阴离子型有机化合物在LDHs上的动力学和热力学研究

本文考察水滑石焙烧产物MgAl-LDO吸附3种阴离子染料AcidRed88（AR88）、AcidOrange 3（AO3）、AcidViolet90（AV90）过程中的热力学和动力学机理,并在不同温度下探究该吸附过程的热力学参数。实验结果表明：MgAl-LDO对染料阴离子的吸附过程复合Langmuir吸附等温模型,且为自发、放热的过程。3种染料在MgAl-LDO上的吸附过程均符合准二级反应动力学模型,且该吸附过程是由MgAl-LDO与阴离子染料之间的反应速率控制而不是两者之间的扩散作用。计算所得的吉布斯自由能绝对值在7~15kJ·mol^-1,这主要是由染料阴离子与MgAl-LDHs层板的氢键作用产生,结合MaterialsStudio 5.5软件模拟染料分子在MgAl-LDHs上的排列分布,推测MgAl-LDO对阴离子染料的吸附机理是表面吸附（占优势）与层间插层的协同作用。     

AB24在MgAl-LDO上的吸附性能及机理研究

本文探讨了nMg/nAl=3的水滑石焙烧产物(MgAl-LDO)对染料酸性黑24(AB24)的吸附性能及其机理。考察了不同因素对MgAl-LDO吸附AB24性能的影响,并研究了吸附过程的热力学和动力学机理。实验结果表明:MgAl-LDO对AB24具有优异的吸附性能,在298 K,pH=10条件下,1.0 g.L-1MgAl-LDO对1 000 mg.L-1AB24溶液的吸附容量和去除率分别达到998.31 mg.g-1和99.83%。动力学和热力学研究表明:MgAl-LDO对AB24的吸附过程同时符合Langmuir和Freundlich等温吸附方程,并且是个放热、自发的过程。计算所得的吉布斯自由能绝对值在10~15 kJ.mol-1,这主要是由染料分子与水滑石层板的氢键作用产生,结合Materials Studio 5.5软件模拟AB24染料分子在MgAl-LDHs上的排列分布,推测MgAl-LDO对AB24的吸附机理是表面吸附(占优势)与层间插层的协同作用。同时,该吸附过程符合准二级反应动力学模型。     

酸性湖蓝7在LDO上吸附性能及机理的研究

探讨了Mg/Al＝3的水滑石焙烧产物(MgAl-LDO)对染料酸性湖蓝7(AB7)的吸附性能及其机理. 考察了不同因素对MgAl-LDO吸附AB7性能的影响, 并研究了吸附过程的热力学机理. 实验结果表明: MgAl-LDO对AB7具有优异的吸附性能, 在288 K, pH＝6.74条件下, 0.33 g·L^-1 MgAl-LDO对150 mg·L^-1AB7溶液的吸附容量和去除率分别达到446.9 mg·g^-1和99.31%. 热力学研究表明: MgAl-LDO对AB7的吸附过程同时符合Langmuir 和 Freundlich等温吸附方程, 并且是个放热、自发的过程. 计算所得的吉布斯自由能绝对值在8～10 kJ·mol^-1, 这主要是由染料分子与水滑石层板的氢键作用产生, 结合Materials Studio 5.5软件模拟AB7染料分子在MgAl-LDHs上的排列分布, 推测MgAl-LDO对AB7的吸附机理是表面吸附作用. 同时, 经4次回收, LDO对AB7的去除率仍达到85%以上.     

Mg/Al水滑石的焙烧产物吸附酸性红88的动力学和热力学机理研究

文章研究了Mg/Al水滑石焙烧产物(LDO)对酸性红88 (AR88)的吸附性能及其机理. 考察了温度对其吸附性能的影响, 探讨了吸附过程的动力学和热力学规律. 热力学研究表明: LDO对AR88的吸附过程稍符合Langmuir等温吸附. 从Langmuir等温式计算的 , 为负值, 表明吸附过程为放热、熵减小的过程, 这是因为LDO在吸附酸性染料后恢复了层状结构|不同温度下 均为负值, 表明吸附过程是自发进行的. 动力学研究表明: 吸附动力学符合准二级动力学模型, 动力学计算吸附过程的活化能E_a＝54.53 kJ•mol^－1. 利用Materials Studio 4.3软件中的CASTEP程序模块和Focite模块模拟了AR88染料分子在Mg/Al水滑石(LDHs)的尺寸大小和排列方式, 推测吸附机理是以表面吸附占主要优势并伴有少部分插层.     

磁性共价有机框架材料吸附甲基橙和茜素绿两种阴离子有机染料

以自制的磁性共价有机框架材料(COF)为吸附剂,采用静态吸附法研究了其对甲基橙(MO)和茜素绿(AG-25)的吸附行为。 结果表明,在25 ℃,pH值6~8的条件下,磁性COF对两种阴离子染料的的吸附量分别为997和1314 mg/g。 两种染料的吸附等温线符合Langmuir等温吸附模型,表明吸附过程为单层吸附;吸附动力学均符合准二级动力学模型,说明吸附过程以化学吸附为主。 磁性COF对水体中的阴离子染料体现出高吸附量和快速吸附的特点,具有潜在的价值。     

具有超高阳离子染料去除能力的磺酸功能化球形共价有机框架

通过三醛基间苯三酚(TFP)与2,2′-联苯胺二磺酸(BDSA)的席夫碱反应, 合成了β-酮烯胺连接的磺酸功能化球形共价有机框架(TFP-BDSA COF). 所得阴离子型TFP-BDSA可迅速吸附如亚甲基蓝(MLB)、 结晶紫(CV)和罗丹明B(RhB)等阳离子染料, 而对如甲基橙(MO)和荧光素钠(FS)等阴离子染料则难以吸附, 该COF可实现基于电荷模式的阴离子、 阳离子染料的分离. TFP-BDSA对阳离子染料的吸附动力学均遵循拟二级吸附动力学模型, 吸附过程符合Langmuir吸附模型, 其对MLB, CV和RhB的最大吸附容量分别高达1116, 1429和1638 mg/g. 与其它COFs材料相比, TFP-BDSA对CV和RhB的吸附容量最高. 该工作可为开发功能COFs材料实现对废水中有机污染物的快速吸附和有效去除提供参考.     

三聚氰胺功能化多孔有机聚合物的合成及其对甲基橙的吸附性能

首先以对三联苯(TP)和对苯二甲酰氯(TC)为单体合成了酮基聚合物前体(TP-TC),而后基于席夫碱反应将三聚氰胺(MA)与之交联得到胺功能化的多孔有机聚合物TP-TC-MA。通过扫描电镜(SEM)、透射电镜(TEM)、傅里叶变换红外光谱(FT-IR)、X射线衍射(XRD)、氮气吸附-脱附(BET)以及零电荷点(pH_pzc)的测定等手段对合成的多孔有机聚合物进行表征。以染料废水中典型的阴离子染料甲基橙为研究对象,研究了TP-TC-MA对其吸附行为,并探讨了吸附机制。利用紫外-可见分光光度计(UV-Vis)得出目标污染物的紫外吸收光谱标准曲线,标准曲线拟合相关系数(R²)为0.999。结果表明,TP-TC-MA由于具有高比表面积(708.5 m²/g)和总孔体积(0.556 cm³/g)以及丰富的含氮基团,对阴离子染料甲基橙表现出优异的吸附性能。TP-TC-MA对水中甲基橙的吸附动力学符合准二级动力学方程,吸附平衡数据可以采用Langmuir等温吸附模型描述。经由Langmuir等温吸附模型计算得到的理论最大吸附容量为156.3 mg/g。选择性实验结果表明,TP-TC-MA对阴离子染料甲基橙具有更强的吸附作用,吸附作用机理可归结为静电相互作用、氢键和π-π相互作用等。在重复使用5次之后,TP-TC-MA对甲基橙仍保持90%以上的去除率,表明材料具有良好的稳定性和重复利用性,在染料废水处理中具有很好的应用前景。     

聚苯胺-氧化铁磁性复合材料的制备及其对甲基橙吸附性能的应用

用"化学一步法"制备了聚苯胺-氧化铁(PANI@Fe_2O_3)磁性复合材料,并用红外光谱和X射线衍射对其进行了表征。为验证此复合材料作为处理染料废水的吸附剂的性能,选择了甲基橙(MO)作为染料模型化合物,对其在不同的酸度、吸附时间、温度以及盐度等条件下的吸附情况进行试验。结果表明:PANI@Fe_2O_3对MO的吸附经30min已达到平衡;根据相关参数,可确定此吸附过程符合准二级动力学模型。在试验的温度范围(293～313K)内,温度升高,PANI@Fe_2O_3对MO的吸附量增大。染料废液在弱酸性条件下(如pH 5)有利于此吸附剂对染料的吸附。此外盐度(以氯化钠进行试验)的增大,使MO的吸附量显著降低。热力学试验结果表明:上述吸附符合Freundlich等温吸附模型,为自发吸热过程的多层吸附。此外,由于PANI@Fe_2O_3为磁性材料,经吸附处理后在外磁场的作用下易于与水体分离。     

镍铁类水滑石对偶氮阴离子染料的吸附脱色作用

采用镍铁类水滑石作为吸附剂,对偶氮阴离子染料酸性大红G、活性艳红X-3B和直接耐酸大红4BS废水进行脱色处理,研究了时间、镍与铁的物质的量之比、初始pH和无机电解质添加剂等因素对脱色率的影响,并结合红外光谱和X射线衍射分析结果讨论了其吸附脱色机理.结果表明,三种染料在镍铁类水滑石上的吸附均为层间的阴离子交换吸附和外表面的吸附.通过阴离子交换进入层间后,不同于直接耐酸大红4BS阴离子,酸性大红G和活性艳红X-3B两种阴离子与水滑石层间水分子之间产生氢键作用;在化学键合过程中,染料分子被镍铁类水滑石表面Fe3+氧化,同时偶氮键断裂导致脱色.     

纳米TiO_2粒径、孔径对酸性紫43吸附动力学与热力学行为的影响

探究锐钛型纳米TiO2粒径(5-10、25、40、60、100nm)及孔径(96,120,134,143,52)对染料废水(酸性紫43)吸附动力学与热力学行为的影响。假二级方程和准一级方程分别能准确描述TiO2粒径≤100nm吸附动力学过程。经Weber-Morris和Dumwald-Wagner扩散模型分析,吸附速率由膜扩散和内扩散共同控制并受粒径影响。吸附热力学符合Langmuir等温吸附方程,最大吸附量(Qmax)与孔径正相关,与粒径无关,60nm TiO2孔径最大,吸附效果最好,Qm可达104.17mg/g;参数40kJ/mol△H0,吉布斯自由能△G0,受温度影响不大,说明吸附过程是自发的吸热反应,以物理吸附为主。     

Thermodynamics and Kinetics of Bacterial Cellulose Adsorbing Persistent Pollutant from Aqueous Solutions

The adsorption capability of bacterial cellulose(BC) for anionic dye acid fuchsine was studied. Meanwhile, the processes of the adsorption were investignted and fitted by adsorption isotherm models, adsorption thermodynamics and adsorption kinetics models, respectively. The changes of BC before and after adsorbing acid fuchsine were investigated via scanning electron microscopy(SEM) and Fourier transform infrared spectroscopy(FTIR) to further explain the adsorption mechanism. The results show that acid fuchsine could be effectively adsorbed by BC. The adsorption process was fitted well by Langmuir equation and the pseudo-second order kinetics, indicating that the adsorption process was monolayer molecule adsorption with the main action of chemical adsorption. The adsorption process was spontaneous and endothermic. Glucuronic acid groups and hydroxyl groups were responsible for the adsorption of acid fuchsine on BC.     

Hydroxyethyl Starch-g-Poly-(N,N-dimethylacrylamide-co-acrylic acid): An efficient dye removing agent

Hydroxyethyl Starch-g-Poly-(N,N-dimethylacrylamide-co-acrylic acid) was synthesized by solution polymerization technique using potassium peroxydisulfate (K₂S₂O₈) as the initiator at 90 °C. The synthesized graft copolymer was characterized by FTIR, NMR (both ¹H and ¹³C) Spectroscopy, molecular weight determination by GPC, TGA/DTG and SEM analysis. Biodegradation study was carried out by enzymatic hydrolysis. The number of carboxylic acid groups incorporated into the polymer was calculated by measuring neutralization equivalent (N.E) of the graft copolymer titrimetrically. The synthesized graft copolymer was used as the adsorbent for the removal of Malachite green, a cationic dye from its aqueous solution. The operating variables studied were the amount of adsorbent, solution pH, contact time, temperature and the initial dye concentration. The adsorption data were used to fit in the pseudo-first order and pseudo-second order rate equation in order to investigate the sorption mechanism. Equilibrium isotherm was analyzed using the Langmuir and the Freundlich isotherms. In the present investigation it was found that the adsorption kinetics followed a pseudo second order kinetics for the studied dye concentration range. The negative value of free energy change indicates the spontaneous nature of the adsorption and also suggesting a chemisorption process.     

Removal of copper(II) from aqueous solution with rape stalk modified by citric acid

In this paper, rape stalk was modified with citric acid (CA) to prepare copper ion biosorbent. The modified rape stalk (MRS) was characterized by Fourier transforms infrared (FTIR), zeta potential, and thermogravimetric analysis (TGA). The effects of various parameters like initial Cu²⁺ concentration, contact time, initial pH, and temperature on adsorption capacity were studied. The adsorption capacity of MRS at 298 K was 69.84 mg/g, far higher than 18.24 mg/g for native rape stalk (NRS). The adsorption mechanism was also evaluated in terms of kinetics and thermodynamics. The adsorption equilibrium data was well described by the Langmuir isotherm model. The adsorption process followed the pseudo-second-order rate kinetics. Thermodynamic study showed spontaneous and endothermic nature of the adsorption process. The ion exchange of the adsorption mechanism was affirmed. MRS could be a potentially low-cost and green adsorbent for removal of Cu²⁺ from aqueous solution.     

Adsorption Behavior and Dynamic Interactions of Anionic Acid Blue 25 on Agricultural Waste

In this study, adsorption characteristics of a negatively charged dye, Acid Blue 25 (AB25), on pomelo pith (PP) was studied by varying the adsorption parameters, with the aim of evaluating the adsorption mechanism and establishing the role of hydrogen bonding interactions of AB25 on agricultural wastes. The kinetics, intraparticle diffusion, mechanism, and thermodynamics of the AB25 adsorption were systematically evaluated and analyzed by pseudo-first-order and pseudo-second-order kinetic models, the Weber–Morris intraparticle and Boyd mass transfer models, the Langmuir, Freundlich, Dubinin–Radushkevich, and Temkin isotherm models, and the Van’t Hoff equation. It was found that AB25 adsorption followed pseudo-second-order kinetics, governed by a two-step pore-volume intraparticle diffusion of external mass transfer of AB25 onto the PP surface. The adsorption process occurred spontaneously. The adsorption mechanism could be explained by the Langmuir isotherm model, and the maximum adsorption capacity was estimated to be 26.9 mg g⁻¹, which is comparable to many reported adsorbents derived from agricultural wastes. Changes in the vibrational spectra of the adsorbent before and after dye adsorption suggested that AB25 molecules are bound to the PP surface via electrostatic and hydrogen bonding interactions. The results demonstrated that the use of pomelo pith, similar to other agricultural wastes, would provide a basis to design a simple energy-saving, sustainable, and cost-effective approach to remove negatively charged synthetic dyes from wastewater.     

阴离子树脂D02吸附2-酮基-L-古龙酸的热力学和动力学研究

应用一种新型的阴离子树脂D02直接吸附发酵液中的2-酮基-L-古龙酸.研究了D02树脂对水溶液中2-酮基-L-古龙酸的吸附热力学和吸附动力学特性.热力学研究表明,2-酮基-L-古龙酸在D02树脂上的吸附平衡数据遵循Langmuir吸附等温方程.吸附过程△G＜0,△S＞0,△H＞0,表明此吸附过程吸热,升高温度有利于吸附反应的发生.动力学研究显示,D02树脂对2-酮基-L-古龙酸的吸附过程主要受内扩散控制.     

Adsorption mechanism of Cu from aqueous solution by chitosan-coated magnetic nanoparticles modified with α-ketoglutaric acid

In order to better understand the adsorption mechanism of chitosan-coated magnetic nanoparticles modified with α-ketoglutaric acid (α-KA-CCMNPs), the removal of Cu²⁺ by α-KA-CCMNPs from aqueous solution was investigated in a batch system at 18, 35 and 50 °C. Different experimental approaches were applied to show mechanistic aspects, such as adsorption isotherms, kinetics and thermodynamics studies. Adsorption equilibrium studies showed that Cu²⁺ adsorption followed Langmuir model. The kinetics of the interactions was best described by pseudo-second-order mechanism. The thermodynamic parameters (ΔG°, ΔH° and ΔS°) analysis predicted that the adsorption process was strongly dependent on temperature of medium, and spontaneous and endothermic process. The XPS combined with FT-IR spectra revealed that N atom of –NH– group and O atom of carboxyl group in α-KA-CCMNPs coordinated with Cu²⁺. Experimental results from this study provide data that would be required if this heavy metal adsorption system was to be “scaled up” for industrial application.     

Applicability of waste materials--bottom ash and deoiled soya--as adsorbents for the removal and recovery of a hazardous dye, brilliant green

Deoiled soya, an agricultural waste material, and bottom ash, a waste of power plants, have been successfully used for the removal and recovery of the hazardous water-soluble dye brilliant green from water. To remove the dye from water, batch adsorption studies have been carried out by observing the effects of pH, concentration, amounts of adsorbents, size of adsorbent particles, etc. Attempts have also been made to monitor the adsorption process through Langmuir, Freundlich, Tempkin, and D-R adsorption isotherm models. Relevant thermodynamic parameters have also been calculated from these models. The adsorption process has been found endothermic and feasible at all the temperatures. The kinetics of the adsorption was also recorded and indicates pseudo-second-order kinetics in both cases. Kinetic operations also reveal the involvement of a film diffusion mechanism for the deoiled soya adsorption at all the temperatures, while bottom ash undergoes through a particle diffusion mechanism at only 30 °C and at higher temperatures a film diffusion mechanism operates. Bulk removal of the dye has been carried out through column studies for both adsorbents. Attempts have also been made to recover the dye from exhausted columns by eluting sulfuric acid of pH 3.     

硫辛酸在3种不同树脂上的吸附热力学和动力学研究

研究了硫辛酸在3种不同树脂上的吸附热力学和动力学。研究结果表明,硫辛酸在NG-16树脂上的吸附等温线符合Langmuir等温吸附方程,是单分子层吸附,吸附过程符合一级动力学吸附方程。硫辛酸在NDA-100和ND-90树脂上的吸附等温线符合Langmuir等温吸附方程,但并不只是单分子层吸附,对于中高浓度(大于400mg/L)的硫辛酸溶液更重要的是微孔填充作用。硫辛酸在NDA-100和ND-90树脂上的吸附过程分为大孔、中孔区的表面吸附和微孔区的微孔填充两个阶段,两个阶段都符合一级动力学吸附方程。     

2-噻吩乙酸在3种树脂上的吸附行为研究

通过静态吸附实验 ,研究了XAD 4、NDA 10 0和ND 90吸附树脂对水溶液中 2 噻吩乙酸的吸附热力学及动力学特性 ,结果表明 ,2 噻吩乙酸在XAD 4树脂上是单层吸附 ,符合Langmuir等温吸附方程 ,吸附过程符合准一级动力学吸附方程 .2 噻吩乙酸在NDA 10 0和ND 90树脂上的吸附也能用Langmuir等温吸附方程表示 ,但并不只是单层吸附而主要是由毛细管凝聚和微孔填充作用造成的 ,吸附过程可分为大孔和中孔区的吸附以及微孔区的吸附两个阶段 ,两个阶段都符合准一级动力学吸附方程