还原态氧化石墨烯对Zn(Ⅱ)的吸附动力学与热力学

以乙二胺(EDA)还原氧化石墨烯(GO)制得一种吸附材料,即还原态氧化石墨烯(RGO)。 采用批量平衡法研究了RGO对Zn(Ⅱ)的吸附动力学与热力学,利用Lagergren准一级及准二级动力学方程、Langmuir和Freundlich等温方程对实验数据进行了拟合分析。 研究结果表明,Lagergren准二级吸附动力学模型能够较好地描述实验结果,表明该吸附过程以化学吸附为主。 RGO的吸附在所研究的Zn(Ⅱ)浓度范围内更符合Langmuir等温吸附经验式,ΔH0=-21.60 kJ/mol,吸附焓变小于零,表明该吸附为放热过程;吸附吉布斯自由能变化ΔG0为正值,表明该吸附是一个非自发的过程。     

巯基化石墨烯对水中Pb(Ⅱ)的吸附性能研究

采用改进的Hummers法制备氧化石墨烯,在交联剂EDC作用下,巯基乙胺与氧化石墨烯上的羧基进行缩合反应,合成巯基化石墨烯。运用FTIR、SEM及XPS等手段对合成材料进行表征,结果表明,巯基乙胺成功接枝在氧化石墨烯表面。将巯基化石墨烯用于吸附去除水中的Pb(Ⅱ),结果表明,合成的巯基化石墨烯对Pb(Ⅱ)的吸附效果好,吸附量高达205.25mg/g。吸附动力学遵循准二级模型,且等温吸附数据可用Langmuir吸附等温线很好地拟合。本文报道的巯基化石墨烯对废水处理和净化有很大的潜在应用。     

RGO/Fe_2O_3的制备及其对四环素的吸附性能研究

采用改进的hummer法制备氧化石墨烯,以氧化石墨烯(GO)为前驱体,六水合氯化铁为铁源,通过溶剂热法一步合成RGO/Fe_2O_3材料。使用X射线衍射、热重、红外光谱法等对所得材料进行了表征。考察了此材料对四环类抗生素的吸附性能。结果表明,该材料对四环素类抗生素的吸附量随溶液初始浓度和温度的升高而增加。当初始浓度大于6 mmol·L-1时吸附量趋于平衡。所得材料对四环素(TC)的静态饱和容量为783.53 mg·g~(-1),吸附过程对Langmuir以及Freundlich方程均呈现出的拟合度良好。将RGO/Fe_2O_3作为固相萃取剂,对牛奶样品进行加标回收实验,平均回收率为99.1%~99.6%,相对标准偏差(RSD)为5.2%~6.0%,该吸附材料RGO/Fe_2O_3可以用于四环素类抗生素的富集分离测定,结果稳定性好,并且能重复使用。     

还原态氧化石墨烯载Pd纳米催化剂对甲酸氧化的电催化性能

采用改进的Hummers法氧化石墨后,对其超声剥离成氧化石墨烯水溶液,继之通过乙二醇还原Pd金属离子和氧化石墨烯,得到了还原态氧化石墨烯（RGO）负载Pd纳米催化剂,并用于甲酸的电催化氧化.透射电子显微镜和X射线衍射结果显示：负载于RGO上的Pd粒子平均粒径为3.8nm,其优先在RGO的褶皱和边缘处生长.电化学测试表明：RGO上残存的含氧基团降低了Pd催化剂受CO毒化的程度,Pd/RGO催化剂表现出了较商业化Pd/C更高的电催化活性和更好的稳定性.     

十六烷基三甲基溴化铵改进Hummers法制备石墨烯的研究

将阳离子表面活性剂（十六烷基三甲基溴化铵,CTAB）作为絮凝剂,利用其与氧化石墨烯（GO）产生静电吸引的原理,实现中间产物CTAB-GO复合物的快速分离和纯化,并利用水合肼还原制得还原氧化石墨烯（RGO）。采用UV-Vis、 SEM、 TEM、 AAS和XPS对石墨烯的形貌、纯度、制备过程及机理进行了分析表征。结果显示,CTAB能通过静电力吸附在GO表面,形成CTAB-GO复合物的絮凝沉淀。当CTAB和GO的质量比为1:2时,可以达到最佳的絮凝效果。该絮凝沉淀仅通过低压过滤或低速离心（3 000 rpm, 3 min）便能实现快速分离和纯化,得到CTAB-GO复合物。AAS和XPS证实CTAB-GO复合物中不存在杂质离子。此外,CTAB-GO复合物经过水合肼还原后,CTAB能快速完全脱除,从而得到高纯度RGO。     

不同表面修饰石墨烯载Pd催化剂对甲酸氧化的电催化性能

采用对氨基苯磺酸对氧化石墨烯（GO）进行表面功能化,进而负载贵金属Pd,解决了Pd团聚和不易在载体表面负载的问题,从而提高了Pd基催化剂对于甲酸的催化能力。 实验研究了相同实验条件下,Pd在氧化石墨烯、还原石墨烯（RGO）和磺化处理的石墨烯（SGO）表面的分散和负载量以及得到的复合催化剂的催化性能。 实验结果表明,SGO更容易负载贵金属,得到的催化剂对O2气的电催化还原能力优于Pd/GO和Pd/RGO,此外Pd/SGO催化剂对CO的耐受力也明显提升,这可能是苯环上的π-π键和-SO3H的范德华力协同作用更有利于Pd的固定与分散。 对Pd/SGO催化氧还原的机理也进行了分析,该氧还原为2电子反应过程。     

氧化石墨烯水热还原前后的发光光谱

分别采用改进Hummers方法和水热还原法制备了氧化石墨烯(GO)和还原氧化石墨烯(RGO)。 GO和RGO经透射电子显微镜(TEM)、紫外-可见吸收光谱(UV-Vis)、红外光谱(IR)、荧光发射和激发光谱(PL、PLE)等技术手段进行了表征。 荧光发射光谱显示,氧化石墨烯(GO)在可见光的激发下可以得到波长在600~800 nm范围内的宽谱近红外荧光。 通过比较氧化石墨烯水热还原前后的光谱变化,发现氧化石墨烯近红外荧光起源于氧化石墨烯的表面含氧基团,如C=O、COOH。 近红外荧光穿透性好、对生物组织损坏小,非常适合于生物成像,预示着氧化石墨烯在生物成像方面的应用潜力。     

双功能气凝胶吸附-降解协同处理染料废水

针对吸附法处理染料废水易产生二次污染和基于过一硫酸氢盐(PMS)的高级氧化技术降解有机污染物易受水体复杂成分影响的问题,设计构筑具有吸附和活化PMS功能的铁掺杂纤维素纳米纤维/还原氧化石墨烯气凝胶(CNFs/RGO/Fe)用于吸附-降解协同处理染料废水.CNFs/RGO/Fe对阳离子染料具有良好的选择性吸附功能,其对亚甲基蓝(MB)、罗丹明B (RhB)和结晶紫(CV)的最大吸附容量分别高达655.1 mg/g、696.5 mg/g和962.1 mg/g,吸附过程符合准二级动力学模型和Langmuir等温模型.将吸附染料的CNFs/RGO/Fe置于PMS溶液中,可以促进PMS活化产生大量·OH,实现对吸附质的降解和气凝胶的再生.经5次吸附-降解循环后,CNFs/RGO/Fe对染料去除率仍保持在75%以上,表现出良好的重复使用性.本研究有望为去除复杂水体中有机污染物提供新思路.     

磁性氧化石墨烯/MIL-101(Cr)表面金属离子印迹聚合物制备及其对Cu(Ⅱ)和Pb(Ⅱ)选择性吸附

本文以磁性氧化石墨烯/MIL-101(Cr)复合材料为载体,以Cu(Ⅱ)和Pb(Ⅱ)模板,多巴胺(DA)为功能单体,采用表面印迹技术成功制备一种对Cu(Ⅱ)和Pb(Ⅱ)具有高选择吸附性能的磁性离子印迹聚合物。 采用傅里叶变换红外光谱、扫描电子显微镜和振动样品磁强计等技术对该磁性离子印迹聚合物的形貌、粒径大小和磁性能进行表征。 详细探讨了该磁性离子印迹聚合物对Cu(Ⅱ)和Pb(Ⅱ)的吸附动力学、等温吸附性能及吸附选择性,结果表明该磁性离子印迹聚合物对Cu(Ⅱ)和Pb(Ⅱ)最大吸附量分别为144.92和322.58 mg/g。 优化了磁固相萃取条件,该磁性离子印迹聚合物成功用于水样中微量Cu(Ⅱ)和Pb(Ⅱ)的分离和检测,Cu(Ⅱ)和Pb(Ⅱ)的回收率分别为81.99%~89.91%和81.24%~95.15%。     

一步法制备还原态氧化石墨烯载铂纳米粒子及其对甲醇氧化的电催化性能

以天然石墨为原料,采用改进的Hummers法制备氧化石墨.然后采用简单的一步化学还原法在乙二醇(EG)中同时还原氧化石墨烯(GO)和H₂PtCl₆制备高分散的铂/还原态氧化石墨烯(Pt/RGO)催化剂.采用傅里叶变换红外(FTIR)光谱、X射线衍射(XRD)和透射电子显微镜(TEM)对催化剂的微结构、组成和形貌进行表征.结果表明, GO已被还原成RGO, Pt纳米粒子均匀分散在RGO表面,粒径约为2.3 nm.采用循环伏安法和计时电流法评价催化剂对甲醇氧化的电催化性能,测试结果表明, Pt/RGO催化剂对甲醇氧化的电催化活性和稳定性与Pt/C和Pt/CNT相比有了很大提高.另外其对甲醇电催化氧化的循环伏安图中正扫峰电流密度(I_f)和反扫峰电流密度(I_b)的比值高达1.3,分别是Pt/C和Pt/CNT催化剂的2.2和1.9倍,表明Pt/RGO催化剂具有高的抗甲醇氧化中间体CO_ad的中毒能力.     

Preparation of Ag-MnFe2O4-bentonite Magnetic Composite for Pb(Ⅱ)/Cd(Ⅱ) Adsorption Removal and Bacterial Inactivation in Wastewater

An Ag-MnFe₂O₄-bentonite composite was synthesized by a chemical co-precipitation method and used for adsorption removal of Pb(Ⅱ), Cd(Ⅱ) and disinfection. The result of X-ray diffraction indicate that the diffraction peaks of MnFe₂O₄ and Ag can be perfectly indexed to the cubic spinel MnFe₂O₄(JCPDS No.88-1965) and metallic Ag(JCPDS No.41-1402), respectively. The results of scanning electron microscopy and energy dispersive X-ray spectroscopy manifest the deposition of MnFe₂O₄ and Ag on the bentonite surface and the presence of Mn, Fe and Ag. The result of X-ray photoelectron spectroscopy displayed that the composition of Ag-MnFe₂O₄-bentonite was Mn(Ⅱ), Fe(ⅡI) and metallic Ag. The analysis of Brunauer-Emmett-Teller showed that the specific surface area of Ag-MnFe₂O₄-bentonite was the largest compared with that of bentonite, MnFe₂O₄ and MnFe₂O₄-bentonite. Thermodynamic studies revealed that the adsorption of Pb(Ⅱ) and Cd(Ⅱ) ions was spontaneous and endothermic. Langmuir model showed an adsorption capacity of 129.87 mg/g for Pb(Ⅱ) and 48.31 mg/g for Cd(Ⅱ) ions. The adsorption kinetics of Pb(Ⅱ) and Cd(Ⅱ) ions onto Ag-MnFe₂O₄-bentonite can be best described by a pseudo-second-order model. The adsorption rate constant of the pseudo-second-order model was 0.0019 g·mg^-1·min^-1 for Pb(Ⅱ) and 0.0065 g·mg^-1·min^-1 for Cd(Ⅱ) ions. In addition to the adsorption experiment, the antibacterial properties of Ag-MnFe₂O₄-bentonite were studied through plate count method. Gram-negative(G-) bacteria Escherichia coli and Gram-positive(G+) bacteria Lactobacillus plantarum were used to test the antibacterial properties. The results showed that the composite demonstrated excellent antibacterial activity. Thus, Ag-MnFe₂O₄-bentonite can be employed as an adsorbent as well as an antimicrobial agent.     

SiO2/graphene composite for highly selective adsorption of Pb(II) ion

SiO(2)/graphene composite was prepared through a simple two-step reaction, including the preparation of SiO(2)/graphene oxide and the reduction of graphene oxide (GO). The composite was characterized by UV-Vis spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscope, and X-ray photoelectron spectroscopy, and what is more, the adsorption behavior of as-synthesized SiO(2)/graphene composite was investigated. It was interestingly found that the composite shows high efficiency and high selectivity toward Pb(II) ion. The maximum adsorption capacity of SiO(2)/graphene composite for Pb(II) ion was found to be 113.6 mg g(-1), which was much higher than that of bare SiO(2) nanoparticles. The results indicated that SiO(2)/graphene composite with high adsorption efficiency and fast adsorption equilibrium can be used as a practical adsorbent for Pb(II) ion.     

水溶液体系中氧化石墨烯的γ射线辐射还原

石墨烯是一种碳原子以二维蜂窝状晶格结构构成的单片层材料,由于其具有优异的电传导性、力学性能和热传导性近年来受到广泛关注.本文采用γ射线辐射技术分别处理水溶液和对苯二胺(PPD)水溶液中的氧化石墨烯(GO),得到辐照还原氧化石墨烯(RGO)和胺基化修饰的还原氧化石墨烯(RGON).通过傅里叶变换红外(FTIR)光谱、X射线光电子能谱(XPS)、拉曼(Raman)光谱、X射线衍射(XRD)和热失重分析(TGA)等表征分析产物的化学结构和元素组成;通过四探针测试仪和接触角测量仪研究产物的导电性能和亲水性.实验结果表明,在水溶液及PPD水溶液中γ射线辐射均可高效还原GO,还原后得到的RGO和RGON电导率均显著增大.PPD的胺基在辐射还原过程中还可以修饰到石墨烯的表面,因此RGON的亲水性比RGO好,但胺基的存在会干扰石墨烯表面π电子的传导,导致其电导率下降.     

Synthesis of adenine-modified reduced graphene oxide nanosheets

We report here a facile strategy to synthesize the nanocomposite of adenine-modified reduced graphene oxide (AMG) via reaction between adenine and GOCl which is generated from SOCl(2) reacted with graphite oxide (GO). The as-synthesized AMG was characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), UV-vis absorption spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, Raman spectroscopy, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and galvanostatic discharge analysis. The AMG owns about one adenine group per 53 carbon atoms on a graphene sheet, which improves electronic conductivity compared with reduced graphene oxide (RGO). The AMG displays enhanced supercapacitor performance compared with RGO accompanying good stability and good cycling behavior in the supercapacitor.     

氮掺杂还原氧化石墨烯负载铂催化剂的制备及甲醇电氧化性能

采用高温热解聚苯胺修饰的氧化石墨烯（PANI-GO）,得到了氮掺杂的还原氧化石墨烯碳材料（N-RGO）,以其负载Pt 制备了Pt/N-RGO纳米结构电催化剂. 采用透射电镜（TEM）、X射线光电子能谱（XPS）、X 射线衍射（XRD）谱及拉曼光谱等技术对N-RGO和Pt/N-RGO的形貌及结构进行了表征,用循环伏安、计时电流等电化学技术研究了Pt/N-RGO电极催化剂对CO溶出反应和甲醇电氧化反应的催化性能. 结果表明：高温热解PANIGO可同时实现GO的还原及其氮掺杂的过程,氮掺杂引起还原氧化石墨烯碳材料表面缺陷结构和导电性的增加;与相应的未掺杂氮样品Pt/RGO相比较,Pt/N-RGO样品上Pt 颗粒的分散更均匀,显示出更强的抗CO毒化能力和更高的甲醇电氧化催化活性及稳定性.     

氮掺杂还原氧化石墨烯负载铂催化剂的制备及甲醇电氧化性能

采用高温热解聚苯胺修饰的氧化石墨烯(PANI-GO),得到了氮掺杂的还原氧化石墨烯碳材料(N-RGO),以其负载Pt制备了Pt/N-RGO纳米结构电催化剂.采用透射电镜(TEM)、X射线光电子能谱(XPS)、X射线衍射(XRD)谱及拉曼光谱等技术对N-RGO和Pt/N-RGO的形貌及结构进行了表征,用循环伏安、计时电流等电化学技术研究了Pt/N-RGO电极催化剂对CO溶出反应和甲醇电氧化反应的催化性能.结果表明:高温热解PANIGO可同时实现GO的还原及其氮掺杂的过程,氮掺杂引起还原氧化石墨烯碳材料表面缺陷结构和导电性的增加;与相应的未掺杂氮样品Pt/RGO相比较,Pt/N-RGO样品上Pt颗粒的分散更均匀,显示出更强的抗CO毒化能力和更高的甲醇电氧化催化活性及稳定性.     

Adsorption of metal ions onto Moroccan stevensite: kinetic and isotherm studies

The aim of this paper is to study the adsorption of the heavy metals (Cd(II), Cu(II), Mn(II), Pb(II), and Zn(II)) from aqueous solutions by a natural Moroccan stevensite called locally rhassoul. We carried out, first, a mineralogical and physicochemical characterization of stevensite. The surface area is 134 m2/g and the cation exchange capacity (CEC) is 76.5 meq/100 g. The chemical formula of stevensite is Si3.78Al0.22Mg2.92Fe0.09Na0.08K0.08O10(OH)2.4H2O. Adsorption tests of Cd(II), Cu(II), Mn(II), Pb(II), and Zn(II) in batch reactors were carried out at ambient temperature and at constant pH. Two simplified models including pseudo-first-order and pseudo-second- order were used to test the adsorption kinetics. The equilibrium time and adsorption rate of adsorption were determined. The increasing order of the adsorption rates follows the sequence Mn(II) > Pb(II) > Zn(II) > Cu(II) > Cd(II). The Dubinin-Radushkevich (D-R), Langmuir, and Redlich-Peterson (R-P) models were adopted to describe the adsorption isotherms. The maximal adsorption capacities at pH 4.0 determined from the D-R and Langmuir models vary in the following order: Cu(II) > Mn(II) > Cd(II) > Zn(II) > Pb(II). The equilibrium data fitted well with the three-parameter Redlich-Peterson model. The values of mean energy of adsorption show mainly an ion-exchange mechanism. Also, the influence of solution pH on the adsorption onto stevensite was studied in the pH range 1.5-7.0.     

Improving the catalytic activity of magnetic Fe3O4/ZnO-CdO/reduced graphene oxide for ultrasonic degradation of the organic pollutants and the green oxidation of olefins

Magnetic Fe₃O₄/ZnO-CdO/reduced graphene oxide (MFZC/RGO) has been synthesized by simple hydrothermal method. The structure and morphology were investigated by X-ray diffraction (XRD), Transmission electron microscopy (TEM), Scanning electron microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDS), Diffuse reflectance spectroscopy (DRS), Vibrating sample magnetometer (VSM), Raman and Fourier-transform infrared spectroscopy (FTIR). MFZC/RGO was applied as catalyst in degradation of methylene blue (MB), rhodamin B (RhB) and methylorange (MO) under ultrasonic irradiation. Based on the results, excellent degradation efficiencies of MB, RhB and MO (>99%) were achieved within 10, 20 and 20 min, respectively under oxygen flow. Moreover the catalytic property of MFZC/RGO was investigated in oxidation of styrene, α-methyl styrene, cyclohexene and cyclooctene under oxygen flow. In addition, MFZC/RGO can be easily collected and separated by an external magnet. The catalyst displayed negligible loss in activity and selectivity within several successive runs due to super paramagnetism.