CN105521765B - 一种以碳纤维为骨架的石墨烯复合膜的制备方法及其应用 - Google Patents

一种以碳纤维为骨架的石墨烯复合膜的制备方法及其应用 Download PDF

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CN105521765B
CN105521765B CN201511024229.XA CN201511024229A CN105521765B CN 105521765 B CN105521765 B CN 105521765B CN 201511024229 A CN201511024229 A CN 201511024229A CN 105521765 B CN105521765 B CN 105521765B
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李海涛
刘迎亚
包丹丹
刘明凯
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Abstract

本发明公开一种以碳纤维为骨架的石墨烯复合膜的制备方法，用取氧化石墨烯液溶液，超导炭黑材料EC600JD制备混合液，装好抽滤装置，在滤膜上放上软碳布，取混合溶液进行抽滤，抽滤干后再放一层软碳布，再加混合液进行抽滤，最终得到以碳纤维为骨架的石墨烯复合膜。本发明以碳纤维布为骨架，可有效改善碳膜的承压能力，同时，使用GO改性EC600JD形成复合膜，既具有较好的机械性能和柔韧性，又对抗生素有高效的吸附能力。

Description

一种以碳纤维为骨架的石墨烯复合膜的制备方法及其应用
技术领域
本发明涉及一种以碳纤维为骨架的石墨烯复合膜的制备方法及其应用。
背景技术
自Alexander Fleming于1928年发现青霉素(Penicillin)以来，抗生素作为人类医疗史上一项重大发明，广泛用于人类和动物疾病的医疗保健以及农业产业化。然而抗生素药物的滥用使得全球各地已不断发现许多耐药性基因，日常的大量频繁性连续输入，在环境中表现为“虚拟持久性”特征，不断富集于各类水体、土壤和底泥中，使得频繁的检测出这些药物残留物。最近的一份学术报告称，检测我国地表水，发现68种抗生素，且浓度较高。抗生素进入水体后，给水生生态系统造成不良影响，不仅诱导产生耐药性细菌，也使水生生物受到影响；还可在农副产品中残留，通过饮水、食物链等方式对人体健康构成潜在的威胁，严重干扰人体的各项生理机能，破坏人体免疫系统，降低人体的免疫功能，如，如青霉素等β-内酰胺类抗生素可引起人体的过敏反应，庆大霉素对肾脏的毒性很大，喹诺酮类可增加人体对光线的敏感性，四环素类严重影响儿童牙齿发育等。
目前，我国现有的水处理技术有物理方法，包括利用各种孔径大小不同的滤材，利用吸附或阻隔方式，将水中的杂质排除在外，但是无法彻底清除水中抗生素。因此，寻找去除水中抗生素的方法，可以兼备吸附和阻隔方式的过滤效果已经是我们研究的重点内容。
氧化石墨烯或称功能化的石墨烯(functionalized graphene)是石墨烯重要的派生物，它的结构与石墨烯大体相同，只是在一层碳原子构成的二维空间无限延伸的基面上连有羰基、羟基、羧基等的官能团，它和石墨烯的关系，就像功能化的碳纳米管和碳纳米管一样。虽然各自有独特的特点，但很多性质又完全一致。图1为单片层氧化石墨烯的示意图，理论上认为完美的石墨烯表面无任何含氧功能团，而氧化石墨烯表面含有大量功能性基团，如–OH、–COOH、–O–、C＝O等，这些功能性基团赋予氧化石墨烯一些新的特性，如分散性、亲水性、与聚合物的兼容性等。氧化石墨烯成膜以其较好的机械性能和柔韧性而用于水中杂质的过滤。但是，单纯使用氧化石墨烯不能完全去除水中的抗生素。
因此，急需一种吸附性能良好、化学稳定性强、耐高温水浸、用法灵活多变、费用低廉的辅助性过滤材料。活性炭纳米材料比表面积大，因而表面能和活性增大，吸附能力增强，在水处理领域具有良好的应用前景。
鉴于以上优点，我们将氧化石墨烯做成石墨烯碳膜，既具有较好的成膜性能，又具有高效的抗生素吸附能力，但是作为一种滤材，需要考虑硬度问题，因此加入软碳布增强柔韧性能。因此，使用碳纤维为骨架的石墨烯膜对抗生素吸附性优良。
发明内容
针对上述现有技术存在的问题，本发明提供一种以碳纤维为骨架的石墨烯复合膜的制备方法及其应用，其生产出来的复合膜既具有较好的成膜性能，又具有高效的抗生素吸附能力。为了实现上述目的，本发明采用的技术方案是：一种以碳纤维为骨架的石墨烯复合膜的制备方法，用取氧化石墨烯液溶液，超导炭黑材料EC600JD制备混合液，
装好抽滤装置，在滤膜上放上软碳布，取混合溶液进行抽滤，抽滤干后再放一层软碳布，再加混合液进行抽滤，最终得到以碳纤维为骨架的石墨烯复合膜。
所述混合液由氧化石墨烯液溶液和超导炭黑材料EC600JD制备，质量比为4：1，加入到烧杯中，振荡15min，超声5min，重复振荡超声5次，得到混合液。
所述的滤膜孔径大小为0.45um。
一种碳纤维为骨架的石墨烯复合膜在水体中吸附抗生素的应用。
本发明以碳纤维布为骨架，可有效改善碳膜的承压能力，同时，使用GO改性EC600JD形成复合膜，既具有较好的机械性能和柔韧性，又对抗生素有高效的吸附能力。
附图说明
图1为单片层氧化石墨烯的示意图；
图2为BP2000、EC600JD和EC300J制的复合膜吸附效果图；
图3为软布和硬布的吸附性能比较图。
图4为复合膜光学照片；
图5为复合膜部分柔韧性检测；
图6为复合膜剖面SEM图；
图7为负载TCH的GO/CNT碳膜的EDS成像。
具体实施方式
下面对本发明作进一步说明。
如图1所示，一种以碳纤维为骨架的石墨烯复合膜的制备方法，用取氧化石墨烯液溶液，超导炭黑材料EC600JD制备混合液，
装好抽滤装置，在滤膜上放上软碳布，取混合溶液进行抽滤，抽滤干后再放一层软碳布，再加混合液进行抽滤，最终得到以碳纤维为骨架的石墨烯复合膜。
所述混合液由氧化石墨烯液溶液和超导炭黑材料EC600JD制备，质量比为4：1，当然了质量比也可以是3:1，但质量比为4：1时，石墨烯复合膜的吸附效果最好。
加入到烧杯中，振荡15min，超声5min，重复振荡超声5次，得到混合液。
所述的滤膜孔径大小为0.45um,
上述以碳纤维为骨架的石墨烯复合膜在水体中吸附抗生素的应用，
以碳纤维为骨架的石墨烯复合膜在水体中抗生素检测方面的应用，装好抽滤装置，放上石墨烯复合膜，滴加2mL,2mmol/L的盐酸四环素溶液，进行抽滤，滤液用紫外可见吸收光谱测量；
计算吸附容量：
Q＝(S0-S1)/S0*100％
Q——吸附容量
S0——原液积分面积
S1——滤液积分面积。
经分析计算，吸附率可达99.9％以上。
本发明以碳纤维布为骨架，可有效改善碳膜的承压能力，同时，使用GO改性EC600JD形成复合膜，既具有较好的机械性能和柔韧性，又对抗生素有高效的吸附能力。
本申请的复合膜是具有弱极性的多孔性吸附剂，具有发达的细孔结构和巨大的比表面积，对水中有机物有较好的吸附特性。为了探索其过滤效果，我们选择了分子较小，较难以过滤的盐酸四环素进行过滤效果的探究，并与其他活性炭所做的复合膜吸附性能的进行对比，由图4和5可知，EC600J/GO形成的复合碳
膜具有较好的机械性能和柔韧性能。从图6，可以看出，EC600J/GO形成的复合碳膜是一种超轻超薄的材料，厚度只有10um左右。由图7，GO/CNT碳膜的EDS图像，可以看到碳膜上吸附了很多盐酸四环素，证明其吸附性能优良
由图可知，三种活性炭所做的复合膜的吸附性能大小为BP2000>EC600JD>EC300J。BP2000复合膜和EC600JD复合膜的吸附性能相差不是很大，但是，EC600JD复合膜的吸附时间却大大减少，因此，EC600JD是用作合成复合膜较好的活性炭。

Claims (1)

1.一种以碳纤维为骨架的石墨烯复合膜的制备方法，其特征在于包括，用取氧化石墨烯液溶液，超导炭黑材料EC600JD制备混合液，装好抽滤装置，在滤膜上放上软碳布，取混合溶液进行抽滤，抽滤干后再放一层软碳布，再加混合液进行抽滤，最终得到以碳纤维为骨架的石墨烯复合膜;所述混合液由氧化石墨烯液溶液和超导炭黑材料EC600JD制备，质量比为4：1，加入到烧杯中，振荡15min，超声5min，重复振荡超声5次，得到混合液； 所述的滤膜孔径大小为0.45μm。
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CN105802589A (zh) * 2016-05-09 2016-07-27 中国石油大学(北京) 一种高强度导热膜及其制备方法
CN108579452A (zh) * 2018-06-15 2018-09-28 南京水杯子科技股份有限公司 一种氧化石墨烯复合炭膜及其制备方法
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