CN108126682B - 一种石墨烯杂化光催化剂水凝胶 - Google Patents
一种石墨烯杂化光催化剂水凝胶 Download PDFInfo
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Abstract
本发明公开了一种石墨烯杂化光催化剂水凝胶,属于纳米材料领域,用于治理水污染,包括以氧化石墨和光催化剂为原料,经还原反应和超声处理得到的产物;本发明能够促进氧化石墨烯在水中的分散,避免纳米光催化剂在水凝胶形成过程中发生进一步聚集,可明显提高比表面积和吸附能力,具有更加明显的三维相互交联的中孔微结构,可实现吸附富集与光催化降解的协同效应,使吸附富集污染物的原位催化降解能力显著增强,可大幅度提高污染物的矿化和去除效率。
Description
技术领域
本发明涉及石墨烯,尤其是一种石墨烯杂化光催化剂水凝胶,属于纳米材料领域,用于治理水污染。
背景技术
水污染是环境污染的一个重要方面,严重制约了生活质量的提高。水中污染物种类繁多,不仅有重金属离子的污染,还存在低浓度的有毒有害难降解有机物的污染,如苯酚、4-氯酚、多氯联苯、多溴联苯醚、全氟辛酸(磺酸)、双酚A等。这些污染物质具有环境持久性、生物累积性、高毒性和难降解特性,对人类健康和生态安全构成了严重威胁。
在处理水中低浓度高毒性有机污染上,还存在很多关键性技术难题,难以同时满足技术和经济上的要求,在实际应用中具有很大的局限性。尽管吸附法(如仅使用石墨烯吸附性材料)和光催化法都对于处理水中有机污染物的有一定的作用,但单独使用时都存在一些弊端和关键问题需要解决,无法高效去除水中有机污染物。
专利文献CN107020073A公开了一种基于石墨烯的光催化剂材料的制备方法,以氯化镧、钛源和石墨烯为原料,经沉淀曝气反应得到钛酸镧,并与石墨烯进行超声与光照反应得到石墨烯-钛酸镧材料,但存在制备方法步骤较为繁琐、生产成本高、石墨烯容易发生团聚、催化活性和处理效率不高的问题。
发明内容
本发明需要解决的技术问题是提供一种石墨烯杂化光催化剂水凝胶,能够克服石墨烯容易发生团聚的问题,具有比表面积大、分散效果好、机械强度高、制备方法简单、原料易得的优点,能够有效吸附水中有机污染物,并具有良好的去除效果。
为解决上述技术问题,本发明所采用的技术方案是:
一种石墨烯杂化光催化剂水凝胶,包括以氧化石墨和光催化剂为原料,经还原反应和超声处理得到的产物。
本发明的技术方案的进一步改进在于:所述光催化剂为TiO2、ZnO、CdS、BiPO4、Bi2WO6、Bi2MoO6中的任一种或几种的混合。
本发明的技术方案的进一步改进在于制备方法包括如下步骤:
A.将氧化石墨制备成氧化石墨烯水溶液后进行机械剥离,去除未剥离的氧化石墨烯;
B.将剥离得到的氧化石墨烯与光催化剂混合,超声分散后搅拌;
C.加入还原剂反应,然后加热,取沉淀干燥后得到石墨烯杂化光催化剂;
D.将石墨烯杂化光催化剂先与氧化石墨烯水溶液混合,再加入还原剂反应后得到石墨烯杂化光催化剂水凝胶。
本发明的技术方案的进一步改进在于:所述氧化石墨采用Hummers’法制备得到,氧化石墨烯水溶液的制备方法为将氧化石墨在去离子水中用超声分散80~150min,氧化石墨烯水溶液浓度为1.0~2.0mg/ml。
本发明的技术方案的进一步改进在于:机械剥离的离心条件为2000~4000rpm,去除未剥离的氧化石墨烯的方式为离心。
本发明的技术方案的进一步改进在于:步骤B中氧化石墨烯与光催化剂的质量比为1:100~1000,超声分散的时间为10~60min,搅拌的速度为400~600rpm,搅拌的时间为6~36h。
本发明的技术方案的进一步改进在于:所述还原剂为抗坏血酸、水合肼、对苯二酚、硼氢化钠、氢氧化钠、乙二胺、氢碘酸、硫脲中的任一种。
本发明的技术方案的进一步改进在于:步骤C中加入还原剂的质量为光催化剂质量的5~20倍,反应时间为10~60min,然后80~100℃水浴锅中加热30~80min,干燥温度为60~90℃,干燥时间为8~15小时。
本发明的技术方案的进一步改进在于:步骤D中石墨烯杂化光催化剂与氧化石墨烯水溶液的质量比为1:4~4:1,混合方式为超声分散10~60min,石墨烯杂化光催化剂与还原剂的质量比为1:5~20,反应前先搅拌15~40min,反应温度为80~100℃,反应时间为20~80min。
由于采用了上述技术方案,本发明取得的技术进步是:
本发明能够促进氧化石墨烯在水中的分散,避免纳米光催化剂在水凝胶形成过程中发生进一步聚集,可明显提高比表面积和吸附能力,具有更加明显的三维相互交联的中孔微结构,可实现吸附富集与光催化降解的协同效应,使吸附富集污染物的原位催化降解能力显著增强,可大幅度提高污染物的矿化和去除效率。
本发明通过将氧化石墨烯的胶凝化以及与光催化剂进行结合,可以形成对污染物同时具有吸附富集和原位光催化降解性能的复合水凝胶,克服了单一吸附方法和光催化方法在处理水中有机污染物的局限性,其中的光催化剂还能够起到促进氧化石墨烯的分散的作用,从而获得更高比表面积和吸附能力,进一步提高污染物的去除和矿化性能,大幅度提高污染物的降解效率。
本发明利用了石墨烯表面的吸附富集特性及对光催化活性物种的优异传导能力,可以实现吸附富集与光催化深度矿化降解的协同效应,解决了水中有毒有害难降解污染物难以高效去除的问题,尤其可大幅度提高水中低浓度有机污染物的矿化能力和去除效率,对保护水资源、减少环境污染具有重要意义。
本发明能够形成网状结构的水凝胶,比表面积大,具有快速吸附富集特点,并且有很好的机械强度,同时保持了石墨烯的片层结构,易于实现拆分、分离。这样的结构不仅可以解决石墨烯吸附剂及光催化剂在净化处理后的分离去除污染物问题,还可以大幅度降低石墨烯的聚集态,提高吸附容量,解决吸附剂的饱和与二次污染的问题。而且本发明具有自再生性能,可实现反复循环使用,无需进行脱附处理,大大减少了污染处理的成本和难度。
本发明的制备方法具有操作简单、反应条件温和、原料来源丰富的优点,并且将反应原料的配比和工艺条件控制在最适宜的范围内,使反应高效进行,减少副反应的发生,提高收率和纯度,并使产物保持很高的活性。通过采用还原剂还原与超声结合的方法,利用含有共轭大π键的氧化石墨烯与光催化剂剂进行表面杂化,可大幅度提高光催化活性、抑制光腐蚀发生以及实现可见光活性,还可以成倍提高光催化的降解和矿化性能。
附图说明
图1为本发明与对照组的循环使用测试结果。
具体实施方式
下面是本发明的一些具体实施方式,用以作进一步详细说明。
一种石墨烯杂化光催化剂水凝胶,包括以氧化石墨和光催化剂为原料,经还原反应和超声处理得到的产物;所述光催化剂为TiO2、ZnO、CdS、BiPO4、Bi2WO6、Bi2MoO6中的任一种或几种的混合。
其制备方法包括如下步骤:
A.将氧化石墨与去离子水混合后用超声分散80~150min,制备成浓度为1.0~2.0mg/ml的氧化石墨烯水溶液,然后进行机械剥离,机械剥离时的离心条件为2000~4000rpm,然后离心去除未剥离的氧化石墨烯。
所述氧化石墨采用Hummers’法制备得到,具体的制备方法为:利用3.0g石墨粉放入的三口圆底烧瓶中,将圆底烧瓶置于冰浴中固定,加入70mL浓硫酸并搅拌10min,使石墨粉与浓硫酸混合均匀。然后加入1.5g硝酸钠,待硝酸钠溶解以后,取三倍于石墨粉量的高锰酸钾缓慢加入到上述混合溶液中,继续搅拌2.5h,搅拌过程中水浴温度严格控制在20℃以下。加热到35℃继续对石墨粉进行氧化3.5h,然后向圆底烧瓶中加入150mL蒸馏水,并加快体系的搅拌速度,促进热量的散失,在95℃下进行水浴反应1.5h。反应结束以后,向圆底烧瓶中加入150mL蒸馏水与20mL的H2O2,此过程为石墨粉的氧化过程,此时混合溶液呈现土黄色,静置,用稀盐酸与去离子水洗至溶液pH显示中性,即完成氧化石墨的制备。
B.将剥离得到的氧化石墨烯与光催化剂按质量比为1:100~1000混合,超声分散10~60min后剧烈搅拌6~36h,搅拌的速度为400~600rpm。
C.向步骤B中得到的溶液中加入还原剂,加入还原剂的质量为光催化剂质量的5~20倍,反应10~60min,然后在80~100℃水浴锅中加热30~80min,取沉淀在60~90℃下干燥8~15小时后得到石墨烯杂化光催化剂。
D.将石墨烯杂化光催化剂先与氧化石墨烯水溶液按质量比为1:4~4:1混合,超声分散10~60min,再加入还原剂,石墨烯杂化光催化剂与加入的还原剂的质量比为1:5~20,先搅拌15~40min,然后加热至80~100℃反应20~80min得到石墨烯杂化光催化剂水凝胶。
步骤B和C中的还原剂为抗坏血酸、水合肼、对苯二酚、硼氢化钠、氢氧化钠、乙二胺、氢碘酸、硫脲中的任一种,下面的实施例1~4仅使用了其中四种还原剂,使用其余的还原剂或者将其中任意几种混合使用时,也同样能起到相似的技术效果,达到本发明的目的。
实施例1~4
实施例1~4与上述制备反应步骤相同,所不同的反应条件如下表所示。其中,“超声A”表示步骤A中超声分散的时间,“浓度”表示氧化石墨烯水溶液的浓度,“离心”表示机械剥离时的离心条件,“质量比X”表示步骤B中氧化石墨烯与光催化剂的质量比,“超声B”表示步骤B中超声分散的时间,“质量比W”表示步骤C中光催化剂与还原剂的质量比,“质量比Y”表示步骤D中石墨烯杂化光催化剂先与氧化石墨烯水溶液的质量,“超声D”表示步骤D中超声分散的时间,“质量比Z”表示步骤D中石墨烯杂化光催化剂与加入的还原剂的质量比。
为了更好地验证本发明的制备方法的优越性,使用本发明实施例1~4中所制备得到的石墨烯杂化光催化剂水凝胶进行了产品检测及分析,具体检测结果如下,本发明的制备方法平均收率能达到94%,得到的纯度平均可达到99.3%。
收率(%) | 纯度(%) | |
实施例1 | 93 | 99.2 |
实施例2 | 94 | 99.5 |
实施例3 | 97 | 99.4 |
实施例4 | 92 | 99.1 |
平均值 | 94 | 99.3 |
为了更好地验证本发明在处理水污染效果上的优越性,使用本发明实施例1~4中所制备得到的石墨烯杂化光催化剂水凝胶对含有有机污染物的水质进行了处理,并在处理前后进行了取样检测与分析,检测结果如下。处理各个样品中污染水中主要有害成分平均含量为多环芳烃含53.49μg/L,苯[α]并芘含0.45μg/L,氰化物含0.39mg/L,使用本发明实施例1~4的产品处理后水中各成分含量如下:
由以上数据可以看出,本发明可使COD去除率和色度去除率均高达85%以上,使多环芳烃在50μg/L以下,苯并芘在0.03μg/L以下,氰化物达到0.2mg/L以下,符合国家对废水排放的限值要求。
发明人使用本发明实施例制备的产品和其他吸附性材料的污水处理剂对同样的污水样品进行循环使用试验。图1为产品测试结果,实验组为本发明实施例1~4的产品处理的平均值,对照组为采用三种市售普通吸附性材料处理的平均值,使用频次为将产品循环使用的次数。
从循环使用测试结果中可以看出,本发明的产品能够反复循环使用,而且多次使用后仍能对污水有较高的处理效率,使用频次对使用效果的影响很小。而对照组多次使用后处理效率会大大降低,无法循环使用。
Claims (7)
1.一种石墨烯杂化光催化剂水凝胶,其特征在于,制备方法包括如下步骤:
A.将氧化石墨制备成氧化石墨烯水溶液后进行机械剥离,去除未剥离的氧化石墨烯;
B.将剥离得到的氧化石墨烯与光催化剂混合,超声分散后搅拌;
C.加入还原剂反应,然后加热,取沉淀干燥后得到石墨烯杂化光催化剂;
D.将石墨烯杂化光催化剂先与氧化石墨烯水溶液混合,再加入还原剂反应后得到石墨烯杂化光催化剂水凝胶。
2.根据权利要求1所述的一种石墨烯杂化光催化剂水凝胶,其特征在于:所述氧化石墨采用Hummers’法制备得到,氧化石墨烯水溶液的制备方法为将氧化石墨在去离子水中用超声分散80~150min,氧化石墨烯水溶液浓度为1.0~2.0mg/ml。
3.根据权利要求1所述的一种石墨烯杂化光催化剂水凝胶,其特征在于:机械剥离的离心条件为2000~4000rpm,去除未剥离的氧化石墨烯的方式为离心。
4.根据权利要求1所述的一种石墨烯杂化光催化剂水凝胶,其特征在于:步骤B中氧化石墨烯与光催化剂的质量比为1:100~1000,超声分散的时间为10~60min,搅拌的速度为400~600rpm,搅拌的时间为6~36h。
5.根据权利要求1所述的一种石墨烯杂化光催化剂水凝胶,其特征在于:所述还原剂为抗坏血酸、水合肼、对苯二酚、硼氢化钠、氢氧化钠、乙二胺、氢碘酸、硫脲中的任一种。
6.根据权利要求1所述的一种石墨烯杂化光催化剂水凝胶,其特征在于:步骤C中加入还原剂的质量为光催化剂质量的5~20倍,反应时间为10~60min,然后80~100℃水浴锅中加热30~80min,干燥温度为60~90℃,干燥时间为8~15小时。
7.根据权利要求1所述的一种石墨烯杂化光催化剂水凝胶,其特征在于:步骤D中石墨烯杂化光催化剂与氧化石墨烯水溶液的质量比为1:4~4:1,混合方式为超声分散10~60min,石墨烯杂化光催化剂与还原剂的质量比为1:5~20,反应前先搅拌15~40min,反应温度为80~100℃,反应时间为20~80min。
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