四乙烯五胺功能化纳米高分子材料对Cr(VI)与磷酸盐共存体系的吸附机理

合成了四乙烯五胺功能化纳米高分子材料(TEPA-NP),采用傅里叶变换红外光谱分析(FTIR)、有机元素分析(EA)、X射线光电子能谱分析(XPS)等手段对其进行了表征,重点考察了其对水中Cr(VI)与磷酸根离子共存时的吸附机理.结果表明,溶液p H对TEPA-NP的吸附性能影响较大.对于Cr(VI)或磷酸盐单一体系,p H 2.5时TEPA-NP的吸附效果最佳;吸附热力学均符合Langmuir模型,吸附动力学均符合准二级速率方程.TEPA-NP对Cr(VI)的饱和吸附量为123.5 mg/g;吸附过程为吸热熵增的自发过程,ΔH为16.06 k J/mol,ΔS为59.02 J/(mol K),308 K时ΔG为-2.10 k J/mol;吸附活化能为30.28 k J/mol.TEPA-NP对磷酸盐的饱和吸附量为149.2 mg/g;吸附过程为放热熵增的自发过程,ΔH为-1.74 k J/mol,ΔS为1.91J/(mol K),308 K时ΔG为-2.32 k J/mol;吸附活化能为18.85 k J/mol.当磷酸盐的共存浓度小于100 mg/L时,磷酸盐对TEPA-NP吸附Cr(VI)几乎没有影响;而当Cr(VI)的共存浓度大于5 mg/L时,Cr(VI)对TEPA-NP吸附磷酸盐的影响已较为明显,可使TEPA-NP吸附磷酸盐的饱和吸附量减小17.3%;结合红外和XPS表征可以推测TEPA-NP对Cr(VI)的吸附涉及静电与配位相互作用,而对磷酸盐以静电吸附为主;Cr(VI)与磷酸盐共存时,TEPA-NP优先吸附Cr(VI).Cr(VI)可以通过竞争取代吸附在TEPA-NP上的磷酸根,且随着Cr(VI)初始浓度增大,TEPA-NP上吸附的总磷脱附的比例增大;而磷酸根对Cr(VI)的竞争吸附较难实现.     

IC-ICP-MS联用法测定玩具材料中可迁移的六价铬与三价铬

建立了一种IC与ICP-MS联用分析玩具材料中可迁移的Cr(III)与Cr(VI)的分析方法。采用胃酸模拟溶液萃取玩具材料中的Cr(III)与Cr(VI),萃取液用氨水调至中性,以NH4Cl为流动相,季铵盐离子交换柱为分离柱的离子色谱分离,最后用ICP-MS外标法定量。Cr(III)和Cr(VI)的线性范围分别为0.05～5 mg/kg和0.005～0.5 mg/kg;加标回收率90.0%～105.4%;RSD为2.0%～7.2%;Cr(III)和Cr(VI)的检出限(S/N=3)分别为0.25μg/L和0.029μg/L。     

超支化胶原纤维吸附剂对Cr(VI)的吸附特性和机理研究

超支化聚合物改性胶原纤维(CF-HBPN)作为吸附剂处理含Cr(VI)模拟废水,研究了CF-HBPN吸附Cr(VI)时溶液pH、吸附剂用量和Cr(VI)初始浓度等对去除效率的影响;采用XPS,SEM-EDS等分析检测方法对CF-HBPN表面组成和结构进行表征,探索吸附机理.结果显示:CF-HBPN对Cr(VI)的去除率随溶液pH降低而升高,在pH为3.0时达到最大,随吸附剂用量增大而增大,随Cr(VI)初始浓度增加而减小.CF-HBPN对Cr(VI)的吸附容量随吸附剂用量增加而减小,随Cr(VI)初始浓度增加而增加,最后趋于稳定.30℃时,4.0 g L-1的CF-HBPN对50 mg L-1Cr(VI)溶液的去除率可达99.57%,最大吸附容量为38.94 mg g-1.0.18 mol L-1的NaOH溶液对吸附Cr(VI)后的CF-HBPN解吸效果最好.SEM-EDS分析结果表明CF-HBPN表面较粗糙,是一种具有空间网状结构的材料,吸附过程存在离子交换.XPS分析结果表明Cr(VI)主要吸附在CF-HBPN表面,铬酸根阴离子与质子化氨基的静电吸附作用为主要吸附作用.     

氨基改性核桃壳对废水中Cr(Ⅵ)的静态吸附研究

对1.0~1.6mm的新疆核桃壳进行改性,在其表面引入氨基基团,以此作为吸附剂,研究其对含Cr(VI)模拟废水的静态吸附性能。实验结果表明,改性核桃壳对Cr(VI)有很好的吸附作用,对于50m L浓度为20mg/L模拟水样,当温度为25℃,水样初始p H值为5.89,吸附剂用量为0.50g,吸附时间为180min时,Cr(VI)的去除率可以达到98.6%,并且随着体系温度的升高,改性核桃壳对Cr(VI)的吸附量逐渐增加。吸附等温线拟合结果表明,Langmuir吸附等温模型能更好地描述上述吸附过程。     

流动注射壳聚糖在线微柱预富集电热原子吸收光谱法测定痕量Cr(VI)

以天然高分子材料壳聚糖作在线预富集柱填料,流动注射与电热原子光谱联用测定痕量Cr(VI)。采样体积5.80mL,采样频率22样/h,富集倍数51倍,线性范围0.02μg/L～0.12μg/L,该方法的检出限(3s,n=11)0.69ng/L,相对标准偏差5.1%(CCr(VI)=0.10μg/L,n=11)。将该方法用于环境水样、茶叶样品和头发样品中Cr(VI)的测定,结果满意。     

用玫瑰茎制备多孔炭及其水溶液中对铬(Ⅵ)的吸附研究

以玫瑰茎为原料,制备了多孔炭材料,并将其应用于含Cr(VI)的污染水净化。研究结果表明,用玫瑰茎制备的炭材料具有多孔结构,且具有较高的比表面积。应用EDS分析和傅立叶红外光谱分析进一步证明了该炭材料具有含氧官能团活性位点,是一种潜在的吸附材料。将其应用于含Cr(VI)污染水净化研究结果表明,净化过程符合准二级动力学,最大吸附量可达344.83 mg/g,明显高于市售污水净化用炭材料Norit CGP(最大吸附量305.81 mg/g)。这种炭材料有望成为性能优异的含Cr(VI)污水的净化剂。     

薄膜梯度扩散-分光光度法富集测量水中痕量Cr(VI)

建立了薄膜梯度扩散(DGT)-二苯碳酰二肼(DPC)分光光度法富集测量水中痕量Cr(VI)的分析方法。先以聚季铵盐(PQAS)溶液为结合相的DGT技术(PQAS DGT)原位分离富集水中Cr(VI),再以DPC分光光度法测定DGT结合相中Cr(VI)的含量,最后依据DGT方程计算水中Cr(VI)的浓度。DGT-DPC法测得配制水中Cr(VI)的回收率为95.1%~101.3%,相对标准偏差为1.60%~3.58%;测得工业废水中Cr(VI)的浓度为18.54~137.61μg/L,加标回收率为94.3%~101.8%。当采样时间为48h,PQAS DGT对水中Cr(VI)富集近10倍,可显著降低分析方法的检测限,实现水中痕量Cr(VI)的定量检测。     

氨基功能化纳米Fe3O4磁性高分子吸附剂对废水中Cr(VI)的吸附研究

采用分散聚合法通过共聚、开环反应, 对纳米Fe3O4进行表面功能化修饰, 得到富含NH2官能团的纳米磁性高分子复合材料. 通过透射电镜(TEM)、振动样品磁强计(VSM)、热重差热分析(TGA)、X射线衍射(XRD)、红外光谱(IR)等对其进行表征, 着重研究了其作为吸附剂对Cr(VI)的吸附性能. 结果表明: 该吸附剂对Cr(VI)的吸附能在10 min内达到平衡; 废水溶液pH值能显著影响吸附剂对Cr(VI)的吸附效果, pH为2.5时效果最佳. 废水中Cr(VI)的初始浓度、吸附时间、温度等因素对吸附效果均有不同程度的影响. 结合相应pH值下Cr(VI)的形态分布, 探讨了这种新型材料对Cr(VI)的吸附机理. 结果表明: 其吸附机理及吸附容量与废水中Cr(VI)的离子形式有关; 吸附过程以离子交换与静电引力为主. 等温吸附数据符合Langmuir模型, T＝308 K, pH＝2.5, V＝40 mL时, 吸附剂的饱和吸附容量qm＝25.58 mg/g. 吸附为吸热过程, 焓变ΔH＝8.64 kJ/mol.     

不同复合体系对含钛高炉渣光催化还原Cr(VI)的影响

采用煅烧的硫酸盐掺杂的含钛高炉渣(sulfate-modified titanium-bearing blast furnace slag, STBBFS)作为光催化剂, 研究了Cr(VI)-柠檬酸[Cr(VI)-CA]复合体系和Cr(VI)-柠檬酸-硝酸铁[Cr(VI)-CA-FN]复合体系对 STBBFS催化剂光催化活性的影响. 结果表明: 酸性条件下, 不同复合体系对STBBFS催化剂光催化活性的促进作用按Cr(VI)-CA-FN复合体系＞Cr(VI)-CA复合体系＞Cr(VI)单一体系增强. Cr(VI)-CA复合体系在pH＝2.5, 反应50 min后STBBFS催化剂光催化活性为0.426 mg•min―1•g―1时将溶液中的Cr(VI)全部还原; 而Cr(VI)-CA-FN复合体系在pH＝2.5, 反应16 min后STBBFS催化剂光催化活性为1.2425 mg•min―1•g―1时将溶液中的Cr(VI)全部还原. 两种复合体系中, Cr(VI)离子的光催化还原过程都遵循L-H动力学规律, 虽然加入CA和FN后, 降低了吸附对光催化还原Cr(VI)的影响, 但是Cr(VI)吸附至催化剂表面仍然是整个反应过程的关键.     

石墨烯量子点/TiO_2纳米线复合材料的制备及其光催化性能

采用可控的电泳沉积法制备了结合力强、光催化效率高的石墨烯量子点(GQDs)修饰的TiO_2纳米线(TNWs)壳核结构复合材料。在模拟太阳光下,GQDs/TNWs壳核结构复合材料光催化还原Cr(VI)的反应速率较纯TNWs提升了48%,其光催化活性提升的主要原因可归结为:GQDs作为敏化剂提高复合材料的光谱吸收能力;GQDs超好的导电性促进界面间光生电子的传输;核壳结构使GQDs与TNWs两相间具有最大的接触面积,进一步促进载流子的分离。GQDs/TNWs壳核结构复合材料不仅展现出较强的还原Cr(VI)能力,而且对新型层状光催化材料的设计提供了新的思路。     

Highly active nanoscale zero-valent iron (nZVI)-Fe3O4 nanocomposites for the removal of chromium(VI) from aqueous solutions

For the first time, nanoscale zero-valent iron (nZVI)-Fe(3)O(4) nanocomposites, prepared by an in situ reduction method, are employed for chromium(VI) removal in aqueous environment. 96.4% Cr(VI) could be removed by these novel materials within 2h under pH of 8.0 and initial Cr concentration of 20 mg L(-1), compared with 48.8% by bare nFe(3)O(4) and 18.8% by bare nZVI. Effects of several factors, including mass composition of nZVI-Fe(3)O(4) nanocomposites, initial pH and Cr(VI) concentration, were evaluated. The optimal ratio of nFe(3)O(4) to nZVI mass lies at 12:1 with a fixed nZVI concentration of 0.05 g L(-1). Low pH and initial Cr(VI) concentration could increase both the Cr(VI) removal efficiency and reaction rate. Corresponding reaction kinetics fitted well with the pseudo second-order adsorption model. Free energy change (ΔG) of this reaction was calculated to be -4.6 kJ mol(-1) by thermodynamic study, which confirmed its spontaneous and endothermic characteristic. The experimental data could be well described by the Langmuir and Freundlich model, and the maximum capacity (q(max)) obtained from the Langmuir model was 100 and 29.43 mg g(-1) at pH 3.0 and 8.0, respectively. The reaction mechanism was discussed in terms of the mutual benefit brought by the electron transfer from Fe(0) to Fe(3)O(4).     

Simultaneous determination of Cr(III) and Cr(VI) with prechelation of Cr(III) using phthalate by ion interaction chromatography with a C-18 column

Ion interaction chromatography has been successfully used for the simultaneous determination of Cr(III) and Cr(VI) in waste water. A C-18 column which had been dynamically coated with octylamine was used for the separation of Cr(III) and Cr(VI) based on anionic interaction. Cr(III) was chelated with potassium hydrogen phthalate (KHP) before injecting into the column since the Cr(III) did not exist in an anionic form like the Cr(VI) (Cr₂O₇²⁻) presented at the optimum condition. The analytes were detected at 200 nm and linear relationship between absorption with the concentration of Cr(III) or Cr(VI) was 0.1-50 mg/L. Most of the interested interferences including alkali metals, heavy metals and organic materials have no significant effect on Cr(III)-KHP complexation and Cr(VI) stability, only NH₄⁺ and ascorbic acid yielded the serious effect on the Cr(VI) stability. The relative standard deviations calculated from both of peak area and retention time were 0.75-2.20%. The sensitivity of the method at the level concentration of sub mg/L enabled the simultaneous determination of Cr(III) and Cr(VI) contents in waste water samples without any special sample preparation step.     

Hybrid materials: Magnetite-Polyethylenimine-Montmorillonite, as magnetic adsorbents for Cr(VI) water treatment

Hybrid materials formed by the combination of a sodium rich Montmorillonite (MMT), with magnetite nanoparticles (40nm, Fe(3)O(4) NPs) coated with Polyethylenimine polymer (PEI 800g/mol or PEI 25000g/mol) were prepared. The intercalation of the magnetite nanoparticles coated with PEI among MMT platelets was achieved by cationic exchange. The resulting materials presented a high degree of exfoliation of the MMT sheets and a good dispersion of Fe(3)O(4) NPs on both the surface and among the layers of MMT. The presence of amine groups in the PEI structure not only aids the exfoliation of the MMT layers, but also gives to the hybrid material the necessary functionality to interact with heavy metals. These hybrid materials were used as magnetic sorbent for the removal of hexavalent chromium from water. The effect that pH, Cr(VI) concentration, and adsorbent material composition have on the Cr(VI) removal efficiency was studied. A complete characterization of the materials was performed. The hybrid materials showed a slight dependence of the removal efficiency with the pH in a wide range (1-9). A maximum amount of adsorption capacity of 8.8mg/g was determined by the Langmuir isotherm. Results show that these hybrid materials can be considered as potential magnetic adsorbent for the Cr(VI) removal from water in a wide range of pH.     

Removal of Chromium(VI) from Groundwater Using Oil Shale Ash Supported Nanoscaled Zero-valent Iron

Oil shale ash(OSA) supported nanoscaled zero-valent iron(OSA-nZVI) was used as a rapid and efficient reductant for Cr(VI) reduction. The optimal mass ratio of nZVI to OSA and the optimal dosage were explored. The effects of initial pH, reaction temperature, initial Cr(VI) concentration, and common cations and anions in groundwater on Cr(VI) reduction were determined in batch experiments. The results show that the optimum initial pH is 5.0. The reaction temperature has a positive effect on Cr(VI) reduction while the real groundwater has a negative effect. Additionally, 84.22% Cr(VI) was still reduced by 3 g/L OSA-nZVI(1:2)(mass ratio of OSA to Fe⁰ was 1:2) within 120 min for 50 mg/L Cr(VI) under conditions of 10℃ and unadjusted pH.     

Speciation of Cr(III) and Cr(VI) in potable waters by using activated neutral alumina as collector and ET-AAS for determination

The speciation of Cr(III) and Cr(VI) has been performed by using activated neutral alumina as adsorbent. Both species were quantitatively adsorbed on a small column filled with neutral alumina. The adsorbed Cr(III) was eluted with 4 mol L(-1) HNO(3) and Cr(VI) with 1.0 mol L(-1) ammonia solution. Recoveries of Cr(III) and Cr(VI) were 99% and 100%, respectively. Using ET-AAS for Cr determination the limit of detection in the sample was 0.01 microg L(-1). The combined procedure is fast and sensitive. It can be applied for routine analysis of water samples at sub-microg L(-1) levels with a relative standard deviation (RSD) of 2-10% (three determinations).     

Adsorption-reduction performance of tea waste and rice husk biochars for Cr(VI) elimination from wastewater

In the current study tea waste and rice husk biochars were used for the elimination of Cr(VI) from wastewater with the objectives to study the effect of pH (3–10), shaking time (0.016–24 h), sorbent dose (0.1–1.3 g L⁻¹) and initial concentration of Cr(VI) (10–250 mg L⁻¹). The Cr(VI) sorption was studied under various factors in which solution pH played a main role and at pH 5.2, maximum 99.3% and 96.8% Cr(VI) were removed by tea waste biochar (TWB) and rice husk biochar (RHB), respectively. In comparison, 197.5 mg g⁻¹ and 195.24 mg g⁻¹ Cr(VI) were sorbed by TWB and RHB, respectively with 120 mg L⁻¹ initial Cr(VI) concentration. In contact time study, after 2 h, equilibrium was achieved for both biochars which indicated that the Cr(VI) elimination from aqueous medium is a fast process. Kinetic and isotherm modeling data showed that pseudo-second order model and Langmuir (monolayer sorption) models provided the best fit for sorption of Cr(VI) onto both biochars. The –OH, COO– and –NH₂ functional groups were involved in the sorption of Cr(VI) onto biochars according to FTIR. Biochars produced from both biomass effectively removed Cr(VI) from polluted water, however in comparison sorption capacity of TWB was slightly higher than RHB. It was concluded that TWB and RHB could provide a cost-effective and viable option for elimination of Cr(VI) from wastewater.     

Speciation of Cr(III) and Cr(VI) by Means of Melamine-Urea-Formaldehyde Resin and FAAS

 A method is described for the quantitative preconcentration and separation of trace chromium in water by adsorption on melamine-urea-formaldehyde resin. Cr(VI) is enriched from aqueous solutions on the resin. After elution the Cr(VI) is determined by FAAS. The capacity of the resin is maximal at ∼ pH 2. Total chromium can be determined by the method after oxidation of Cr(III) to Cr(VI) by hydrogen peroxide. The relative standard deviations (10 replicate analyses) for 10 mg/L levels of Cr(VI), Cr(III) and total chromium were 1.5, 3.5 and 2.8% respectively. The procedure has been applied to the determination and speciation of chromium in lake water, tap water and chromium-plating baths.     

Selective voltammetric determination of chromium (VI) with DTPA and nitrate

A voltammetric determination of Cr(VI) in a flow system is described based on the selective accumulation of the reduction product of Cr(VI) on an HMDE, its complexation with DTPA and subsequent reduction of the complex in presence of nitrate. The calibration graphs were linear up to 100 and 5 nmol/L for deposition times 120 and 600 s, respectively. The relative standard deviation was 2.8% (n = 5) for Cr(VI) concentrations of 5 × 10^–8 mol/L. The detection limits (3 σ) for Cr(VI) were 1.0 and 0.12 nmol/L at deposition times of 120 and 600 s, respectively. Typical interferences derived from real water samples are discussed. The method has been applied for the determination of Cr(VI) in spiked natural water samples.     

Optimization of Parameters for Cr(VI) Adsorption on Used Black Tea Leaves

Dynamic characteristics of Cr(VI) sorption on used black tea leaves (UBTLs) as a low-cost adsorbent are studied. Batch experiments were conducted to evaluate the effects of Cr(VI) concentration, solution pH and temperature on the removal process. Both of adsorption and reduction, involved in the process, are affected by the processing parameters. The adsorption kinetics is described successfully using pseudo-second order rate equation and the rate constant decreases with increasing the initial concentration of Cr(VI) up to 150 mg/L (for 0.1 g/L UBTLs) then becomes slow. Experimental and calculated kinetic data for equilibrium are well expressed by Langmuir isotherm. The solution pH has a profound effect on the adsorption rate. The rate constant increases linearly with an increase in temperature, and the low value of activation energy of adsorption, 16.3 kJ/mol, indicates that Cr(VI) is easily adsorbed on UBTLs. The maximum Cr(VI) adsorptive conditions, with a minimum reduction, were achieved from the dynamics of operational parameters: the initial Cr(VI) concentration < 150 mg/L (for 0.1 g/L UBTLs); the initial solution pH = 1.54–2.00 and the processing temperature < 50 ^∘C, for the possibility of its practical application.     

Synthesis of Calcium Silicate Hydrate from Coal Gangue for Cr(VI) and Cu(II) Removal from Aqueous Solution

Both the accumulation of coal gangue and potentially toxic elements in aqueous solution have caused biological damage to the surrounding ecosystem of the Huainan coal mining field. In this study, coal gangue was used to synthesize calcium silicate hydrate (C-S-H) to remove Cr(VI) and Cu(II)from aqueous solutions and aqueous solution. The optimum parameters for C-S-H synthesis were 700 °C for 1 h and a Ca/Si molar ratio of 1.0. Quantitative sorption analysis was done at variable temperature, C-S-H dosages, solution pH, initial concentrations of metals, and reaction time. The solution pH was precisely controlled by a pH meter. The adsorption temperature was controlled by a thermostatic gas bath oscillator. The error of solution temperature was controlled at ± 0.3, compared with the adsorption temperature. For Cr(VI) and Cu(II), the optimum initial concentration, temperature, and reaction time were 200 mg/L, 40 °C and 90 min, pH 2 and 0.1 g C-S-H for Cr(VI), pH 6 and 0.07 g C-S-H for Cu(II), respectively. The maximum adsorption capacities of Cr(VI) and Cu(II) were 68.03 and 70.42 mg·g⁻¹, respectively. Furthermore, the concentrations of Cu(II) and Cr(VI) in aqueous solution could meet the surface water quality standards in China. The adsorption mechanism of Cu(II) and Cr(VI) onto C-S-H were reduction, electrostatic interaction, chelation interaction, and surface complexation. It was found that C-S-H is an environmentally friendly adsorbent for effective removal of metals from aqueous solution through different mechanisms.