三维全碳多孔结构对亚甲基蓝吸附性能的动力学探究

采用低温-烧结法,以碳纳米管(CNTs)为基本骨架,聚甲基丙烯酸甲酯(PMMA)微球为造孔剂,制备了一种孔径可调的三维全碳多孔结构(ACPs);利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射分析(XRD)、拉曼光谱(Raman)、比表面积及孔结构分析等对ACPs的形貌、组成、结构及比表面积进行了表征;考察了ACPs对模拟污染物亚甲基蓝的吸附效果.结果表明,该ACPs为内部含有大孔、介孔及微孔的三维连通孔隙结构,具有较大的比表面积.ACPs对亚甲基蓝的吸附过程符合伪二级动力学模型,对亚甲基蓝的平衡吸附量qe与亚甲基蓝溶液的平衡浓度ce的关系满足Langmuir等温吸附模型,由Langmuir模型计算得到ACPs对亚甲基蓝的最大吸附容量为151.3 mg/g.     

介孔C/SiO2粉体的制备及对阳离子型染料的吸附

采用吸附法处理染料废水需要合适的吸附剂。利用溶剂蒸发自组装法,以甲阶酚醛树脂为碳源、介孔SiO2粉体为载体制备介孔C/SiO2粉体,表征所制C/SiO2粉体的结构,研究C/SiO2粉体对阳离子型染料亚甲基蓝和阳离子红X-GRL的吸附性能,并与相同条件下制备的非负载的多孔C粉体以及介孔SiO2载体进行比较。结果表明,介孔C/SiO2粉体的孔窗口为11~18 nm,比表面积为303 m2.g-1,比孔容为1.11 cm3.g-1;C/SiO2粉体对这两种染料吸附量均高于C粉体和SiO2载体;在pH≤10的范围内,吸附量随pH值增大而显著提高。     

β-环糊精微球对染料分子吸附作用研究

以环氧氯丙烷为交联剂,采取反相乳液聚合得到β-环糊精微球(EPI-β-CD),经丁二酸酐酰化后得到微球表面具有羧基的β-环糊精微球(SUC-EPI-β-CD),分别采用红外光谱、扫描电镜和激光粒度分析仪表征了其结构及形貌特征.选择染料亚甲基蓝(MB)和甲基橙(MO)作为模型分子,考察了所合成微球的吸附性能.结果表明:由于β-CD与两种染料分子的相互作用力不同,微球EPI-β-CD吸附亚甲基兰染料的能力强于甲基橙;两种微球对MB的吸附等温数据与Freundlich方程拟合较好,且均为优惠吸附;羧丁基酰化β-环糊精微球(SUC-EPI-β-CD)表现出较明显的pH敏感性.     

亚甲基蓝及NH4+,Na+,K+与SiO2的表面配位常数测定

采用动电位、等温吸附方法研究了不同pH条件下SiO2的表面电性和对有机染料-亚甲基蓝的吸附行为,运用WinSGW软件计算得出亚甲基蓝在SiO2颗粒表面配位常数.研究发现亚甲基蓝通过静电和氢键作用吸附,相应的化学反应模型和表面配位常数分别为≡Si2O-+MB+≡Si2OMB(lg K=4.48)和≡SiOH+MB+≡SiOHMB+(lg K=2.30).在此基础上研究了一价阳离子NH+4,Na+,K+对亚甲基蓝在SiO2表面吸附的影响,根据WinSGW软件模拟得到的NH+4,Na+,K+与SiO2表面的配位常数分别为:≡Si2O-+M+≡Si2OM[lg K=3.76,2.73,2.58(M+=NH+4,Na+,K+).在铵根离子浓度高时,还会在表面上发生≡SiOH+NH3+MB+≡SiOHNH3MB+(lg K=6.69)化学反应而生成包含有三种组分的≡SiOHNH3MB+表面三元配合物.研究结果可为了解有机染料和氨氮在被污染土壤和水体中的分布提供一定的理论依据.     

新型功能介孔吸附剂NiNb_2O_6的合成及其吸附性能研究

通过柠檬酸溶胶-凝胶反应,合成了新型功能介孔NiNb2O6吸附剂,通过X-射线粉末衍射仪(XRD)、透射电镜(TEM)和比表面积及孔径分析(BET)对其结构进行表征。通过影响因素实验、吸附动力学实验和等温吸附实验,探讨了NiNb2O6吸附剂对水溶液中亚甲基蓝的吸附性能和机理。结果表明,NiNb2O6介孔吸附剂具有正交相晶体结构,平均粒径为30~200nm,比表面积为66.3m2/g。吸附剂用量、温度和pH值均对吸附行为有一定的影响;在35℃时,亚甲基蓝在吸附剂上吸附行为符合Langmuir方程,吸附动力学符合拟二级动力学方程,初始浓度为40mg/L,pH值为7.03时,0.2g介孔吸附剂NiNb2O6对亚甲基蓝的吸附量最大,吸附过程中液膜扩散为主要速率控制步骤。     

有序介孔炭的合成及液相有机大分子吸附性能研究

分别采用有序介孔氧化硅SBA-15和NaY分子筛为硬模板合成了系列有序介孔炭OMC和微孔炭CFY. N₂静态吸附测试表明, 所合成的介孔炭具有丰富的介孔结构和集中的介孔分布. 以亚甲基蓝为探针分子, 研究其在有序介孔炭OMC和微孔炭CFY上的吸附行为. 研究结果表明, 有序介孔炭中大于3.5 nm的大介孔孔容是决定亚甲基蓝吸附容量和吸附速率的关键因素. 吸附动力学理论研究表明, 准二级动力学方程可以很好地描述亚甲基蓝分子在介孔炭上吸附动力学行为.     

用实验和模拟计算确定SiO2空心微球的孔径分布

用巨正则系综蒙特卡罗（GCMC）模拟方法结合统计积分方程（SIE）计算了SiO2空心微球球壳上的孔径分布（PSD）.HRTEM、XRD及氮气吸附等实验测试表明,SiO2空心微球的球壳上有无序的介孔孔道.在模拟中,基于实验数据,将SiO2空心微球模型化为具有一定孔径分布的园柱孔,流体模型化为Lennard-Jones(LJ)球,流体分子和孔壁间的相互作用采用Wang等人[10]最近提出的完全解析的势函数描述.模拟结果显示,用孔径分布拟合的吸附数据和实验吸附等温线吻合良好,说明PSD能够十分有效地表示SiO2空心微球的微孔结构.     

超细粉煤灰吸附亚甲基蓝的机理研究

以西安西郊热电厂粉煤灰(XFA),西安灞桥热电厂粉煤灰(BFA)和陕西渭河电厂粉煤灰(WFA)为原料,球磨后经旋风分级再用布袋收集逸出物分别得到超细粉煤灰XUFA、BUFA和WUFA。研究了超细粉煤灰对亚甲基蓝的吸附动力学、热力学以及pH值对吸附的影响。结果表明,超细粉煤灰对亚甲基蓝的吸附性能明显好于原粉煤灰。超细粉煤灰对亚甲基蓝的吸附性能按顺序为WUFA>XUFA>BUFA。粉煤灰颗粒粒度、比表面积和活性组分(SiO2 Al2O3)含量是影响粉煤灰吸附性能的主要因素。WUFA对亚甲基蓝的吸附符合Langmuir吸附等温式,而XUFA和BUFA对亚甲基蓝的吸附符合Freundlich吸附等温式。超细粉煤灰对亚甲基蓝的吸附均符合二级吸附动力学模型,吸附过程由颗粒内扩散过程控制。当溶液pH由2增加到8时,超细粉煤灰吸附量增加,后随pH值增加,吸附量略有下降。     

锌离子掺杂的二氧化钛介孔空心微球的制备及光催化性能

以二氧化硅为模板,钛酸四丁酯(TBOT)为钛源,硝酸锌为锌源,采用溶胶凝胶法制备了锌离子掺杂的介孔二氧化钛空心微球。采用X射线衍射(XRD)、比表面积(BET)、透射电镜(TEM)、扫描电镜(SEM)和X射线光电子能谱(XPS)等技术对样品进行表征,以亚甲基蓝(MB)的光催化降解为目标反应评价其光催化活性。结果表明,去核之后的复合微球为空心微球,壁厚为20 nm左右。钛酸四丁酯溶液的滴加时间对微球的形貌影响较大,当滴加时间大于15 min时,可以得到结构清晰的空心微球。用氢氧化钠溶液去除二氧化硅核,反应90 min,二氧化硅可以被完全去除。X射线衍射表明,实验得到的掺杂锌离子的空心微球和没有掺杂锌离子的空心微球都是锐钛矿。当锌离子的摩尔分数为0.3%时,二氧化钛空心微球的晶粒尺寸最小,比表面积最大,催化亚甲基蓝降解的效率最高。     

活化赤泥对染料废水吸附性能研究

以赤泥为原料,十二烷基苯磺酸钠为活化剂,制备出活化赤泥吸附剂,并对亚甲基蓝(MB)染料废水吸附性能进行研究。结果表明,活化赤泥对亚甲基蓝的吸附效果有一定提高。振荡时间15min,活化赤泥6g·L~(-1),中性条件下,对40mg·L~(-1)亚甲基蓝吸附率可达90%。吸附符合Langmuir和Freundlich吸附等式,最大吸附量为16.37mg·g~(-1)。活化赤泥吸附亚甲基蓝为放热反应,低温利于亚甲基蓝吸附。     

Modification of microcrystalline cellulose with pyridone derivatives for removal of cationic dyes from aqueous solutions

Microcrystalline cellulose (MCC) was modified with pyridone derivatives such as pyridone diester (PDE) and pyridone diacid (PDA) by using succinic acid anhydride as a linker. The modified MCCs were characterized by the fourier transform infrared spectroscopy, scanning electron microscopy, thermal gravimetric analysis, elemental analysis and solid state ¹³C NMR. The adsorption capacities of the modified MCCs to cationic dyes were examined by using methylene blue (MB) as a model dye. It was found that the kinetic adsorption data followed the pseudo-second-order kinetic model, and the adsorption equilibriums were reached less than 10 min. The isothermal adsorption data were fitted with the Langmuir isotherm model very well, from which the maximum adsorption capacities of the MCCs modified with PDE and PDA were determined to be 101.01 and 142.86 mg/g, respectively. Further investigation showed that the modified MCCs were pH-dependent for adsorption of MB in aqueous solutions. The modified MCCs could be used for removal of MB from an aqueous solution at pH 8, and reused by regeneration in an acidic solution. It was tested that the modified MCCs had a high reusability for removal of MB from aqueous solutions, and still maintained high adsorption capacities even after multiple cycles of desorption–adsorption processes. Hence, the MCCs modified with PDE and PDA could be an effective and efficient approach to removal of cationic dyes from aqueous solutions.     

Fast Removal and Recovery of Methylene Blue by Activated Carbon Modified with Magnetic Iron Oxide Nanoparticles

A magnetic adsorbent was synthesized by modification of activated carbons with magnetic iron oxide nanoparticles (AC‐MIONs). The preparation method is fast and could be carried out in an ordinary condition. The AC‐MIONs were used as quite efficient adsorbents for separation of methylene blue (MB) from aqueous solution in a batch process. The effect of different parameters such as pH, temperature, electrolyte concentration, contact time and interfering ions on the removal of MB were studied. The adsorption data were analyzed by Langmuir and Freundlich isotherm models and a maximum adsorption amount of 47.62 mg g^‐1 and a langmuir adsorption equilibrium constant of 3.0 L mg^‐1 were obtained. The obtained results revealed that AC‐MIONs were effective adsorbents for fast removal of MB from different aqueous solutions. This adsorbent was successfully used for removal of MB from Karoon River water.     

Selective and effective adsorption of methyl blue by barium phosphate nano-flake

We report the synthesis of barium phosphate (BP) nano-flake and its adsorption behavior to methyl blue (MB) in aqueous solution. The as-obtained BP nano-flake revealed pure rhombohedral crystal structure. The adsorption capacity of MB onto BP reached 1500mgg(-1). The adsorption equilibrium results fitted well with the Freundlich isotherm model. The adsorption process took less than 30min to reach equilibrium. The adsorption kinetics was elucidated by the pseudo-second-order kinetic equation. It followed 2-stage and 3-stage intra-particle diffusion models for the low and high concentration of dye solutions, respectively. The adsorption of MB using the BP nano-flake was highly selective, compared with the adsorption of other dyes. The interactions between MB and BP were mainly the ionic interaction and hydrogen bonds, which were confirmed by the X-ray photoelectron spectroscopic results and the density functional theory calculations. The BP nano-flake revealed less than 5% decrease in adsorption amount when it was recycled and reused five times. The present work shows that the BP nano-flake is promising for practical applications in MB removal from aqueous solutions.     

ADSORPTION OF METHYLENE BLUE FROM AQUEOUS SOLUTION ON ATTAPULGITE

Batch adsorption experiments were carried out for the removal of methylene blue （MB） from aqueous solution using attapulgite as adsorbent. The effects of various parameters such as temperature, contact time, the pH value, and attapulgite dosage on the adsorption performance were investigated. The standard curve and regression equation were established by spectrophotometry. The adsorption experimental results showed that the adsorption equilibrium data were well in accord with Langmuir adsorptive model. The optimal result was acquired under the experimental condition of attapulgite dosage 0.18g, MB concentration 50.0mg/L, pH 10, and adsorption time 20min at room temperature.     

Monodisperse Mw-Pt NPs@VC as Highly Efficient and Reusable Adsorbents for Methylene Blue Removal

Addressed herein, monodisperse Vulcan carbon supported Pt nanoparticles (Mw-Pt NPs@VC) have been reproducibly synthesized using the microwave assisted method and their application for methylene blue (MB) removal from aqueous solutions was investigated through the adsorption mechanism. The prepared nanomaterials were characterized by X-ray diffraction, transmission electron microscopy, high resolution transmission electron microscopy and X-ray photoelectron spectroscopy. All results show that highly crystalline and colloidally stable nanoparticles have been formed and Mw-Pt NPs@VC were found to be one of the the most active catalyst. The results showed that the Mw-Pt NPs@VC nanoparticles had remarkable MB adsorption capacity of 271.15 mg/g. The equilibrium for MB adsorption was attained in ～55 min. Moreover, Mw-Pt NPs@VC is a reusable and promising material for MB removal since it preserves 95.6 % of its initial efficiency after six successive cycles of adsorption–desorption.     

Experimental and Theoretical Insights on Methylene Blue Removal from Wastewater Using an Adsorbent Obtained from the Residues of the Orange Industry

Chemical and thermochemical transformations were performed on orange peel to obtain materials that were characterized and further tested to explore their potential as adsorbents for the removal of methylene blue (MB) from aqueous solutions. The results show the high potential of some of these materials for MB adsorption not only due to the surface area of the resulting substrate but also to the chemistry of the corresponding surface functional groups. Fitting of the kinetic as well as the equilibrium experimental data to different models suggests that a variety of interactions are involved in MB adsorption. The overall capacities for these substrates (larger than 192.31 mg g⁻¹) were found to compare well with those reported for activated carbon and other adsorbents of agro-industrial origin. According to these results and complementary with theoretical study using Density Functional Theory (DFT) approximations, it was found that the most important adsorption mechanisms of MB correspond to: (i) electrostatic interactions, (ii) H-bonding, and (iii) π (MB)–π (biochar) interactions. In view of these findings, it can be concluded that adsorbent materials obtained from orange peel, constitute a good alternative for the removal of MB dye from aqueous solutions.     

Removal of dyes from water by conducting polymeric adsorbent

Chemically synthesized conducting polyaniline (PANI) was investigated as adsorbent for its possible application in the removal of organic dyes, such as methylene blue (MB) and procion red (PR) from their aqueous solution. PANI adsorbent behaves as a charged surface upon post‐synthesis treatment of the polymer with acid and base. The adsorbent thus treated shows a high selectivity for the removal of dyes in the adsorption process. The Langmuir adsorption isotherm was used to represent the experimental adsorption data. The cationic dye, MB can be preferentially removed by the base‐treated PANI while the anionic dye, PR is predominately removed by the acid‐treated one. These observations were further evidenced from the measurements of molar conductance and pH of the dye solutions employed for adsorption. The finding can be explained considering the electrostatic nature of adsorption coupled with the morphology of the PANI surface thus treated. Copyright © 2004 John Wiley & Sons, Ltd.     

Adsorption of methylene blue dye from aqueous solution by agricultural waste: Equilibrium,thermodynamics, kinetics,mechanism and process design

The adsorption of methylene blue (MB) dye from aqueous solution onto a cashew nut shell (CNS) was investigated as a function of parameters such as solution pH, CNS dose, contact time, initial MB dye concentration and temperature. The CNS was shown to be effective for the quantitative removal of MB dye, and the equilibrium was reached in 60 min. The experimental data were analysed by two-parameter isotherms (Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models) using nonlinear regression analysis. The characteristic parameters for each isotherm and the related correlation coefficients were determined. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were also evaluated, the sorption process was found to be spontaneous and exothermic. Pseudo-first-order, pseudo-second-order and Elovich kinetic models were used to analyze the adsorption process. The results of the kinetic study suggest that the adsorption of MB dye matches the pseudo-second-order equation, suggesting that the adsorption process is presumably chemisorption. The adsorption process was found to be controlled by both surface and pore diffusion. Analysis of adsorption data using a Boyd kinetic plot confirmed that the external mass transfer is a rate determining step in the sorption process. A single-stage batch adsorber was designed for different CNS doses to effluent volume ratios using the Freundlich equation. The results indicated that the CNS could be used effectively to adsorb MB dye from aqueous solutions.     

Enhancement of methylene blue removal by anodic oxidation using BDD electrode combined with adsorption onto sawdust

Studies on the removal of methylene blue (MB) from aqueous solutions by anodic oxidation (AO) using a boron-doped diamond (BDD) electrode, adsorption onto sawdust, and combined treatment have been undertaken. The results proved that AO presents a high efficiency in removing both color and COD in a wide pH interval. The total mineralization of the dye solution was performed in 6 h, which corresponds to relatively high-energy consumption. On the other hand, high sawdust dosage (12 g·L⁻¹) was needed to ensure 98% of color and 81% of COD removal. Combining AO and adsorption onto sawdust constitute a very interesting technology. For instance, AO for 1 h followed by sorption permits a reduction in energy consumption by 80 W·h·g_COD⁻¹, a reduction of more than 24 times the adsorbent dose and an enhancement of color and COD removal, indicating that sawdust is efficient in removing not only the MB initial molecules but also the electrogenerated by-products.