的悬浮液;
(2)无氧环境下向所得悬浮液中加入FeCl3和FeCl2的混合溶液并持续搅拌,反应4~6小时,然后调节pH至11~11.5,升高水浴温度至70~80℃继续反应2~3小时,得含有CNT/Fe3O4的混合液;
(3)向所得混合液中依次加入MnSO4溶液和KMnO4和KOH的混合溶液,反应2~4小时,得到含有CNT/Fe3O4/MnO2的混合液;
(4)含有CNT/Fe3O4/MnO2的混合液经过滤、洗涤、烘干处理得CNT/Fe3O4/MnO2纳米复合材料。
优选地,步骤(1)中投加的CNT质量与纯净水体积比为1/1.5~1/2.0mg/mL,CNT可以是多壁碳纳米管(MWCNT)、单壁碳纳米管(SWCNT)中的一种或其混合物,多壁碳纳米管、单壁碳纳米管又可是羟基化、羧基化、羰基化、氨基化等功能化碳纳米管中的一种或多种混合物,CNT可通过市售获得,也可利用市售的氧化CNT进一步功能化获得羟基化、羧基化、羰基化、氨基化等功能化碳纳米管;投加的PEG与CNT质量比为5~10,PEG优选PEG-400、PEG-600、PEG-800。
优选地,步骤(1)中水浴温度为30℃,超声时间为1小时。
步骤(1)中用浓度为25mg/mL的氨水调pH。
优选地,步骤(2)中调节pH前的反应温度为20~40℃、搅拌速度为1400~1600rpm,调节pH后的搅拌速度为2800~3200rpm。
进一步优选地,步骤(2)中调节pH前的反应温度为30℃、搅拌速度为1500rpm,调节pH后的搅拌速度为3000rpm、反应温度为75℃。
优选地,步骤(2)中FeCl2与CNT质量比为1/1~1.5/1;FeCl3与FeCl2摩尔比为2/1。
优选地,步骤(3)中反应温度为70~80℃、搅拌速度为2800~3200rpm。
进一步优选地,步骤(3)中反应温度为75℃、搅拌速度为3000rpm。
优选地,步骤(3)中MnSO4与FeCl2和FeCl3总质量比为0.6/1~0.75/1;KMnO4与MnSO4质量比为1/1.1~1/1.2;KOH与MnSO4和KMnO4总质量比为0.9/1~1/1。
优选地,步骤(4)中烘干温度为140~160℃,烘干时间为20~25小时。
优选地,步骤(2)中先通N2除氧1小时然后再加入FeCl3和FeCl2的,然后继续通N2持续反应5小时。
本发明以碳纳米管(CNT)为载体,依次在CNT上原位沉淀生长Fe3O4和MnO2纳米粒子,利用原位生长的Fe3O4和MnO2纳米粒子阻止CNT间的团聚;同时利用CNT作为Fe3O4和MnO2纳米粒子固定载体,以阻止Fe3O4和MnO2纳米粒子的团聚。
本发明以CNT为载体,首先选用FeCl3和FeCl2为前驱体,PEG为还原剂和纳米粒子分散稳定剂,采用沉淀法制备CNT/Fe3O4纳米复合物,再以MnSO4和KMnO4为前驱体,通过沉淀法制备CNT/Fe3O4/MnO2纳米复合材料。本方法制备的CNT/Fe3O4/MnO2纳米复合材料用于染料废水的吸附和光催化降解去除,表现出较好的去除性能,且可利用外加磁场从水体中分离、回收。
本发明的新颖之处表现为制备的CNT/Fe3O4/MnO2纳米复合材料,通过CNT、Fe3O4与MnO2的纳米复合及协同作用,纳米复合材料不仅具有了优良的染料吸附能力,而且具有良好的光催化降解性能,同时还具有一定的磁性,可利用外加磁场从水体中分离、回收。本发明提供的CNT/Fe3O4/MnO2纳米复合材料方法具有绿色环保、快速简便的特点。
与现有技术相比,本发明具有如下优点:
本发明采用两步沉淀法制备CNT/MnO2/Fe3O4纳米复合材料,在复合物的制备过程中,Fe3O4和MnO2纳米粒子在CNT上原位沉淀生长,利用CNT的管壁结构固载和分散Fe3O4和MnO2纳米粒子,同时阻止CNT的团聚。所制备的CNT/MnO2/Fe3O4纳米复合材料,通过CNT、MnO2与Fe3O4的纳米复合及相互协同作用,显示出优良的染料吸附能力和光催化降解性能,同时还可以外加磁场从水体中分离、回收。
附图说明
图1是本发明实施例1、对比例1、对比例2、对比例4所制备的纳米复合材料的透射电镜(TEM)照片。(A:实施例1;B:对比例1;C:对比例2;D:对比例4)
图2是本发明实施例1、对比例1、对比例2所制备的纳米复合材料的拉曼光谱(Raman)图。
具体实施方式
下面介绍的为本发明较为优选的实施例,但并不用于对本发明的限定。
CNT/Fe3O4/MnO2纳米复合材料的染料吸附性能评价:
实验选取亚甲基蓝(MB)为目标物进行CNT/Fe3O4/MnO2纳米复合材料的吸附性能评价,取8mg的MB和80mL的纯净水加到250mL锥形瓶中配制MB溶液,然后将50mg超声分散好的CNT/Fe3O4/MnO2加入到上述混合液中,放入30℃恒温水浴磁力搅拌。每隔5min用一次性注射器吸取2mL的溶液,用0.45μm滤膜过滤,用分光光度计测定过滤液的吸光度(λ=664nm),通过朗伯比尔定律计算出过滤液中MB的浓度,并由下式计算MB的吸附去除率。
吸附去除率=(c0-ct)/c0
式中,c0:MB的初始浓度;ct:吸附t分钟后MB的浓度。
CNT/Fe3O4/MnO2纳米复合材料的染料催化降解性能评价:
实验选取亚甲基蓝(MB)为目标物进行CNT/Fe3O4/MnO2纳米复合材料的催化降解评价,取8mg的MB和80ml的纯净水加到250mL锥形瓶中配制MB溶液,用0.1mg/L的HCl溶液调节pH至5.0,再加入50mg超声分散好的CNT/Fe3O4/MnO2,放入30℃恒温水浴中磁力搅拌30min至吸附平衡,量取2mL、30%H2O2加入到上述混合液中反应60min。每隔5min用一次性注射器吸取2mL的反应溶液,用0.45μm滤膜过滤,用分光光度计测定过滤液的吸光度(λ=664nm),通过朗伯比尔定律计算出过滤液中MB的浓度,并由下式计算MB的催化降解去除率。
催化降解去除率=(C0-Ct)/C0
式中,C0:MB的初始浓度;Ct:反应t分钟后MB的浓度。
实施例1
分别称取200mg的CNT(含氧功能基团为5.2wt%)和1000mg的PEG-600溶于350ml去离子水中,30℃下超声1小时形成均匀的悬浮液。1500rpm磁力搅拌下并通N2除氧1小时,30℃下将浓度分别为100mg/mL(0.789mmol/mL)、256mg/mL(1.578mmol/mL)的FeCl2和FeCl3的混合溶液2mL缓慢滴加到上述悬浮液中,继续搅拌并通N2除氧5小时,紧接着快速加入氨浓度为25mg/mL的氨水调节pH至11,然后将磁力搅拌速率调至3000rpm,恒温水浴温度升至75℃下反应3小时。3000rpm磁力搅拌作用下,75℃的恒温水浴中向上述混合液中加入浓度为120mg/mL的MnSO4溶液4mL,再快速加入浓度分别为60mg/mL、120mg/mL的KMnO4和KOH的混合溶液7mL,反应3小时。用抽滤瓶对上述获得的混合物进行过滤,并用去纯净水对过滤沉积物进行多次洗涤;最后将过滤﹑洗涤后所得产物放置于50℃真空烘箱中干燥24小时,得到CNT/Fe3O4/MnO2纳米复合材料。
本实施例所制备的CNT/Fe3O4/MnO2纳米复合材料的透射电镜(TEM)照片如图1中A所示;所制备的CNT/Fe3O4/MnO2纳米复合材料的拉曼光谱(Raman)图参见图2中A。
本实施例所制备的CNT/Fe3O4/MnO2纳米复合材料的染料吸附和催化降解性能见表1。
实施例2
分别称取200mg的CNT(含氧功能基团为5.2wt%)和1200mg的PEG-600溶于350ml去离子水中,30℃下超声1小时形成均匀的悬浮液。1500rpm磁力搅拌下并通N2除氧1小时,30℃下将浓度分别为100mg/mL(0.789mmol/mL)、256mg/mL(1.578mmol/mL)的FeCl2和FeCl3的混合溶液2.5mL缓慢滴加到上述悬浮液中,继续搅拌并通N2除氧5小时,紧接着快速加入氨浓度为25mg/mL的氨水调节pH至11,然后将磁力搅拌速率调至3000rpm,恒温水浴温度升至75℃下反应3小时。3000rpm磁力搅拌作用下,75℃的恒温水浴中向上述混合液中加入浓度为120mg/mL的MnSO4溶液4.5mL,再快速加入浓度分别为60mg/mL、120mg/mL的KMnO4和KOH的混合溶液8mL,反应3小时。用抽滤瓶对上述获得的混合物进行过滤,并用去纯净水对过滤沉积物进行多次洗涤;最后将过滤﹑洗涤后所得产物放置于50℃真空烘箱中干燥24小时,得到CNT/Fe3O4/MnO2纳米复合材料。
本实施例所制备的CNT/Fe3O4/MnO2纳米复合材料的染料吸附和催化降解性能见表1。
实施例3
分别称取200mg的CNT(含氧功能基团为5.2wt%)和1400mg的PEG-600溶于350ml去离子水中,30℃下超声1小时形成均匀的悬浮液。1500rpm磁力搅拌下并通N2除氧1小时,30℃下将浓度分别为100mg/mL(0.789mmol/mL)、256mg/mL(1.578mmol/mL)的FeCl2和FeCl3的混合溶液3mL缓慢滴加到上述悬浮液中,继续搅拌并通N2除氧5小时,紧接着快速加入氨浓度为25mg/mL的氨水调节pH至11,然后将磁力搅拌速率调至3000rpm,恒温水浴温度升至75℃下反应3小时。3000rpm磁力搅拌作用下,75℃的恒温水浴中向上述混合液中加入浓度为120mg/mL的MnSO4溶液6mL,再快速加入浓度为分别为60mg/mL、120mg/mL的KMnO4和KOH的混合溶液11mL,反应3小时。用抽滤瓶对上述获得的混合物进行过滤,并用去纯净水对过滤沉积物进行多次洗涤;最后将过滤﹑洗涤后所得产物放置于50℃真空烘箱中干燥24小时,得到CNT/Fe3O4/MnO2纳米复合材料。
本实施例所制备的CNT/Fe3O4/MnO2纳米复合材料的染料吸附和催化降解性能见表1。
对比例1
分别称取200mg的CNT(含氧功能基团为5.2wt%)和1000mg的PEG-600溶于350ml去离子水中,30℃下超声1小时形成均匀的悬浮液。1500rpm磁力搅拌下并通N2除氧1小时,30℃下将浓度分别为100mg/mL(0.789mmol/mL)、256mg/mL(1.578mmol/mL)的FeCl2和FeCl3的混合溶液2mL缓慢滴加到上述悬浮液中,继续搅拌并通N2除氧5小时,紧接着快速加入氨浓度为25mg/mL的氨水调节pH至11,然后将磁力搅拌速率调至3000rpm,恒温水浴温度升至75℃下反应3小时。用抽滤瓶对上述获得的混合物进行过滤,并用去纯净水对过滤沉积物进行多次洗涤;最后将过滤﹑洗涤后所得产物放置于50℃真空烘箱中干燥24小时,得到CNT/Fe3O4纳米复合材料。
本对比例所制备的CNT/Fe3O4纳米复合材料的透射电镜(TEM)照片如图1中B所示;所制备的CNT/Fe3O4纳米复合材料的拉曼光谱(Raman)图参见图2中B。
本对比例所制备的CNT/Fe3O4纳米复合材料的染料吸附和催化降解性能见表1。
对比例2
分别称取200mg的CNT(含氧功能基团为5.2wt%)和1200mg的PEG-600溶于350ml去离子水中,30℃下超声1小时形成均匀的悬浮液。3000rpm磁力搅拌作用下,75℃的恒温水浴中向上述悬浮液中加入浓度为120mg/mL的MnSO4溶液4.5mL,再快速加入浓度分别为60mg/mL、120mg/mL的KMnO4和KOH的混合溶液8mL,反应3小时。用抽滤瓶对上述获得的混合液进行过滤,并用去纯净水对过滤沉积物进行多次洗涤;最后将过滤﹑洗涤后所得产物放置于50℃真空烘箱中干燥24小时,得到CNT/MnO2纳米复合材料。
本对比例所制备的rGO/MnO2纳米复合材料的透射电镜(TEM)照片如图1(C)所示;所制备的CNT/MnO2纳米复合材料的拉曼光谱(Raman)图参见图2中C。
本对比例所制备的CNT/MnO2纳米复合材料的染料吸附和催化降解性能见表1。
对比例3
称取1400mg的PEG-600溶于350ml去离子水中,30℃下超声1小时形成均匀的溶液。1500rpm磁力搅拌下并通N2除氧1小时,30℃下将浓度分别为100mg/mL(0.789mmol/mL)、256mg/mL(1.578mmol/mL)的FeCl2和FeCl3的混合溶液3mL缓慢滴加到上述溶液中,继续搅拌并通N2除氧5小时,紧接着快速加入氨浓度为25mg/mL的氨水调节pH至11,然后将磁力搅拌速率调至3000rpm,恒温水浴温度升至75℃下反应3小时。3000rpm磁力搅拌作用下,75℃的恒温水浴中向上述混合液中加入浓度为120mg/mL的MnSO4溶液6mL,再快速加入浓度为分别为60mg/mL、120mg/mL的KMnO4和KOH的混合溶液11mL,反应3小时。用抽滤瓶对上述获得的混合物进行过滤,并用去纯净水对过滤沉积物进行多次洗涤;最后将过滤﹑洗涤后所得产物放置于50℃真空烘箱中干燥24小时,得到Fe3O4/MnO2纳米复合材料。
本对比例所制备的Fe3O4/MnO2纳米复合材料的染料吸附和催化降解性能见表1。
对比例4
分别称取200mg的CNT(含氧功能基团为5.2wt%)和1000mg的PEG-600溶于350ml去离子水中,30℃下超声1小时形成均匀的悬浮液。用抽滤瓶对上述获得的悬浮液进行过滤,并用去纯净水对过滤沉积物进行多次洗涤;最后将过滤﹑洗涤后所得产物放置于50℃真空烘箱中干燥24小时,得到CNT纳米材料。
本对比例所制备的CNT纳米材料的透射电镜(TEM)照片如图1中D所示。
图1中A、B、C分别为实施例1、对比例1、对比例2所制备的CNT/Fe3O4/MnO2、CNT/Fe3O4、CNT/MnO2纳米复合材料的透射电镜(TEM)照片。从图中可以看出Fe3O4/MnO2、Fe3O4、MnO2纳米粒子均匀的沉积在碳纳米管表面。
图2中A、B、C分别为实施例1、对比例1、对比例2所制备的CNT/Fe3O4/MnO2、CNT/Fe3O4、CNT/MnO2纳米复合材料的拉曼光谱(Raman)图。从图中可以明显地看出,CNT/Fe3O4/MnO2、CNT/Fe3O4、CNT/MnO2样品均在约320nm左右处有反射峰,这表明在碳纳米管管壁上沉积了Fe3O4/MnO2、Fe3O4、MnO2纳米粒子。
本对比例所制备的CNT纳米材料的染料吸附和催化降解性能见表1。
表1是本发明实施例所制备的CNT/Fe3O4/MnO2纳米复合材料及对比例1、对比例2、对比例3、对比例4所制备的纳米复合材料的染料吸附和催化降解性能。
表1
表1中分别列出了实施例1-3制备的CNT/Fe3O4/MnO2纳米复合材料、对比例1-4分别制备的CNT/Fe3O4纳米复合材料、CNT/MnO2纳米复合材料、Fe3O4/MnO2纳米复合材料、CNT的MB吸附去除率和催化降解去除率。与CNT/Fe3O4纳米复合材料、CNT/MnO2纳米复合材料、Fe3O4/MnO2纳米复合材料、CNT相比,CNT/Fe3O4/MnO2纳米复合材料不仅具有了优良的染料吸附能力,而且具有良好的光催化降解性能,同时还具有一定的磁性,可利用外加磁场从水体中分离、回收。
Claims (9)
1.一种具有染料吸附和催化降解功能的纳米复合材料的制备方法,其特征在于,包括如下步骤:
(1)20~40℃恒温水浴中,将碳纳米管、聚乙二醇分散在纯净水中,超声形成均匀的悬浮液;
(2)无氧环境下向所得悬浮液中加入FeCl3和FeCl2的混合溶液并持续搅拌,反应4~6小时,然后调节pH至11~11.5,升高水浴温度至70~80℃继续反应2~3小时,得含有CNT/Fe3O4的混合液;FeCl2与CNT质量比为1/1~1.5/1;
(3)向所得混合液中依次加入MnSO4溶液和KMnO4与KOH的混合溶液,反应2~4小时,得到含有CNT/Fe3O4/MnO2的混合液;MnSO4与FeCl2和FeCl3总质量比为0.6/1~0.75/1;KMnO4与MnSO4质量比为1/1.1~1/1.2;KOH与MnSO4和KMnO4总质量比为0.9/1~1/1;
(4)含有CNT/Fe3O4/MnO2的混合液经过滤、洗涤、烘干处理得CNT/Fe3O4/MnO2纳米复合材料。
2.根据权利要求1所述制备方法,其特征在于,步骤(1)中所述碳纳米管为多壁碳纳米管或/和单壁碳纳米管,碳纳米管质量与纯净水体积的比为1/1.7~1/1.8mg/mL,聚乙二醇与碳纳米管的质量比为5~10。
3.根据权利要求1所述制备方法,其特征在于,步骤(1)中水浴温度为30℃,超声时间为1小时。
4.根据权利要求1所述制备方法,其特征在于,步骤(2)中调节pH前的反应温度为20~40℃、搅拌速度为1400~1600rpm,调节pH后的搅拌速度为2800~3200rpm。
5.根据权利要求1所述制备方法,其特征在于,步骤(2)中调节pH前的反应温度为30℃、搅拌速度为1500rpm,调节pH后的搅拌速度为3000rpm、反应温度为75℃。
6.根据权利要求1所述制备方法,其特征在于,步骤(2)中FeCl3与FeCl2摩尔比为2/1。
7.根据权利要求1所述制备方法,其特征在于,步骤(3)中反应温度为70~80℃、搅拌速度为2800~3200rpm。
8.根据权利要求1所述制备方法,其特征在于,步骤(3)中反应温度为75℃、搅拌速度为3000rpm。
9.根据权利要求1所述制备方法,其特征在于,步骤(4)中烘干温度为140~160℃,烘干时间为20~25小时。
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