CN115582107B - 一种含碳纳米管的3d打印多孔材料的制备方法及应用 - Google Patents
一种含碳纳米管的3d打印多孔材料的制备方法及应用 Download PDFInfo
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Abstract
本发明提供了一种含碳纳米管的3D打印多孔材料的制备方法及应用。使用熔融沉积成型（FDM）3D打印机按照三周期极小曲面的结构打印聚乳酸多孔骨架，添加到含有不同表面状态碳纳米管、壳聚糖的乙酸水溶液中，采用负压负载制备获得碳纳米管/壳聚糖/聚乳酸多孔复合材料。所得多孔吸附剂孔隙率为43.5%，可用于作为废水中4‑氯苯酚的吸附材料，其吸附量为115.3mg/g。本发明避免了粉体多壁碳纳米管吸附材料易于发生团聚，提高吸附选择性和吸附效率，且使用简便，使用后不会造成吸附剂的残留易于回收和重复使用。
Description
技术领域
本发明属于材料技术领域，具体涉及一种含碳纳米管的3D打印多孔材料的制备方法及应用。
背景技术
随着工业的高速发展，工业生产中产生的含酚废水不经处理就排放到自然水体中，酚便会挥发进入大气或渗入地下，污染大气、地下水和农作物不仅对水体环境造成严重污染，也严重威胁到人类的健康。吸附法是利用多孔性的固体吸附剂将水体中的一种或数种组分吸附于表面，从而净化水体的一种方法。由于操作简单、效果稳定等特点，成为去除废水中酚类化合物最有效的技术之一。
多壁碳纳米管具有比表面积大、吸附容量大等优点，目前已逐渐被应用于对水中污染物的吸附去除。然而，碳纳米管在水处理方面的应用还存在着较多有待解决的问题，它作为吸附剂应用时会不可避免地发生团聚，吸附后难以从水中分离出来，吸附选择性低，再生效果差，容易造成水体二次污染。
3D打印技术是以一种以数字模型文件为基础，通过3D打印设备逐层增加材料而堆积成型的快速成型技术。该技术可以制造出传统成型方式不能制造的复杂、精细结构，实现产品个性化和定制化。当前，3D打印制备多孔聚合物复合材料的研究多集中于组织工程支架领域，在吸附领域的应用报道较少。
本发明结合3D打印技术，制备出表面负载碳纳米管的结构、尺寸可控的聚乳酸基多孔复合材料。本发明制备条件温和，制备工艺简单，负载稳定，节约成本。吸附完成后吸附剂回收过程简便易操作。
发明内容
本发明的主要目的在于提供一种含碳纳米管的3D打印多孔材料的制备方法及应用。利用3D打印技术制备孔结构可控、尺寸可控的聚乳酸多孔骨架，该结构为极小曲面结构，宏观尺寸为10~12mm，孔径在1.3～1.8 mm范围内，孔隙率为40~60%。再采用负压负载的方法在多孔骨架上负载碳纳米管，并将该材料作为吸附剂应用于4-氯苯酚吸附。
为了实现上述目的，本发明的技术方案如下：
本发明提供一种含碳纳米管的3D打印多孔材料的制备方法，其包括如下步骤：
（1）使用三维绘图软件设计特定形状和尺寸的多孔结构，利用熔融沉积式3D打印机打印所设计的聚乳酸PLA多孔结构。
（2）称取一定质量的碳纳米管于去离子水中，超声分散60~100min，形成CNTs水溶液。待分散完全后，加入一定质量的壳聚糖粉末于CNTs分散液中，在室温下匀速恒温搅拌约90~120min，使CNTs与CTS充分混合，后滴加乙酸，调整乙酸浓度至1-3%（v/v）继续搅拌均匀待新的混合再次均匀后得到碳纳米管/壳聚糖混合溶液。混合液中CTS含量为1~3g/100mL、CNTs含量为0.1~2g/100mL。
（3）将步骤（1）所述3D打印的聚乳酸多孔骨架浸入步骤（2）配制的混合溶液中并采用负压负载CNTs/CTS，在负压状态（0.1Pa~1Pa）下待聚乳酸多孔骨架孔隙内的气体排出使CNTs/CTS溶液能够充分浸入孔隙中，真空干燥，得到CNTs/CTS/PLA多孔材料。
进一步的，碳纳米管为多壁碳纳米管，直径为3~15nm，长度为15~30μm。
作为本发明的再一个方面，提供了一种如上所述的多孔材料在吸附废水中有机污染物4-氯苯酚的应用。
基于上述技术方案，本发明用于4-氯苯酚污染物吸附的多孔材料及其制备方法与应用具有以下有益效果：
（1）在FDM3D打印制备的多孔结构基体表面负载碳纳米管，可以有效解决聚合物缺乏孔结构的情况下活性组分有较大部分会被聚合物包覆，难以发挥吸附作用。
（2）利用3D打印技术对用于吸附废水中有机污染物4-氯苯酚的多孔结构进行加工制造，因此整个制造过程快速简便，加工成本低，多孔结构的形状和尺寸也可按需求设计和制造，以适用不同的场合。
（3）避免了粉体碳纳米管作为吸附材料应用时易于团聚，提高了吸附效率，并且使用简便，易于回收，使用后不会造成碳纳米管的残留，避免了水体二次污染，还可进行多次重复使用。
（4）将碳纳米管加入到壳聚糖的乙酸溶液中，碳纳米管水溶性差的表面被壳聚糖包裹住，使混合液的水溶性大大提高，可以阻止碳纳米管的团聚，使碳纳米管稳定地分散在酸性溶液中。
附图说明
图1为实施例1利用FDM3D打印技术制备的负载碳纳米管前后多孔材料。
图2为实施例1所得聚乳酸骨架表面负载碳纳米管的内部剖开低倍扫描电镜图。
图3为实施例1所得聚乳酸骨架表面负载碳纳米管的内部剖开高倍扫描电镜图。
具体实施方式
下面结合具体实施例对本发明做进一步说明。
实施例1
（1）聚乳酸多孔骨架的制备：使用三维绘图软件设计需要的多孔结构，以STL格式导出模型文件。利用熔融沉积成型（FDM）3D打印机设置合适的工艺参数直接打印出所设计的PLA多孔材料，该结构为全贯通的曲面多孔结构，外形尺寸为直径11mm、孔径分布均匀为1.58mm、质量为0.43g的螺旋球体的多孔结构试样。
（2）碳纳米管、壳聚糖混合液的制备：将0.5g的碳纳米管加入98mL去离子水中，同时超声分散60min。待分散完全后，加入1.5g的壳聚糖粉末，在室温下磁力搅拌90min，待CNTs与CTS充分混合后，按照配比滴加一定量的乙酸，边滴加边搅拌，使其溶解于2%（v/v）的乙酸溶液中，继续搅拌待新的混合再次均匀，得到2%CNTs/CTS溶液。此外，壳聚糖不仅可以分散碳纳米管，而且还具有固载的作用。碳纳米管在壳聚糖溶液中以非共轭形式缔合，并不改变碳纳米管的物理性质，仍然具有良好的电子传递能力。壳聚糖聚阳离子包裹在碳纳米管的表面，起到静电排斥作用，可以有效地防止碳纳米管的团聚及相互缠绕现象，使碳纳米管稳定地分散在酸性溶液中。
（3）负压负载制备CNTs/CTS/PLA多孔材料：将步骤（1）所述3D打印的聚乳酸骨架浸入CNTs/CTS的混合溶液中并保证骨架能被溶液完全覆盖，并在负压0 .1Pa下负载CNTs/CTS到聚乳酸骨架表面和孔隙中，在负压状态下聚乳酸骨架孔隙内的气体排出使CNTs/CTS溶液能够充分进入孔隙内部。待溶液基本不产生气泡后取出进行超声震荡，有助于CNTs/CTS更多的进入到基体内，与基体紧密结合。取出所得产物后放入60℃真空干燥箱中烘干备用。之后用去离子水反复冲洗小球去除残留乙酸等杂质，真空干燥箱烘干，制得CNTs/CTS/PLA多孔材料。对其称重可得负载CNTs/CTS量为0.05g。
实施例2
（1）聚乳酸多孔骨架的制备：使用三维绘图软件设计需要的多孔结构，以STL格式导出模型文件。利用熔融沉积成型（FDM）3D打印机设置合适的工艺参数直接打印出所设计的PLA多孔材料，该结构为全贯通的曲面多孔结构，外形尺寸为直径11mm、孔径分布均匀为1.58mm、质量为0.43g的螺旋球体的多孔结构试样。
（2）羧基化碳纳米管、壳聚糖混合液的制备：将0.5g的羧基化碳纳米管（纯度大于97%，羧基含量为1.23wt%）加入98mL去离子水中，同时超声分散60min。待分散完全后，加入1.5g壳聚糖粉末，在室温下用磁力搅拌约90min，待CNTs-COOH与CTS充分混合后，按照配比滴加一定量的乙酸，边滴加边搅拌，使其溶解于2%（v/v）的乙酸溶液中，继续搅拌待新的混合再次均匀，得到2%CNTs/CTS溶液。此外，壳聚糖不仅可以分散碳纳米管，而且还具有固载的作用。碳纳米管在壳聚糖溶液中以非共轭形式缔合，并不改变碳纳米管的物理性质，仍然具有良好的电子传递能力。壳聚糖聚阳离子包裹在碳纳米管的表面，起到静电排斥作用，可以有效地防止碳纳米管的团聚及相互缠绕现象，使碳纳米管稳定地分散在酸性溶液中。CNTs 表面带羧基基团，而溶解于酸性溶液中的CTS含有氨基，羧基能够与氨基发生酰胺化反应，增强碳纳米管与壳聚糖之间的相互作用，使复合材料的结构更加稳定。
（3）负压负载制备CNTs-COOH/CTS/PLA多孔材料：将步骤（1）所述3D打印的聚乳酸骨架浸入CNTs-COOH/CTS溶液中并保证骨架能被溶液完全覆盖，并在负压0 .1Pa下负载CNTs-COOH/CTS到聚乳酸骨架表面和孔隙中，在负压状态待聚乳酸骨架孔隙内的气体排出，使CNTs-COOH/CTS溶液能够充分进入孔隙内部。待溶液基本不产生气泡后取出进行超声震荡，有助于CNTs-COOH/CTS更多的进入到基体内，与基体紧密结合。取出试样后置于60℃真空干燥箱中烘干备用。之后用去离子水反复冲洗小球去除残留乙酸等杂质，真空干燥箱烘干，制得CNTs-COOH/CTS/PLA多孔材料。对其称重可得负载CNTs-COOH/CTS量为0.05g。
本发明还提供了一种如上所述的多孔材料在吸附4-氯苯酚中的应用。
4-氯苯酚的吸附实验：分别将实施例1和实施例2步骤（3）所得到的多孔材料加入到锥形瓶中，分别向锥形瓶加入100mL浓度为600mg/L的4-氯苯酚溶液。设定温度为25℃、pH=7、转速为150rpm，在恒温水浴振荡器里吸附240min后取出，过滤后用紫外分光光度计测出滤液的吸光度，根据公式（1）分别计算出它们对4-氯苯酚的吸附量。
其中C0为4-氯苯酚的初始浓度（mg/L），Ce为吸附后4-氯苯酚的浓度（mg/L），V为4-氯苯酚溶液的体积（mL），m为吸附剂的质量（g）。
不同表面状态碳纳米管对4-氯苯酚的吸附量如表1所示
表1 试样对4-氯苯酚的吸附量
由表1的实验结果可知，与纯聚乳酸吸附剂相比，本发明所制备的碳纳米管基球形多孔吸附剂对4-氯苯酚均具有较高的吸附能力。碳纳米管表面的羧基官能团可以改变碳纳米管表面的亲疏水性，使碳管表面更加亲水，更适合小分子的吸附。羧基官能团可以通过化学键的方式使4-氯苯酚转移到碳纳米管的孔结构里，使4-氯苯酚得以吸附去除，提高对4-氯苯酚的吸附性能。
由图1可见外形尺寸为直径为11mm的螺旋球体的多孔结构试样。该结构的空间利用率较高，比表面积较大（2.405mm-1），且结构稳定曲面无直线、无镜面，整个曲面造型呈螺旋上升。孔隙率采用称重法利用式（2）计算得到43.5%。
其中m1为多孔结构对应的实体质量，m2为多孔结构质量，P为实际孔隙。
表2多孔结构试样的孔隙率
采用高分辨率台式扫描电镜观察实施例试样表面的孔结构，观察实施例1试样内部剖开形貌，结果如图2、3所示。内部呈现多孔螺旋状，孔隙通透无堵塞，碳纳米管/壳聚糖渗入至聚乳酸骨架的孔隙中成膜状附着。
虽然上述实施例是基于熔融沉积成型3D打印技术来制备多孔结构，但本领域技术人员可以理解，利用其他4-氯苯酚吸附纳米材料通过其他3D打印技术得到的多孔吸附剂也应当具有相同或相近的技术效果。
本发明的方法和应用已通过较佳实施例子进行了描述以上所述的具体实施例，特别需要指出的是，以上所述仅为本发明的具体实施例而已，并不用于限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (1)
1.一种含碳纳米管的3D打印多孔材料用于吸附废水中4-氯苯酚中的应用，其特征在于，所述含碳纳米管的3D打印多孔材料的制备方法包括如下步骤：
（1）聚乳酸多孔骨架的制备：使用三维绘图软件设计需要的多孔结构，以STL格式导出模型文件；利用熔融沉积成型3D打印机设置合适的工艺参数直接打印出所设计的聚乳酸PLA多孔材料，该结构为全贯通的曲面多孔结构，外形尺寸为直径11mm、孔径分布均匀为1.58mm、质量为0.43g的螺旋球体的多孔结构试样；
（2）羧基化碳纳米管CNTs-COOH、壳聚糖CTS混合液的制备：将0.5g的纯度大于97%，羧基含量为1.23wt%的羧基化碳纳米管加入98mL去离子水中，同时超声分散60min；待分散完全后，加入1.5g壳聚糖粉末，在室温下用磁力搅拌90min，待CNTs-COOH与CTS充分混合后，按照配比滴加一定量的乙酸，边滴加边搅拌，使其溶解于体积分数为2%的乙酸溶液中，继续搅拌待新的混合再次均匀，得到2%CNTs-COOH/CTS溶液；
（3）负压负载制备CNTs-COOH/CTS/PLA多孔材料：将步骤（1）所得3D打印的聚乳酸多孔骨架浸入CNTs-COOH/CTS溶液中并保证骨架能被溶液完全覆盖，并在负压0 .1Pa下负载CNTs-COOH/CTS到聚乳酸骨架表面和孔隙中，在负压状态待聚乳酸骨架孔隙内的气体排出，使CNTs-COOH/CTS溶液能够充分进入孔隙内部；待溶液基本不产生气泡后取出进行超声震荡，有助于CNTs-COOH/CTS更多的进入到基体内，与基体紧密结合；取出试样后置于60℃真空干燥箱中烘干备用；之后用去离子水反复冲洗小球去除残留乙酸杂质，真空干燥箱烘干，制得CNTs-COOH/CTS/PLA多孔材料；对其称重得负载CNTs-COOH/CTS的量为0.05g。
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