氧化石墨烯的合成、表征及其对U（Ⅵ）、Th（Ⅳ）、Eu（Ⅲ）的吸附研究
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摘要
石墨烯是当今科学界的研究热点之一,由于其结构中存在着大量的褶皱孔道以及褶皱孔穴,且具有较大的比表面积,作为一种新型的碳纳米吸附材料备受关注。而氧化石墨烯作为其氧化衍生物,不但具有上述性质,而且含有大量配位能力强的酸性氧基功能团,具有更好的吸附性能,更加适用于作为放射性核素的吸附剂,在放射性废物处理领域有潜在的应用价值。
本论文采用改进过的Hummers方法合成了氧化石墨烯,对该样品进行了一系列的表征(XRD,TEM, AFM,FT-IR,Raman,TGA等),用B.E.T法测定了其比表面积。分析结果如下：TEM,AFM表明该方法合成出了形貌上具有少量褶皱的单层和较少层数的氧化石墨烯。XRD,FTIR表明,氧化石墨烯的层间距变大,表面含有大量的羧基、羟基、环氧基等酸性氧基功能团。
采用批示法研究了所合成的氧化石墨烯对U(Ⅵ),Th(Ⅳ)和Eu(Ⅲ)的吸附行为。考察了固液比、溶液pH、背景电解质,腐殖质及水杨酸等对吸附的影响。结果表明,氧化石墨烯是一种较好的吸附材料,对U(Ⅵ),Th(Ⅳ)和Eu(Ⅲ)均有较强的吸附能力,常温下对Eu(Ⅲ)的吸附容量达15.40mg/g；离子强度对U(Ⅵ)在氧化石墨烯上的吸附影响显著,对Th(Ⅳ)、Eu(Ⅲ)在氧化石墨烯上的吸附影响较小；腐殖质、水杨酸均对氧化石墨烯的吸附性能存在着一定的抑制作用。探讨了吸附热力学和吸附动力学规律：U(Ⅵ)、Th(Ⅳ)及Eu(Ⅲ)在氧化石墨烯上的吸附动力学符合准二级动力学方程；热力学研究表明：用Freundlich模型可以更好的拟合U(Ⅵ)、Th(Ⅳ)在氧化石墨烯上的吸附行为；Eu(Ⅲ)在氧化石墨烯表面的吸附更接近于Langmuir吸附模型。
Graphene is one of the most concerning carbon nano-material in scientific communities recently. Because its special surface structure, such as large specific surface area and crumples, it can be concerned as a kind of suitible sorbents to extraction of radionuclides from aquous solutions. As its oxidized derivatives, graphene oxide(GO), with not only the above properties, but also a large number of acidic oxygen-containing functional groups, canbe predicted as a promising sorption material to radionuclides, which showes potential using in the treatment of radioactive waste.
In this paper, graphene oxide was synthesized from flake graphite by modified Hummers method and characterized by a series of methods (such as XRD, TEM, AFM,FT-IR,Raman, TGA etc).The results of TEM and AFM showed that the morphology of graphene oxide synthesized by modified hummers was single-layer with crumples and fewer layers.It was found from XRD and FT-IR that layer spacing of graphene oxide became larger. Meanwhile, a large amount of functional groups including carboxyl, hydroxyl, epoxide derived from oxidation process can be detected on the edge and surface of GO.The specific surface area and average pore size of the graphene oxide were91.27m~2/g and2.82nm respectively using a B.E.T. analyzer.
The sorption of U(Ⅵ)、Th(Ⅳ) and Eu(Ⅲ) on GO was investigated as a function of contact time, solid-to-liquid ratio (m/Ⅴ)、pH, ionic strength, FA and HA using batch technique. The results show that:graphene oxide is a promising sorption material and has high sorption capacity for U(Ⅵ), Th(Ⅳ) and Eu(Ⅲ).The sorption capacities of Eu(Ⅲ) is high than15.40mg/g. The sorption of U(Ⅵ) rather than Th(Ⅳ) and Eu(Ⅲ) on graphene is dependent of ionic strength. It is obvious that the sorption edges of U(Ⅵ),Th(Ⅳ) and Eu(Ⅲ) in the presence of FA, HA and SA were much lower than that in the absence of FA, HA and SA. The sorption processes of U(Ⅵ), Th(Ⅳ) and Eu(Ⅲ) of graphene oxide can be described accurately by the pseudo-second order rate model. Freundlich model fits the sorption of U(VI),Th(IV) data better than Langmuir model.However the sorption of Eu(III) were fitted by Langmuir than Freundlich model。
本论文采用改进过的Hummers方法合成了氧化石墨烯,对该样品进行了一系列的表征(XRD,TEM, AFM,FT-IR,Raman,TGA等),用B.E.T法测定了其比表面积。分析结果如下：TEM,AFM表明该方法合成出了形貌上具有少量褶皱的单层和较少层数的氧化石墨烯。XRD,FTIR表明,氧化石墨烯的层间距变大,表面含有大量的羧基、羟基、环氧基等酸性氧基功能团。
采用批示法研究了所合成的氧化石墨烯对U(Ⅵ),Th(Ⅳ)和Eu(Ⅲ)的吸附行为。考察了固液比、溶液pH、背景电解质,腐殖质及水杨酸等对吸附的影响。结果表明,氧化石墨烯是一种较好的吸附材料,对U(Ⅵ),Th(Ⅳ)和Eu(Ⅲ)均有较强的吸附能力,常温下对Eu(Ⅲ)的吸附容量达15.40mg/g；离子强度对U(Ⅵ)在氧化石墨烯上的吸附影响显著,对Th(Ⅳ)、Eu(Ⅲ)在氧化石墨烯上的吸附影响较小；腐殖质、水杨酸均对氧化石墨烯的吸附性能存在着一定的抑制作用。探讨了吸附热力学和吸附动力学规律：U(Ⅵ)、Th(Ⅳ)及Eu(Ⅲ)在氧化石墨烯上的吸附动力学符合准二级动力学方程；热力学研究表明：用Freundlich模型可以更好的拟合U(Ⅵ)、Th(Ⅳ)在氧化石墨烯上的吸附行为；Eu(Ⅲ)在氧化石墨烯表面的吸附更接近于Langmuir吸附模型。
Graphene is one of the most concerning carbon nano-material in scientific communities recently. Because its special surface structure, such as large specific surface area and crumples, it can be concerned as a kind of suitible sorbents to extraction of radionuclides from aquous solutions. As its oxidized derivatives, graphene oxide(GO), with not only the above properties, but also a large number of acidic oxygen-containing functional groups, canbe predicted as a promising sorption material to radionuclides, which showes potential using in the treatment of radioactive waste.
In this paper, graphene oxide was synthesized from flake graphite by modified Hummers method and characterized by a series of methods (such as XRD, TEM, AFM,FT-IR,Raman, TGA etc).The results of TEM and AFM showed that the morphology of graphene oxide synthesized by modified hummers was single-layer with crumples and fewer layers.It was found from XRD and FT-IR that layer spacing of graphene oxide became larger. Meanwhile, a large amount of functional groups including carboxyl, hydroxyl, epoxide derived from oxidation process can be detected on the edge and surface of GO.The specific surface area and average pore size of the graphene oxide were91.27m~2/g and2.82nm respectively using a B.E.T. analyzer.
The sorption of U(Ⅵ)、Th(Ⅳ) and Eu(Ⅲ) on GO was investigated as a function of contact time, solid-to-liquid ratio (m/Ⅴ)、pH, ionic strength, FA and HA using batch technique. The results show that:graphene oxide is a promising sorption material and has high sorption capacity for U(Ⅵ), Th(Ⅳ) and Eu(Ⅲ).The sorption capacities of Eu(Ⅲ) is high than15.40mg/g. The sorption of U(Ⅵ) rather than Th(Ⅳ) and Eu(Ⅲ) on graphene is dependent of ionic strength. It is obvious that the sorption edges of U(Ⅵ),Th(Ⅳ) and Eu(Ⅲ) in the presence of FA, HA and SA were much lower than that in the absence of FA, HA and SA. The sorption processes of U(Ⅵ), Th(Ⅳ) and Eu(Ⅲ) of graphene oxide can be described accurately by the pseudo-second order rate model. Freundlich model fits the sorption of U(VI),Th(IV) data better than Langmuir model.However the sorption of Eu(III) were fitted by Langmuir than Freundlich model。
引文
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