CN108786892A - 一种氧化石墨相单层c3n4复合膜材料及其制备方法和用途 - Google Patents
一种氧化石墨相单层c3n4复合膜材料及其制备方法和用途 Download PDFInfo
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Abstract
本发明提供一种氧化石墨相单层C3N4复合膜材料及其制备方法和用途,制备的复合膜材料用于光降解水中抗生素和水体中的有机染料,并且通过可见光降解实现自清洁而得以重复使用,用GO和N‑CNT对石墨相单层C3N4进行表面修饰,制备出氧化石墨相单层C3N4复合膜材料。
Description
技术领域
本发明涉及一种氧化石墨相单层C3N4复合膜材料及其制备方法和用途。
背景技术
我国传统的水处理技术是物理方法,包括各种孔径大小的过滤材料,利用材料的吸附或阻隔方式排除水中的杂质,但是这种过滤的方法无法彻底清除水中抗生素和有机染料分子。因此,亟需寻找一种能够彻底去除水中抗生素和有机染料的方法。
光催化氧化法对于含抗生素水和有机染料废水的处理有着独特的优越性,优越性在于通过光催化活性分子的氧化还原反应能够将污染物彻底降解为无毒害的小分子。对于光催化氧化法,最重要的是要寻找到一种优良的光催化剂,目前光催化领域最常用的催化剂是锐钛相二氧化钛。但是二氧化钛催化的一个最大问题是不具有可见光响应,这就限制了其在实际生产生活中的应用,因此亟需开发一种具有可见光响应的催化剂。
石墨相C3N4是一种新型的可见光响应的催化剂,在光催化治理水环境污染方面已经有了许多的研究。主要机理是,光照下产生光生电子和空穴,依赖于电子和空穴的氧化还原反应产生具有强氧化性的自由基分子直接或者间接的彻底氧化污染物分子。
石墨相C3N4比表面积小,与污染物分子的接触面积就较小;且光生电子空穴分离后易复合,能够产生的光催化活性物种数就减少,单一石墨相C3N4作为催化剂时可见光催化降解水体中污染物分子的效果并不好;此外,催化剂的可循环使用性和光催化活性的稳定性也是考察催化剂性能优劣的一个重要指标。
发明内容
针对上述现有催化剂存在的问题,本专利提供一种氧化石墨相单层C3N4复合膜材料及其制备方法和用途,制备的复合膜材料用于光降解水中抗生素和水体中的有机染料,并且通过可见光降解实现自清洁而得以重复使用。具体解决的技术问题如下:
一种氧化石墨相单层C3N4复合膜材料的制备方法,用GO和N-CNT对石墨相单层C3N4进行表面修饰,制备出氧化石墨相单层C3N4复合膜材料。包括以下步骤:分别称取O-g-C3N4和N-CNT于两支离心管中,分别加入浓盐酸,超声,将浓盐酸处理后的O-g-C3N4和N-CNT在同一离心管中混合,离心,水洗,保留沉淀物,加入GO,混合超声2h,得到混合液,装好抽滤装置,取所述混合液进行抽滤,抽滤干后取出,干燥,在滤膜背面滴加乙醇溶液,将O-g-C3N4/GO/N-CNT膜从滤膜上揭下,最终得到氧化石墨相单层C3N4复合膜材料。
所述的氧化石墨相单层C3N4复合膜材料在光催化降解水中抗生素分子方面的用途。
所述的氧化石墨相单层C3N4复合膜材料在光催化降解水体中有机染料污染物分子方面的用途。
所述的氧化石墨相单层C3N4复合膜材料在通过光催化自清洁实现对污染物分子的循环光降解方面的用途。
(1)针对石墨相C3N4比表面积小,本专利采用一种氧化石墨相单层C3N4,与块状和多层石墨相C3N4相比,等量的单层材料与污染物分子的接触面积大大增加,有利于加快光催化反应的进行。
(2)针对石墨相C3N4的光生电子和空穴分离后易复合,本专利采用氧化石墨烯(GO)和氮掺杂碳纳米管(N-CNT)对其进行表面修饰,制备出一种氧化石墨相单层C3N4复合膜材料。GO是一种二维层状结构,其比表面积大,电导率高,具有优异的吸附性能,是一种修饰氧化石墨相单层C3N4的优良助催剂。N-CNT是一种管状结构,具有一定的吸附性能,能够定向输送光生载流子,加速光催化活性物种的产生。制备的复合膜材料中三组分紧密接触,有利于光生电子的传递和转移,抑制光生电子空穴对的复合,从而大大提高了光催化降解性能。
(3)针对催化剂的可循环使用性和稳定性,本专利以罗丹明6G分子为目标物,考察了氧化石墨相单层C3N4复合膜材料的可循环使用性和光催化活性的稳定性。结果表明,本专利氧化石墨相单层C3N4复合膜材料是可循环使用的,光催化活性高且十分稳定。
与现有技术相比,本发明:
(1)使用比表面积相对较大的氧化石墨相单层C3N4为光催化剂,GO和N-CNT的吸附性能将污染物分子富集在催化剂氧化石墨相单层C3N4的表面,加快了光降解过程的进行。
(2)GO和N-CNT共同修饰在氧化石墨相单层C3N4的表面,三组分的密切接触加快了光生载流子的转移和输送,抑制了光生电子空穴对的复合率,促进产生更多的光催化活性物种,从而有利于增强光催化氧化降解污染物分子的效率。
(3)本专利一种氧化石墨相单层C3N4复合膜材料具有可循环使用性和优异的光催化活性稳定性。
附图说明
图1为本发明氧化石墨相单层C3N4复合膜材料的合成过程示意图。
图2为本发明氧化石墨相单层C3N4复合膜材料的光学图片。
图3为本发明氧化石墨相单层C3N4复合膜材料的SEM图。
图4为本发明氧化石墨相单层C3N4复合膜材料对盐酸四环素的可见光降解率图。
图5为本发明氧化石墨相单层C3N4复合膜材料对罗丹明6G的可见光降解率图。
图6为本发明氧化石墨相单层C3N4复合膜材料的催化稳定性测试。
具体实施方式
本发明所述的实例是对本发明的说明而不能限制本发明,在与本发明相当的含义和范围内的任何改变和调整,都应认为是在本发明的范围内。下面对本发明作进一步说明。
实验1:一种氧化石墨相单层C3N4复合膜材料的制备方法,包括氧化石墨相单层C3N4纳米片(O-g-C3N4),氧化石墨烯分散液(GO)和氮掺杂碳纳米管(N-CNT)。
如图1所示,一种氧化石墨相单层C3N4复合膜材料的制备方法,包括以下步骤:分别称取O-g-C3N4和N-CNT于两支离心管中,分别加入浓盐酸,超声90min。将浓盐酸处理后的O-g-C3N4和N-CNT在同一离心管中混合,离心,水洗3次,保留沉淀物。加入GO,混合超声2h,得到混合液。装好抽滤装置,取所述混合液进行抽滤,抽滤干后取出,干燥,在滤膜背面滴加乙醇溶液,将O-g-C3N4/GO/N-CNT膜从滤膜上揭下,最终得到氧化石墨相单层C3N4复合膜材料,如图2,图3所示。从图2光学图片中可以看出,该膜可随意弯曲且不损坏,具有良好的柔韧性。从图3SEM图中可以看出,管状的N-CNT成功嵌在GO和O-g-C3N4的片层中,即GO,N-CNT与O-g-C3N4通过静电作用成功合成氧化石墨相单层C3N4复合膜材料。
最佳实施例
分别称取1mg O-g-C3N4和0.5mg N-CNT于两支离心管中,分别加入3mL浓盐酸。超声90min后,O-g-C3N4颜色由浅黄色变白色,N-CNT完全分散于浓盐酸溶液中。将浓盐酸处理后的O-g-C3N4和N-CNT在离心管中混合,以5000r/min转速离心10min除去多余酸液,水洗3次,保留沉淀物。加入1mL GO(2mg/mL),混合超声2h,得到混合液。装好抽滤装置,取所述混合液在孔径大小为0.2μm的滤膜上进行抽滤,抽滤干后取出,在40℃烘箱中干燥5min,在滤膜背面滴加乙醇溶液(ACS≥99.5%),将O-g-C3N4/GO/N-CNT膜从滤膜上揭下,最终得到氧化石墨相单层C3N4复合膜材料。
实验2:上述的氧化石墨相单层C3N4复合膜材料的用途。
对于水中抗生素和水体有机染料污染物具有优异的光降解性能,并且通过可见光降解实现自清洁而得以重复使用,为目前的光催化氧化法处理水污染提供了一种策略。
实施例1:氧化石墨相单层C3N4复合膜材料在光催化降解水中抗生素分子方面的用途。准确取20mL浓度为10mg/L的盐酸四环素溶液于石英光反应器内,取样0.5mL于1.5mL离心管中标记为-30,之后向反应器内加入氧化石墨相单层C3N4复合膜材料,在暗处通风搅拌30min后取样0.5mL于1.5mL离心管中标记为0。依次开启循环冷凝水装置和氙灯光源(氙灯光源处有400nm滤光片),开始光催化反应过程,每隔30min取样0.5mL于1.5mL离心管中并做好标记,光反应进行到360min时结束。将所取样在10000r/min下离心30min,用紫外可见分光光度计测定上清液中盐酸四环素的吸光度,并通过积分面积法计算氧化石墨相单层C3N4复合膜材料对盐酸四环素的降解率。
计算降解率:
η=(A-A0)/A0×100%
η——降解率
A0——原液积分面积
A——上清液积分面积
如图4所示,经分析计算,对盐酸四环素的降解率达93.45%。
实施例2:,氧化石墨相单层C3N4复合膜材料在光催化降解水体中有机染料污染物分子方面的用途。准确取20mL浓度为10mg/L的罗丹明6G溶液于石英光反应器内,取样0.5mL于1.5mL离心管中标记为-30,之后向反应器内加入氧化石墨相单层C3N4复合膜材料,在暗处通风搅拌30min后取样0.5mL于1.5mL离心管中标记为0。依次开启循环冷凝水装置和氙灯光源(氙灯光源处有400nm滤光片),开始光催化反应过程,每隔30min取样0.5mL于1.5mL离心管中并做好标记,光反应进行到360min时结束。将所取样在10000r/min下离心30min,用紫外可见分光光度计测定上清液中罗丹明6G的吸光度,并通过积分面积法计算氧化石墨相单层C3N4复合膜材料对罗丹明6G的降解率。
计算降解率:
η=(A-A0)/A0×100%
η——降解率
A0——原液积分面积
A——上清液积分面积
如图5所示,经分析计算,对罗丹明6G的降解率达80%。
实验3:如图6所示,氧化石墨相单层C3N4复合膜材料在通过光催化自清洁实现对污染物分子的循环光降解方面的用途。搭好抽滤装置,待氧化石墨相单层C3N4复合膜抽干后,加入2mL浓度为20mg/L的盐酸四环素溶液继续抽滤以富集盐酸四环素分子。抽滤干后,取出富集盐酸四环素的复合膜并将其置于玻璃片上,向复合膜材料中滴加一滴水,开启氙灯光源。光照360min后取出复合膜材料,用乙醇(ACS≥99.5%)萃取出盐酸四环素分子,取部分萃取液离心,测定上清液的紫外可见吸光度A,同时测定盐酸四环素母液的紫外可见吸光度A0,通过积分面积法计算其降解率η;将含有乙醇溶液的复合膜材料经抽滤重新制备成氧化石墨相单层C3N4复合膜,并将其再次用于富集和光降解盐酸四环素。重复三次,考察氧化石墨相单层C3N4复合膜对盐酸四环素的光降解效率的变化。从图中可以看出,重复使用三次后,氧化石墨相单层C3N4复合膜对盐酸四环素的光降解效率下降很小,几乎没有变化,很好地通过光催化自清洁实现了对水体中污染物分子的循环光降解应用。
Claims (7)
1.一种氧化石墨相单层C3N4复合膜材料的制备方法,其特征在于,采用GO和N-CNT对石墨相单层C3N4进行表面修饰,制备出氧化石墨相单层C3N4复合膜材料。
2.根据权利要求1所述的一种氧化石墨相单层C3N4复合膜材料的制备方法,其特征在于,包括以下步骤:分别称取O-g-C3N4和N-CNT于两支离心管中,分别加入浓盐酸,超声,将浓盐酸处理后的O-g-C3N4和N-CNT在同一离心管中混合,离心,水洗,保留沉淀物,加入GO,混合超声2h,得到混合液,装好抽滤装置,取所述混合液进行抽滤,抽滤干后取出,干燥,在滤膜背面滴加乙醇溶液,将O-g-C3N4/GO/N-CNT膜从滤膜上揭下,最终得到氧化石墨相单层C3N4复合膜材料。
3.根据权利要求1所述的一种氧化石墨相单层C3N4复合膜材料的制备方法,其特征在于,分别称取1mg O-g-C3N4和0.5mg N-CNT于两支离心管中,分别加入3mL浓盐酸,超声90min后,O-g-C3N4颜色由浅黄色变白色,N-CNT完全分散于浓盐酸溶液中,将浓盐酸处理后的O-g-C3N4和N-CNT在离心管中混合,以5000r/min转速离心10min除去多余酸液,水洗3次,保留沉淀物,加入1mL GO,混合超声2h,得到混合液,装好抽滤装置,取所述混合液在孔径大小为0.2μm的滤膜上进行抽滤,抽滤干后取出,在40℃烘箱中干燥5min,在滤膜背面滴加乙醇溶液,将O-g-C3N4/GO/N-CNT膜从滤膜上揭下,最终得到氧化石墨相单层C3N4复合膜材料。
4.一种由权利要求1-3任意一种方法得到的氧化石墨相单层C3N4复合膜材料。
5.权利要求4所述的氧化石墨相单层C3N4复合膜材料在光催化降解水中抗生素分子方面的用途。
6.权利要求4所述的氧化石墨相单层C3N4复合膜材料在光催化降解水体中有机染料污染物分子方面的用途。
7.权利要求4所述的氧化石墨相单层C3N4复合膜材料在通过光催化自清洁实现对污染物分子的循环光降解方面的用途。
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