CN108380213A - 一种可磁性回收的石墨烯/二氧化钛光催化复合材料及其制备方法 - Google Patents
一种可磁性回收的石墨烯/二氧化钛光催化复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种可磁性回收的石墨烯/二氧化钛光催化复合材料及其制备方法。具体步骤如下:(1)制备聚丙烯酸修饰的四氧化三铁溶液;(2)制备石墨烯/二氧化钛光催化材料;再将其用水分散;(3)制备聚乙烯亚胺修饰的石墨烯/二氧化钛溶液;(4)利用静电自组装,将聚丙烯酸修饰的四氧化三铁溶液和聚乙烯亚胺修饰的石墨烯/二氧化钛溶液常温孵化,离心,得到磁性四氧化三铁修饰石墨烯/二氧化钛复合材料;(5)将上述复合材料热处理,得到可磁性回收的石墨烯/二氧化钛光催化复合材料。本发明制备的光催化复合材料可见光催化降解活性高,光催化表面大,通过调控四氧化三铁的自组装含量,可以实现在复杂环境中的有效回收。
Description
技术领域
本发明属于光催化技术领域,具体的说,涉及一种可磁性回收的石墨烯/二氧化钛光催化复合材料及其制备方法。
背景技术
国内外对于环境污染的处理方法主要有投加絮凝剂、电化学方法、空气氧化法和生物处理等物理和化学方法,但这些方法都存在运行费用高,且仍伴有大量废物产生等缺点。光催化技术具有能耗低、操作简便、反应条件温和、无二次污染等突出优点,因此光催化降解处理技术是目前绿色处理水污染的一个重要研究热点。目前光催化剂主要以二氧化钛(TiO2)为主要成分,但是单一二氧化钛材料存在光转化效率低、禁带宽度单一、光生电子-空穴的复合效率高等缺点,限制二氧化钛的光催化降解效率。石墨烯(G)作为一种零带隙的半导体材料,其碳原子间以独特的sp2杂化结构组成,具有优异的电子传输特性,同时具有巨大的理论表面积,使得其在光学、生物传感、环境科学等领域具有广阔的应用前景。单一的TiO2/G复合材料在环境应用中,存在难回收、易分散等缺点,限制其大规模应用。四氧化三铁(Fe3O4)纳米粒子是一种常见的磁性材料,其制备方法多样、操作简单、成本低廉,是一种具有超顺磁性及高饱和磁化强度的纳米材料。
发明内容
为了克服现有技术的不足,本发明提供一种集磁性、吸附性、光催化活性于一体的可磁性回收的石墨烯/二氧化钛光催化复合材料及其制备方法。本发明通过自组装法,将四氧化三铁纳米颗粒静电自组装于二氧化钛/石墨烯材料上,再经高温处理,得到具有高催化活性、高表面积、高强磁响应性和高吸附特性的光催化材料,其在环境有机染料和污染物的光催化处理等领域具有广泛的应用前景。
本发明的技术方案具体介绍如下。
一种可磁性回收的石墨烯/二氧化钛光催化复合材料的制备方法,包括以下步骤:
(1)纳米四氧化三铁分散液和聚丙烯酸溶液混合搅拌20-50min,得到聚丙烯酸修饰的四氧化三铁溶液;
(2)将钛酸四乙酯醇溶液和氧化石墨烯溶液混合后,130℃-160℃反应24h-48h,得到石墨烯/二氧化钛光催化材料;再将石墨烯/二氧化钛光催化材料用水分散液,得到石墨烯/二氧化钛分散液;
(3)将石墨烯/二氧化钛分散液和聚乙烯亚胺溶液混合搅拌20-50min,得到聚乙烯亚胺修饰的石墨烯/二氧化钛溶液;
(4)利用静电自组装,将步骤(1)得到的聚丙烯酸修饰的四氧化三铁溶液和步骤(3)聚乙烯亚胺修饰的石墨烯/二氧化钛溶液在常温下孵化20-30h,离心,制备得到磁性四氧化三铁修饰石墨烯/二氧化钛复合材料;
(5)将磁性四氧化三铁修饰石墨烯/二氧化钛复合材料进行热处理,得到可磁性回收的石墨烯/二氧化钛光催化复合材料。
本发明中,步骤(1)中,纳米四氧化三铁分散液的浓度为60~80mg/mL,聚丙烯酸溶液的浓度为0.8~1.2mg/mL,纳米四氧化三铁分散液和聚丙烯酸溶液的体积比为60:1~180:1。
本发明中,步骤(2)中,钛酸四乙酯醇溶液中,钛酸四乙酯和醇的体积比为1:4~1:10;氧化石墨烯溶液的浓度为0.5~5mg/mL;钛酸四乙酯醇溶液和氧化石墨烯溶液的体积比为1:5~1:10;石墨烯/二氧化钛分散液的浓度为_0.8~1.5mg/mL。
本发明中,步骤(1)中,纳米四氧化三铁由柠檬酸钠和氯化铁在乙二醇溶液中进行溶剂热反应得到;步骤(2)中,氧化石墨烯通过改进的Hummers法制备得到。
本发明中,步骤(3)中,石墨烯/二氧化钛分散液和聚乙烯亚胺溶液的体积比为30:1~120:1。
本发明中,步骤(4)中,聚丙烯酸修饰的四氧化三铁溶液和聚乙烯亚胺修饰的石墨烯/二氧化钛溶液的体积比为1:4~1:10。
本发明中,步骤(5)中,热处理温度为480-520℃,热处理时间为2-5h。
本发明还提供一种上述的制备方法制备得到的可磁性回收的石墨烯/二氧化钛光催化复合材料。
与现有技术相比,本发明具有的有益效果在于:
1、本发明制备的磁性石墨烯/二氧化钛复合材料不仅有效提高可见光的催化活性,而且在外加磁场条件下可以有效实现催化剂回收。同时高温整合有利于石墨烯与四氧化三铁增强光敏化作用,提高复合材料的光催化性能。
2、本发明采用聚合物静电自组装技术将四氧化三铁修饰于石墨烯/二氧化钛材料表面,磁性物质能够稳定于材料基底,可通过调整四氧化三铁组装量,实现复杂环境中材料的有效回收,具有操作简便、磁性可控、环境污染小、回收率高等特点。
3、本发明制备的磁性石墨烯/二氧化钛复合材料同时具有高表面光催化活性、强磁响应性、高比表面积和高吸附特性。
附图说明
图1是实施例1中制备的氧化石墨烯的扫描电子显微镜图。
图2是实施例1中制备磁性石墨烯/二氧化钛的扫描电子显微镜图。
图3是实施例2中不同材料光催化降解亚甲基蓝的变化过程曲线图。
图4是实施例2中磁性石墨烯/二氧化钛材料降解亚甲基蓝的紫外光谱随时间变化图。
具体实施方式
下面结合附图和实施例对本发明的技术方案进行详细说明。
实施例1
(1)制备磁性四氧化三铁纳米粒子
将0.325g六水合三氯化铁和0.1g柠檬酸三钠溶于10mL乙二醇溶液中,经30min超声分散后再移至聚四氟乙烯水热高压反应釜,在200℃下反应10h,反应完全后冷却至室温,溶液颜色由深黄色变成黑色,用磁铁将磁性物质从溶液中分离出,用去离子水和无水乙醇反复洗涤后再用磁铁分离,然后将分离得到的磁性四氧化三铁纳米粒子在100℃下干燥12h,超声分散于10mL去离子水中,制备出80mg/ml磁性四氧化三铁纳米材料分散液。
(2)制备石墨烯/二氧化钛可见光响应催化剂
利用改进的Hummers法制备氧化石墨烯,主要反应分为三步:低温(0℃),中温(35℃),高温(80℃)进行合成。在冰水浴的条件下,依次在三口烧瓶中加入0.5g石墨粉,0.5g硝酸钠和20mL质量分数为98%的浓硫酸,均匀搅拌5min,然后缓慢加入3g的高锰酸钾,进行石墨的插层和预氧化,溶液黑色;将上述反应溶液转移到35℃的水浴中加热搅拌1h,进一步对石墨插层和氧化,溶液呈深棕色;然后在搅拌条件下加入50mL去离子水,持续加热30min后将温度提升到80℃。再依次加入100mL去离子水,3mL 30%过氧化氢溶液,达到硫酸与石墨层间水解,进一步拉开距离,此时溶液变成黄色。通过10000离心,多次洗涤,制备出氧化石墨烯,如图1,制备的氧化石墨烯具有较大的表面积,有效作为吸附载体。
将钛酸四乙酯与无水乙醇溶液按照体积比1:8进行配制,缓慢滴加到1mg/ml氧化石墨烯溶液中,均匀搅拌得到混合溶液,所述氧化石墨烯与钛酸四乙酯的醇溶液体积比10:1,钛酸四乙酯与石墨烯水解反应生成二氧化钛,于130℃-160℃反应24h-48h,温度低于130℃时,氧化石墨烯反应不充分,为了氧化石墨烯与二氧化钛充分反应,控制温度在140℃左右,反应时间36h,经过溶剂热反应后,二氧化钛生长于石墨烯表面,降低二氧化钛的禁带宽度,制备出具有可见光响应的石墨烯/二氧化钛光催化材料。
(3)采用静电自组装法制备磁性四氧化三铁修饰的石墨烯/二氧化钛材料
将2mL 1mg/mL的聚丙烯酸溶液逐滴加入到200ml磁性四氧化三铁纳米粒子(80mg/ml)的分散液中,室温反应1h,再以5,000rpm的速度离心分离除去多余电解质,制备出60mg/ml修饰磁性四氧化三铁溶液;将2mL 1mg/mL的聚乙烯亚胺溶液逐滴加入到150ml石墨烯二氧化钛的分散液(1.2mg/ml),室温反应1h,以5,000rpm的速度离心分离,除去多余的聚电解质,制备出1mg/ml修饰磁石墨烯二氧化钛溶液,再分别用5ml去离子水超声分散并体积比1:5混合,将四氧化三铁通过静电自组装方法修饰到石墨烯/二氧化钛基底,制备出磁性石墨烯/二氧化钛材料分散液。最后将样品在氮气保护下通过管式炉500℃中煅烧,控制升温时间并保温2h,对三种纳米材料的有机整合,如图2所示,石墨烯表面均匀负载二氧化钛和磁性四氧化三铁纳米粒子,制备的复合材料具有高表面积和强磁性等优点,通过表1,同时通过调控四氧化三铁与石墨烯/二氧化钛的混合体积比分别为1:1,1:5,1:10,从催化降解效率得出制备出体积比1:5的磁性石墨烯/二氧化钛复合材料具有显著的光催化效率,同时可以制备出不同磁性的材料,在外加磁场的条件下,适应于不同强度的磁场回收率。
表1:不同比例复合物在光照条件下降解染料效率
实施例2
将实施例1中制备的磁性石墨烯/二氧化钛复合材料作为光催化材料,应用于测定光降解亚甲基蓝的含量。
取5ml浓度为10mg/ml的亚甲基蓝溶液置于石英管中,添加光催化剂0.02g,依次放入光反应器中,暗区反应30min,待反应吸附达到平衡后,以汞灯,电流20A条件照射,每隔15min取一次样,离心分离,取上清液用紫外分光光度计扫描并在λ=650吸光度,根据原始浓度计算降解率为82%。如图3所示,分析单独二氧化钛、石墨烯/二氧化钛复合材料、磁性四氧化三铁与石墨烯/二氧化钛复合材料的混合、磁性四氧化三铁与石墨烯/二氧化钛进行高温有机整合的复合材料这四种不同材料样品的光催化降解效果,证明本发明所使用热处理进行有机整合的磁性石墨烯/二氧化钛复合材料能够有效降解亚甲基蓝,提高催化的比表面积与降解效率。同时本次制备的磁性四氧化三铁掺杂的石墨烯/二氧化钛复合材料,由于石墨烯与铁原子的引入,改变二氧化钛能级结构,能在半导体价带与导带之间引入一个新的杂质能级,促使可见光催化效率提高。通过图4,根据λ=650吸光度,通过光照时间的降低,亚甲基蓝的紫外信号特征峰明显下降,达到对亚甲基蓝的有效降解,证明该复合材料具有良好的光催化性能,同时在外加磁场能有效回收,提高利用效率,对于有机染料、废水污染处理等提供重要应用价值。
Claims (8)
1.一种可磁性回收的石墨烯/二氧化钛光催化复合材料的制备方法,其特征在于,包括以下步骤:
(1)纳米四氧化三铁分散液和聚丙烯酸溶液混合搅拌20-50min,得到聚丙烯酸修饰的四氧化三铁溶液;
(2)将钛酸四乙酯醇溶液和氧化石墨烯溶液混合后,130℃-160℃反应24h-48h,得到石墨烯/二氧化钛光催化材料;再将石墨烯/二氧化钛光催化材料用水分散液,得到石墨烯/二氧化钛分散液;
(3)将石墨烯/二氧化钛分散液和聚乙烯亚胺溶液混合搅拌20-50min,得到聚乙烯亚胺修饰的石墨烯/二氧化钛溶液;
(4)利用静电自组装,将步骤(1)得到的聚丙烯酸修饰的四氧化三铁溶液和步骤(3)聚乙烯亚胺修饰的石墨烯/二氧化钛溶液在常温下孵化20-30h,离心,制备得到磁性四氧化三铁修饰石墨烯/二氧化钛复合材料;
(5)将磁性四氧化三铁修饰石墨烯/二氧化钛复合材料进行热处理,得到可磁性回收的石墨烯/二氧化钛光催化复合材料。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,纳米四氧化三铁分散液的浓度为60~80mg/mL,聚丙烯酸溶液的浓度在0.8~1.2mg/mL之间,纳米四氧化三铁分散液和聚丙烯酸溶液的体积比为60:1~180:1。
3.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,钛酸四乙酯醇溶液中,钛酸四乙酯和醇的体积比为1:4~1:10;氧化石墨烯溶液的浓度为0.5~5mg/mL;钛酸四乙酯醇溶液和氧化石墨烯溶液的体积比为1:5~1:10;石墨烯/二氧化钛分散液的浓度为0.8~1.5mg/mL。
4.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,纳米四氧化三铁由柠檬酸钠和氯化铁在乙二醇溶液中进行溶剂热反应得到;步骤(2)中,氧化石墨烯通过改进的Hummers法制备得到。
5.根据权利要求1所述的制备方法,其特征在于,步骤(3)中,石墨烯/二氧化钛分散液和聚乙烯亚胺溶液的体积比为30:1~120:1。
6.根据权利要求1所述的制备方法,其特征在于,步骤(4)中,聚丙烯酸修饰的四氧化三铁溶液和聚乙烯亚胺修饰的石墨烯/二氧化钛溶液的体积比为1:4~1:10。
7.根据权利要求1所述的制备方法,其特征在于,步骤(5)中,热处理温度为480-520℃,热处理时间为2-5h。
8.一种根据权利要求1-7之一所述的制备方法制备得到的可磁性回收的石墨烯/二氧化钛光催化复合材料。
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