CN107321340B - 一种多级孔结构的石墨烯复合光催化气凝胶及其制备方法 - Google Patents
一种多级孔结构的石墨烯复合光催化气凝胶及其制备方法 Download PDFInfo
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Abstract
本发明提出了一种多级孔结构的石墨烯复合光催化气凝胶及其制备方法,所述石墨烯复合光催化气凝胶具有层状结构和三维立体结构,并且具有大孔、中孔和微孔的多级孔结构。将石墨烯气凝胶的吸附作用与二氧化钛光催化作用相结合,利用纳米TiO2的光催化作用快速降解吸附在石墨烯气凝胶内部孔隙和表面上的污染物,使石墨烯气凝胶原位再生,从而延长石墨烯气凝胶的吸附饱和时间,大幅提升去污效果。可根据实际应用需求,较为便捷地通过改变加入的活性炭纤维的种类和添加量对复合石墨烯气凝胶内部的多级孔结构加以调控,从而提高其对不同污染物适用的广谱性。并且整套合成工艺简单,化学还原原位自组装过程中无需搅拌,反应条件温和。
Description
技术领域
本发明为气凝胶的制备领域,尤其涉及一种石墨烯复合光催化气凝胶及其制备方法。
背景技术
石墨烯是一种通过碳原子sp2杂化形成的六边形蜂窝状结构二维原子晶体,其特殊的二维结构,致使其在导电性,导热性等诸多方面具有非常优异的性能。但是,石墨烯二维材料往往会因受π-π相互作用而团聚、堆积,导致比表面积缩小,电阻增大,性能大幅降低,从而在一定程度上限制了石墨烯在应用方面的拓展。石墨烯气凝胶(grapheneaerogel,GA)是以二维的石墨烯作为构筑单元,通过纳米片之间的卷曲和堆叠,形成的具有独特三维结构的纳米材料,不但可以很好的解决二维材料在应用上的困难,而且具有超低密度、高比表面积和孔隙率、高电导率等,在吸附、催化剂载体、能量储存、传感器等领域具有很好的应用前景。石墨烯气凝胶的物化性质与其内部孔径大小密切相关,现有石墨烯气凝胶内部孔径大多为毫米级的大孔,对大部分污染物尤其是分子直径较小的污染物的吸附作用力不强,容易扩散,从而降低了其吸附能力,并且孔径分布范围较窄,因而无法满足实际应用中污染物形态多样、组分复杂的使用要求。另一方面,单纯依靠石墨烯气凝胶的吸附作用去除污染物,对污染物只是实现了转移,并没有实现彻底的降解,易脱附产生二次污染;而且石墨烯气凝胶吸附容量有限,吸附饱和后会影响其连续使用,需更换或脱附再生后才能恢复吸附性能。
此外,在合成气凝胶的工艺中,目前较常用的方法是水热法。但是,水热法合成石墨烯气凝胶工艺相对比较复杂,并且对反应条件的要求相对较为苛刻,如高温高压的环境等。
发明内容
本发明的目的在于提出一种多级孔结构的石墨烯复合光催化气凝胶及其制备方法,以解决背景技术中现有的石墨烯气凝胶存在的孔结构单一、吸附能力不足、易产生二次污染、合成工艺复杂、条件苛刻等问题。
为实现上述目的,本发明采用如下技术方案提供一种多级孔结构的石墨烯复合光催化气凝胶,所述石墨烯复合光催化气凝胶具有层状结构和三维立体结构,并且具有大孔、中孔和微孔的多级孔结构;所述石墨烯复合光催化气凝胶包括石墨烯气凝胶、纳米二氧化钛和活性炭纤维,其中,所述纳米二氧化钛和活性炭纤维均匀分散在大孔结构的石墨烯气凝胶内部。
优选的,所述大孔的孔径大于50nm,所述中孔的孔径为大于等于2nm且小于等于50nm,所述微孔的孔径小于2nm。
此外,本发明还提出一种多级孔结构的石墨烯复合光催化气凝胶的制备方法,包括以下步骤:
(1)将氧化石墨烯加入到去离子水中,经超声分散1~4h直至混合均匀,制得质量浓度为0.5~20mg/mL的氧化石墨烯分散液。
(2)按活性炭纤维与所述氧化石墨烯的质量比为(0.01~1):1的比例,将所述活性炭纤维加入到所述氧化石墨烯分散液中,并经所述超声分散或机械搅拌直至混合均匀,制得所述氧化石墨烯和所述活性炭纤维的混合溶液。
(3)按纳米二氧化钛与所述氧化石墨烯的质量比为(1~10):1的比例,将所述纳米二氧化钛加入到所述氧化石墨烯和所述活性炭纤维的混合溶液中,并经所述超声分散或所述机械搅拌直至混合均匀,制得所述氧化石墨烯、所述纳米二氧化钛和所述活性炭纤维的混合溶液。
(4)向所述氧化石墨烯、所述纳米二氧化钛和所述活性炭纤维的混合溶液中加入还原剂,并经所述超声分散或所述机械搅拌直至混合均匀,然后放入80~120℃的水浴锅中,经1~5h原位自组装得到被还原后石墨烯、所述纳米二氧化钛和所述活性炭纤维三维复合光催化水凝胶。
(5)将所述三维复合光催化水凝胶进行冷冻干燥或超临界干燥,制得所述石墨烯、所述纳米二氧化钛和所述活性炭纤维三维复合光催化气凝胶。
优选的,步骤(1)中所述氧化石墨烯采用Hummers化学法制备而成。
优选的,在步骤(2)中所述活性炭纤维,包括粘胶基、聚丙烯腈基、酚醛基或黄麻基等不同种类的活性炭纤维。
优选的,在步骤(4)中所述还原剂为亚硫酸氢钠、硫化钠、水合肼、硼氢化钠、甲醛、糖类化合物、抗坏血酸、氢碘酸或对苯二酚等还原剂。
优选的,在步骤(5)中,所述超临界干燥为乙醇超临界干燥或二氧化碳超临界干燥。
优选的,在步骤(5)中,所述冷冻干燥为定向冷冻干燥或非定向冷冻干燥,冷冻温度为-1~-196℃,干燥温度为0~60℃,干燥真空度为5~50000Pa,干燥时间为10~60h。
优选的,在步骤(2)、(3)、(4)中,所述超声分散的超声功率为40~480W,超声频率为20~80KHz,所述机械搅拌的转速为40~4000r/min。
和现有技术相比,本发明的有益效果主要体现在:将石墨烯气凝胶的吸附作用与二氧化钛光催化作用相结合,利用纳米TiO2的光催化作用快速降解吸附在石墨烯气凝胶内部孔隙和表面上的污染物,使石墨烯气凝胶原位再生,从而延长石墨烯气凝胶的吸附饱和时间,大幅提升去污效果。可根据实际应用需求,较为便捷地通过改变加入的活性炭纤维的种类和添加量对复合石墨烯气凝胶内部的多级孔结构加以调控,从而提高其对不同污染物适用的广谱性。并且整套合成工艺简单,化学还原原位自组装过程中无需搅拌,反应条件温和。
附图说明
图1是本发明制备石墨烯复合光催化气凝胶的工艺流程图;
图2是本发明一实施例中将成品石墨烯复合光催化气凝胶放大300倍后的SEM图;
图3是本发明一实施例中将成品石墨烯复合光催化气凝胶放大1000倍后的SEM图;
图4是本发明一实施例中石墨烯复合光催化气凝胶氮气吸脱附等温线图。
具体实施方案
为使本发明的目的、技术方案和优点更加清楚,下面将对本发明的技术方案做进一步的说明。
在本实施例中,提出了一种多级孔结构的石墨烯复合光催化气凝胶,所述石墨烯复合光催化气凝胶具有层状结构和三维立体结构,并且具有大孔、中孔和的微孔的多级孔结构;所述石墨烯复合光催化气凝胶包括石墨烯气凝胶、纳米二氧化钛和活性炭纤维,其中,所述纳米二氧化钛和活性炭纤维均匀分散在大孔径结构的石墨烯气凝胶内部。
在本实施例中,大孔的孔径大于50nm,中孔的孔径为大于等于2nm且小于等于50nm,微孔的孔径小于2nm。多级孔结构提高了对不同污染物适用的广谱性。
在本实施例中,如图1所述,还包括一种多级孔结构的石墨烯复合光催化气凝胶的制备方法;包括以下步骤:
(1)将氧化石墨烯加入到去离子水中,经超声分散1~4h直至混合均匀,制得质量浓度为0.5~20mg/mL的氧化石墨烯分散液。
(2)按活性炭纤维与所述氧化石墨烯的质量比为(0.01~1):1的比例,将所述活性炭纤维加入到所述氧化石墨烯分散液中,并经所述超声分散或机械搅拌直至混合均匀,制得所述氧化石墨烯和所述活性炭纤维的混合溶液。
(3)按纳米二氧化钛与所述氧化石墨烯的质量比为(1~10):1的比例,将所述纳米二氧化钛加入到所述氧化石墨烯和所述活性炭纤维的混合溶液中,并经所述超声分散或所述机械搅拌直至混合均匀,制得所述氧化石墨烯、所述纳米二氧化钛和所述活性炭纤维的混合溶液。
(4)向所述氧化石墨烯、所述纳米二氧化钛和所述活性炭纤维的混合溶液中加入还原剂,并经所述超声分散或所述机械搅拌直至混合均匀,然后放入80~120℃的水浴锅中,经1~5h原位自组装得到倍还原后石墨烯、所述纳米二氧化钛和所述活性炭纤维三维复合光催化水凝胶。
(5)将所述三维复合光催化水凝胶进行冷冻干燥或超临界干燥,制得所述石墨烯、所述纳米二氧化钛和所述活性炭纤维三维复合光催化气凝胶。
在本实施例中,步骤(1)中所述氧化石墨烯采用Hummers化学法制备而成。
在本实施例中,在步骤(2)中所述活性炭纤维,包括粘胶基、丙烯腈基、酚醛基或黄麻基等不同品种的活性炭纤维。
在本实施例中,在步骤(4)中所述还原剂为亚硫酸氢钠、硫化钠、水合肼、硼氢化钠、甲醛、糖类化合物、抗坏血酸、氢碘酸或对苯二酚等还原剂。
在本实施例中,在步骤(5)中,所述超临界干燥为乙醇超临界干燥或二氧化碳超临界干燥。
在本实施例中,在步骤(5)中,所述冷冻干燥为定向冷冻干燥或非定向冷冻干燥,冷冻温度为-1~-196℃,干燥温度为0~60℃,干燥真空度为5~50000Pa,干燥时间为10~60h。
在本实施例中,在步骤(2)、(3)、(4)中,所述超声分散的超声功率为40~480W,超声频率为20~80KHz,所述机械搅拌的转速为40~4000r/min。
在本实施例中,还包括一组拥有固定成分配比的实验,实验内容如下:
实验试剂:氧化石墨烯、纳米二氧化钛、粘胶基活性炭纤维、亚硫酸氢钠。
(1)称取一定质量的氧化石墨烯,将其直接放入去离子水(即蒸馏水)中,配置成浓度为2mg/mL的氧化石墨烯水溶液,放在超声清洗机中使用350W的功率超声3h,充分超声得到均匀的石墨烯分散液。
(2)将超声完的溶液放置片刻之后,称取相应质量的粘胶基活性炭纤维加石墨烯水溶液中,充分摇匀,放入超声清洗机中以100W的功率超声5min,之后称取相应质量的纳米二氧化钛加入溶液中,以100W的功率再超声5min,即可制得这三种原料的均匀混合溶液,最后加入适量还原剂亚硫酸氢钠以100W超声2min即可。
(3)使用移液管从瓶中量取所需溶液的量,放入适当的容器中,将容器放在水浴锅中,在95℃的恒温水浴中反应2h,得到氧化石墨烯、纳米二氧化钛和粘胶基活性炭纤维三维复合光催化水凝胶。
(4)将所述复合光催化水凝胶从瓶中取出,用实验用的去离子水多次洗涤至中性,也可以浸泡一段时间。
(5)取出所述复合光催化水凝胶放在干净的瓶中,将其放在冰箱中进行2h的预冻,预冻完成后将样品放入冷冻干燥机中以-70℃冷冻干燥48h后取出,得到氧化石墨烯、纳米二氧化钛和粘胶基活性炭纤维三维复合光催化气凝胶。
在本试验中,石墨烯:纳米二氧化钛:粘胶基活性炭纤维三组分含量配比为1:2:0.15。
在本实验中,如图2、图3所示,从图中可以看出石墨烯复合光催化气凝胶具有一定的层状结构,由此可见所述石墨烯复合光催化气凝胶具有三维立体结构;纳米二氧化钛和粘胶基活性炭纤维均匀分散在大孔结构的石墨烯气凝胶的内部。
在本试验中,如图4、以及表1所示,从图中可以看出所述石墨烯复合光催化气凝胶呈现出大孔-中孔-微孔的多级孔结构,并且以中孔为主。各种类型孔所占的比例,可以通过改变各组分占比加以调节。
表1石墨烯/纳米TiO2/粘胶基活性炭纤维复合气凝胶孔结构参数表
Claims (7)
1.一种多级孔结构的石墨烯复合光催化气凝胶的制备方法,其特征在于,包括以下步骤:
(1)将氧化石墨烯加入到去离子水中,经超声分散1~4h直至混合均匀,制得质量浓度为0.5~20mg/mL的氧化石墨烯分散液;
(2)按活性炭纤维与所述氧化石墨烯的质量比为(0.01~1):1的比例,将所述活性炭纤维加入到所述氧化石墨烯分散液中,并经所述超声分散或机械搅拌直至混合均匀,制得所述氧化石墨烯和所述活性炭纤维的混合溶液;
(3)按纳米二氧化钛与所述氧化石墨烯的质量比为(1~10):1的比例,将所述纳米二氧化钛加入到所述氧化石墨烯和所述活性炭纤维的混合溶液中,并经所述超声分散或所述机械搅拌直至混合均匀,制得所述氧化石墨烯、所述纳米二氧化钛和所述活性炭纤维的混合溶液;
(4)向所述氧化石墨烯、所述纳米二氧化钛和所述活性炭纤维的混合溶液中加入还原剂,并经所述超声分散或所述机械搅拌直至混合均匀,然后放入80~100℃的水浴锅中,经1~5h原位自组装得到被还原后石墨烯、所述纳米二氧化钛和所述活性炭纤维三维复合光催化水凝胶;
(5)将所述三维复合光催化水凝胶进行冷冻干燥或超临界干燥,制得所述石墨烯、所述纳米二氧化钛和所述活性炭纤维三维复合光催化气凝胶;
所述石墨烯复合光催化气凝胶具有层状结构和三维立体结构,并且具有微孔、中孔和大孔的多级孔结构;所述石墨烯复合光催化气凝胶包括石墨烯气凝胶、纳米二氧化钛和活性炭纤维,其中,所述纳米二氧化钛和活性炭纤维均匀分散在大孔结构的石墨烯气凝胶内部。
2.根据权利要求1所述的多级孔结构的石墨烯复合光催化气凝胶的制备方法,其特征在于,步骤(1)中所述氧化石墨烯采用Hummers化学法制备而成。
3.根据权利要求1所述的多级孔结构的石墨烯复合光催化气凝胶的制备方法,其特征在于,在步骤(2)中所述活性炭纤维,包括粘胶基、聚丙烯腈基、酚醛基或黄麻基不同种类的活性炭纤维。
4.根据权利要求1所述的多级孔结构的石墨烯复合光催化气凝胶的制备方法,其特征在于,在步骤(4)中所述还原剂为亚硫酸氢钠、硫化钠、水合肼、硼氢化钠、甲醛、糖类化合物、抗坏血酸、氢碘酸或对苯二酚还原剂。
5.根据权利要求1所述的多级孔结构的石墨烯复合光催化气凝胶的制备方法,其特征在于,在步骤(5)中,所述超临界干燥为乙醇超临界干燥或二氧化碳超临界干燥。
6.根据权利要求1所述的多级孔结构的石墨烯复合光催化气凝胶的制备方法,其特征在于,在步骤(5)中,所述冷冻干燥为定向冷冻干燥或非定向冷冻干燥,冷冻温度为-1~-196℃,干燥温度为0~60℃,干燥真空度为5~50000Pa,干燥时间为10~60h。
7.根据权利要求1所述的多级孔结构的石墨烯复合光催化气凝胶的制备方法,其特征在于,在步骤(2)、步骤(3)和步骤(4)中,所述超声分散的超声功率为40~480W,超声频率为20~80KHz,所述机械搅拌的转速为40~4000r/min。
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