高容量亚胺基二乙酸型螯合树脂的制备及吸附性能

以甲基丙烯酸缩水甘油酯(GMA)为单体, 氯甲基化的交联聚苯乙烯树脂(CMCPS)为大分子引发剂, CuBr/2,2'-联吡啶(Bpy)为催化剂, 采用表面引发原子转移自由基聚合(SI-ATRP)技术, 使甲基丙烯酸缩水甘油酯聚合在CMCPS树脂表面, 制得了环氧化聚合物. 将该聚合物与亚胺基二乙酸(IDA)反应, 制备了高容量亚胺基二乙酸型螯合树脂(IDA-PGMA-CMCPS), 用元素分析对其进行了表征. 考察了螯合树脂对Cu²⁺的吸附性能及动力学和热力学参数. 该螯合树脂表面IDA接枝密度达8.15 mg/m². 研究结果表明, 树脂对Cu²⁺的吸附量随离子浓度和温度的升高而增加, 当pH值为2.2时, 对Cu²⁺离子的吸附效果最佳. 树脂的静态饱和吸附容量为1339.66 mg/g, Langmuir和Freundlich方程均呈现良好的拟合度. 通过热力学平衡方程计算ΔG<0, ΔH=270.60 kJ/mol, ΔS>0, 表明该吸附过程是自发、 吸热、 熵增加的过程. 动力学研究结果表明, 准二级动力学方程能较好拟合动力学实验结果, 该过程符合准二级动力学模型.     

Kinetics and Thermodynamics of Adsorption of VB12 onto Mesoporous Carbon Coated with PMMA

Ordered mesoporous carbons CMK-3, CMK-1 coated with poly(methyl methacrylate)(PMMA)(CMK-3- PMMA and CMK-1-PMMA) and pristine mesoporous carbons CMK-3, CMK-1 were employed to adsorb vitamin B12(VB12) from water solution. Adsorption isotherm and kinetics of adsorption were investigated via batch experi- ments. It was found that the adsorption capacity of VB12 at 30, 40 and 50 °C can reach 688.2, 572.4 and 428.7 mg/g, respectively. The adsorption isotherm can be described by Langmuir model. The pseudo first- and second-order kinetic models were employed to fit the dynamic adsorption. It was found that the dynamic adsorption follows the pseudo second-order model. The thermodynamic equilibrium coefficients obtained at different temperatures were used to evaluate the thermodynamic constants ΔG0, ΔH0 and ΔS0. The negative value of Gibbs free energy, ΔG0 indicates that the adsorption occurred via a spontaneous process. The increase in the value of –ΔG0 with increasing temperature indicates that higher temperatures were favourable to the sorption process. The enthalpy values of ΔH040 kJ/mol(66.36 kJ/mol and 56.43 kJ/mol) for CMK-3-PMMA and CMK-1-PMMA confirm that chemisorption were involved in the adsorption process. This is consistent with the IR spectra and is another evidence for the formation of hydrogen bond between PMMA in the pore of CMK-3 and VB12.     

介孔碳CMK-3对苯酚的吸附动力学和热力学研究

研究了介孔碳CMK-3对苯酚的吸附性能, 与传统商用活性碳(CAC)进行了比较, 结果表明, CMK-3比CAC的吸附量大、吸附速率快、达到平衡时间短, 是一种较好的吸附剂. 同时探讨了介孔碳CMK-3对苯酚的吸附热力学和动力学特征. CMK-3对苯酚的吸附行为可用Langmuir和Freundlich等温式进行描述, 相关性都较好, 但更符合Freundlich经验公式. 分别采用模拟一阶反应和二阶反应模型考察了吸附动力学, 并计算了这些动力学模型的速率常数. 模拟二级反应模型和实验数据之间有较好的相关性. 分别计算了热力学参数ΔG0, ΔS0和ΔH0, 结果表明, CMK-3对苯酚的吸附过程是吸热和自发的.     

磁性多壁碳纳米管吸附水中双氯芬酸的热力学与动力学

研究了磁化多壁碳纳米管(MWCNTs)对于水中非甾体抗炎药双氯芬酸的吸附过程.结果表明,双氯芬酸的吸附量随磁性MWCNTs投加量的增加而增大,而且吸附剂量增加到一定阶段后,双氯芬酸的吸附量达到平衡.在磁性MWCNTs的量为0.7g·L-1时,水溶液中双氯芬酸被磁性MWCNTs吸附的量达到最大,为33.37mg·g-1,对应的双氯芬酸去除率为98.1%.双氯芬酸的去除率随溶液pH的增加先增大后下降,随温度的升高而下降.用准一级、准二级模型进行了动力学分析.回归结果表明,准二级模型更准确地反映了吸附动力学.通过实验确定了Langmuir和Freundlich等温线的线性相关系数与标准偏差,结果揭示出Langmuir等温线与实验数据有很好的拟合度.对热力学参数的计算表明,ΔG00,意味着磁性MWCNTs对双氯芬酸的吸附是自发的;ΔH00,指明吸附是一个放热的物理吸附过程,温度低对吸附有利;ΔS00,代表该吸附是熵增过程.     

介孔TiO2对溶菌酶吸附的动力学和热力学

773.15 K下焙烧二钛酸(H₂Ti₂0₅)制备了介孔结构TiO₂。采用比表面分析仪(BET)、扫描电镜(SEM)、拉曼(Raman)光谱和X射线衍射(XRD)仪进行表征研究了介孔TiO₂对溶菌酶的吸附行为和机理。结果表明,该吸附过程较好地满足Langmuir吸附模型;随着溶液pH值的增高,溶菌酶在介孔TiO₂上的吸附量先增大后减小。在pH = 7.2时,达到最大吸附容量72.5 mg·g^-1。该介孔TiO₂对溶菌酶具有良好的吸附稳定性,经过5次循环后吸附的溶菌酶残余量仍有81.6%。动力学研究表明,介孔TiO₂与溶菌酶间的吸附满足准二级动力学模型,吸附传质过程由膜扩散和粒内扩散共同影响与控制。对热力学参数的计算发现,该过程ΔG⁰ < 0, ΔH⁰ > 0, ΔS⁰ > 0,表明介孔TiO₂对溶菌酶的吸附是一个自发的、吸热的熵增过程。     

Studies on Adsorption Behavior and Mechanism of Copper（ Ⅱ ） onto Amino Methylene Phosphonic Acid Resin

IntroductionThe adsorption ability of the functional poly-mer used to enrich metal ions is strong and the op-eration of the functional polymer is convenient.The polymer having adsorbed metal ions can be re-covered by means of an acid or an alkaline solutionand the recovered polymeric material can bereused.The adsorption ability of the polymer withvarious functional groups is different for differentmetals.Because nucleophilic atoms such as oxy-gen,nitrogen,sulphur and phosphorous atoms cancoord…     

改性层状双氢氧化物对铜离子(Ⅱ)和双酚A的协同吸附

采用离子交换法制备了十二烷基苯磺酸根(DBS^-)和柠檬酸根(Cit^3-)复合改性层状双氢氧化物(LDHs),简写为DBS-Cit-LDHs。 利用粉末X射线衍射分析、红外光谱分析、比表面积测定以及元素分析等技术手段对样品进行了表征。 结果表明,DBS^-和Cit^3-已柱撑进入LDHs层间。 研究了DBS-Cit-LDHs对水中重金属离子Cu²⁺和有机污染物双酚A(BPA)的协同吸附性能。 吸附实验结果表明,DBS-Cit-LDHs能同时高效去除Cu²⁺和BPA;对Cu²⁺的强吸附能力缘于DBS-Cit-LDHs层间Cit^3-与Cu²⁺形成了稳定配合物;对BPA的强吸附能力缘于分配作用,且吸附能力与样品比表面积无关。 DBS-Cit-LDHs对Cu²⁺的吸附动力学和热力学分别符合准二级动力学方程和Freundlich等温式;对BPA的吸附分别符合准一级动力学方程和Linear等温式。 二者吸附过程的ΔG^o和ΔH^o均为负值,表明吸附为自发放热过程。     

一种阴离子型三维金属有机框架材料Cu(BDC-NH_2)(4,4'-Bipy)_(0.5)(BDC=对苯二甲酸根,Bipy=联吡啶)的制备及其对甲基紫的吸附性能

以2-氨基对苯二甲酸、4,4'-联吡啶配体和硝酸铜为原料,在溶剂热的条件下,合成了一种的阴离子型三维金属有机框架(MOF)材料Cu(BDC-NH_2)(4,4'-Bipy)_(0.5)(BDC=对苯二甲酸根,Bipy=联吡啶)。通过IR、XRD、SEM、TG、N_2吸附法测比表面积等技术手段表征材料的结构和性能。研究了Cu(BDC-NH_2)(4,4'-Bipy)_(0.5)材料对甲基紫的吸附性能,探讨了甲基紫溶液的初始p H值和初始浓度以及不同吸附温度对吸附量的影响。结果表明,等温吸附模型符合Langmuir等温吸附模型,动力学符合拟二级动力学。热力学参数ΔG0、ΔΗ0和ΔS0,表明Cu(BDC-NH_2)(4,4'-Bipy)_(0.5)对甲基紫的吸附是自发和放热的,在溶液p H=9,温度为20℃条件下,Cu(BDC-NH_2)(4,4'-Bipy)_(0.5)对甲基紫的吸附量为60.09 mg/g,说明Cu(BDC)(4,4'-Bipy)_(0.5)材料可以通过氨基改性,提高其对染料的吸附能力。     

立方体纳米Cu2O吸附热力学及动力学的粒度效应研究

采用不同粒径的单一(100)晶面的立方体纳米Cu₂O作为模型材料, 研究了粒径和温度对其吸附动力学和吸附热力学性质的影响规律. 基于已建立的纳米材料吸附热力学和动力学理论, 推导出了单一(100)晶面立方体纳米Cu₂O材料的吸附热力学和吸附动力学性质与粒径之间的关系式. 实验结果与理论预测结果一致: 随着纳米Cu₂O粒径的减小, 吸附速率常数增大而吸附活化能和吸附指前因子减小; 标准摩尔吸附Gibbs自由能 Δ_a $G^{\rlap{-}0}_{m}$减小而标准吸附平衡常数ln $K^{\rlap{-}0}$、 标准摩尔吸附焓 Δ_a $H^{\rlap{-}0}_{m}$和标准摩尔吸附熵 Δ_a$S^{\rlap{-}0}_{m}$均增大, 且以上参数均与粒度的倒数具有较好的线性关系.     

Removal of Thiram from Aqueous Solutions

In this study activated carbon was used for the removal of thiram from aqueous solutions. Adsorption experiments were carried out as a function of time, initial thiram concentration and temperature. Equilibrium data fitted well to the Freundlich and Langmuir equilibrium models in the studied concentration range. Adsorption kinetics followed a pseudo second‐order kinetic model rather than pseudo first‐order model. The results from kinetic experiments were used to describe the adsorption mechanism. Both boundary layer and intraparticle diffusion played important role in the adsorption mechanism of thiram. Thermodynamic parameters (ΔG₀, ΔH₀, and ΔS₀) were determined and the adsorption process was found to be an endothermic one. The negative values of ΔG⁰ at different temperatures were indicative of the spontaneity of the adsorption process.     

Isotherm, kinetic and thermodynamic studies of lead and copper uptake by H2SO4 modified chitosan

The kinetic and thermodynamic adsorption and adsorption isotherms of Pb(II) and Cu(II) ions onto H₂SO₄ modified chitosan were studied in a batch adsorption system. The experimental results were fitted using Freundlich, Langmuir and Dubinin–Radushkevich isotherms; the Langmuir isotherm showed the best conformity to the equilibrium data. The pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models were employed to analyze the kinetic data. The adsorption behavior of Pb(II) and Cu(II) was best described by the pseudo-second order model. Thermodynamic parameters such as free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) were determined; the adsorption process was found to be both spontaneous and exothermic. No physical damage to the adsorbents was observed after three cycles of adsorption/desorption using EDTA and HCl as eluents. The mechanistic pathway of the Pb(II) and Cu(II) uptake was examined by means of Fourier transform infrared (FTIR) and Energy dispersive X-ray (EDX) spectroscopy. The equilibrium parameter (R_L) indicated that chitosan–H₂SO₄ was favorable for Pb(II) and Cu(II) adsorption.     

埃洛石纳米管稳定的Pickering高内相乳液模板制备大孔聚合泡沫吸附分离三氟氯氰菊酯

利用天然粘土埃洛石纳米管和少量非离子表面活性剂吐温80为乳化剂构建了水包油（O/W）型Pickering高内相乳液（HIPEs）,并以其为模板制备了大孔聚合泡沫（MPFs）。MPFs具有开口的大孔结构、丰富的内部交联孔道和亲水的表面,且在水中呈悬浮状态,这些特点均有利于吸附水体系中的菊酯类农药。结合静态吸附实验研究了MPFs吸附三氟氯氰菊酯的平衡与动力学行为。结果表明,准一级动力学方程与Langmuir等温方程分别较好地拟合了吸附动力学与平衡数据（相关性系数（R²）>0.99）,证明了吸附过程是一个单分子层的化学吸附过程。298 K时MPFs对三氟氯氰菊酯的吸附平衡时间和饱和吸附容量分别为240 min和23.98 μmol·g^-1,且吸附容量随着温度与三氟氯氰菊酯初始浓度的升高而逐渐增大。研究证明了水中呈悬浮状态的MPFs是理想和稳定的吸附剂,可有效去除水溶液中疏水性有机污染物。     

酸性和碱性介质中甘氨酸解离吸附和氧化的EQCM研究

用电化学石英晶体微天平(EQCM)研究酸性和碱性介质中甘氨酸在Pt电极上的吸附和氧化过程.结果表明,甘氨酸的解离吸附和氧化行为与溶液的酸碱性密切相关.酸性溶液中甘氨酸吸附较弱,碱性溶液中则产生强吸附物,且当电位低于0V(vs.SCE)时可吸附于Pt电极表面.此外,碱性溶液中甘氨酸还表现出较高的电氧化活性.通过EQCM定量检测上述过程中Pt电极表面的质量变化,测定了不同电位区间(氢区、双电层区和氧区)每传递一个电子所对应的电极表面吸附物种的平均摩尔质量.     

Adsorption of Heavy Metal Ions from Aqueous Solutions by Zeolite Based on Oil Shale Ash: Kinetic and Equilibrium Studies

Na-A zeolite was successfully synthesized via the alkaline fusion method with oil shale ash as the raw material. The adsorption capacity of it was tested by removing Cu²⁺, Ni²⁺, Pb²⁺ and Cd²⁺ from aqueous solutions. The results reveal the maximum adsorption capacity of adsorbent for Pb²⁺, Cu²⁺, Cd²⁺ and Ni²⁺ were 224.72, 156.74, 118.34 and 53.02 mg/g, respectively. The effects of contact time and pH value of solutions on the adsorption efficiency of the zeolite were evaluated. Besides, The equilibrium adsorption data and the batch kinetic data were correlated with Langmuir and Freundlich models and the pseudo-first-order and pseudo-second-order models separately. The results show that the Langmuir isotherm and the pseudo-second-order equation were more suitable for the adsorption of Na-A zeolite for the metal ions. In addition, Thermodynamic parameters of the adsorption(the Gibbs free energy, entropy, and enthalpy) were also evaluated and discussed. The results demonstrate that the adsorption process was spontaneous and endothermic under natural conditions and the synthesized zeolite was an effective adsorbent for the removal of metal ions from aqueous solution.     

磷钼钨杂多酸修饰金属有机骨架MOF-5复合材料吸附亚甲基蓝

采用水热合成法,在合成金属有机骨架MOF-5的过程中引入活性组分磷钼钨杂多酸(H₆P₂Mo₁₅W₃O₆₂),制备出一种新型吸附剂H₆P₂Mo₁₅W₃O₆₂/MOF-5。 利用H₆P₂Mo₁₅W₃O₆₂/MOF-5材料对亚甲基蓝溶液进行了材料的吸附性能研究,探讨了亚甲基蓝溶液的初始pH值和初始浓度以及不同吸附温度对吸附量的影响。 结果表明,在较低的温度和亚甲基蓝溶液较低的初始pH值的条件下,有利于H₆P₂Mo₁₅W₃O₆₂/MOF-5对亚甲基蓝的吸附。 实验结果能够较好地符合Langmuir吸附等温式以及二级动力学模型,对亚甲基蓝的最大吸附量可达401.6 mg/g。 热力学参数ΔG<0、ΔH<0和ΔS>0,表明H₆P₂Mo₁₅W₃O₆₂/MOF-5对亚甲基蓝的吸附过程是自发、放热的。 此外,还探讨了H₆P₂Mo₁₅W₃O₆₂/MOF-5对甲基紫、孔雀石绿、罗丹明B和甲基橙等其它染料的吸附性能,结果表明,H₆P₂Mo₁₅W₃O₆₂/MOF-5对阳离子染料有较好的吸附效果。     

Selective removal of nitrate by using a novel macroporous acrylic anion exchange resin

An anion exchange resin NDP-5 has been prepared successfully and applied on the selective removal of nitrate from SO₄^2-/ NO₃^- binary co-existence system.The composition and morphology of NDP-5 were confirmed by FT-IR and SEM.The NDP-5 resin exhibits the completely different behavior on the adsorption capacity,adsorption kinetic and the effect of the completing anion in the absence or presence of sulfate,compared to D213.And,the resultants of kinetic are well fitted by the pseudo-first-order and pseudo-second-order models.These results are very important to develop novel resins with great features.     

PREPARATION AND CHARACTERIZATION OF NOVEL CHITOSAN DERIVATIVES:ADSORPTION EQUILIBRIUM OF IRON(Ⅲ)ION

The adsorption of Fe(Ⅲ)ions from aqueous solution by chitosan alpha-ketoglutaric acid(KCTS)and hydroxamated chitosan alpha-ketoglutaric acid(HKCTS)was studied in a batch adsorption system.Experiments were carried out as function of pH,temperature,agitation rate and concentration of Fe(Ⅲ)ions.The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and isotherm constants were determined.The Langmuir model agrees very well with experimental data.The pseudo-first-order and second-order kinetic models were used to describe the kinetic data and the rate constants were evaluated.The dynamical data fit well with the second-order kinetic model.The pseudo second-order kinetic model was indicated with the activation energy of 19.61 and 7.98 KJ/mol for KCTS and HKCTS,respectively.It is suggested that the overall rate of Fe(Ⅲ)adsorption is likely to be controlled by the chemical process.Results also showed that novel chitosan derivatives(KCTS and HKCTS)were favorable adsorbents.     

H3PO4改性PS-EDTA树脂对水相中Cu2+、Zn2+和Cd2+的吸附性能研究

大孔氯甲基化聚苯乙烯小球先后与乙二胺、2-氯乙酸反应得EDTA型螯合树脂(PS-EDTA),再用磷酸在室温处理得PS-EDTA/P树脂。PS-EDTA/P树脂被用于水相中Cu2+、Zn2+和Cd2+的吸附净化处理,探讨了溶液的pH值、初始金属离子浓度、时间、温度等因素对吸附性能的影响,并研究了其对重金属离子的吸附动力学和热力学。结果表明,PS-EDTA/P树脂对Cu2+和Zn2+的吸附符合Langmuir等温式、对Cd2+的吸附符合Freundlich等温式,准二级吸附动力学方程能够很好地描述3种金属离子在树脂上的吸附动力学行为。同时,PS-EDTA/P树脂对重金属吸附的热力学参数表明,PS-EDTA/P树脂对Cu2+、Zn2+和Cd2+的吸附是一个自发的、吸热的过程。已吸附Cu2+、Zn2+和Cd2+的树脂可以用0.1mol/L HCl解吸,解吸后的树脂对Cu2+、Zn2+和Cd2+仍具有较高的吸附量。     

Adsorption and desorption kinetics of CmE8 on impulsively expanded or compressed air–water interfaces

The adsorption kinetics of C_mE₈ (m=10, 12, and 14) at an air–water interface are investigated. A pendant bubble is formed in aqueous surfactant solution and allowed to attain equilibrium. The bubble is then impulsively expanded or compressed with some change of area large enough to appreciably deplete or enrich the surface concentration and change the surface tension. The surfactant is then allowed to re-equilibrate. The surface tension evolution during this process is measured using video images of the pendant drop. The surface tension evolution is compared to mass transfer arguments. First, the re-equilibration of interfaces laden with C₁₄E₈ are studied. For compressed interfaces, surfactant must desorb to restore equilibrium. The surface tension rises more slowly than predicted by a diffusion-controlled evolution, implying that the re-equilibration is mixed diffusive-kinetic controlled. By analyzing the surface tension evolution in terms of a mixed kinetic-diffusive model, values for the kinetic constants for adsorption and desorption are found. These results are compared to those obtained previously for C_mE₈ (m=10 and 12). For all of these molecules, the adsorption rate constant is similar (β₁=5.6±1.0×10⁻⁶ cm³ (mol s)⁻¹). However, the desorption rate constant (₁) varies strongly. Increasing m by 2 lowers the desorption rate constant ₁ by nearly a factor of 15. This is consistent with an increased resistance to re-immersion into water with the length of a hydrocarbon chain.     

Denatured Thermodynamics of Proteins in Weak Cation－exchange Chromatography

The thermostability of some proteins in weak cation-exchange chromatography was investigated at 20—80 ℃. The results show that there is a fixed thermal denaturation transition temperature for each protein. The appearance of the thermal transition temperature indicates that the conformations of the proteins are de-stroyed seriously. The thermal behavior of the proteins in weak cation-exchange and hydrophobic interaction chromatographies were compared in a wide temperature range. It was found that the proteins have a higher thermostability in a weak cation-exchange chromatography system. The thermodynamic parameters (△H^0,△S^0) of those proteins were determined by means of Van′t t Hoff re|ationship(lnk′-1/T). According to stan-dard entropy change(△S^0) , the conformational change of the proteins was judged in the chromatographic pro-cess. The linear relationships between △H^0 and △S^0 can be used to evaluate “compensation temperature“ (β) at the protein denaturation and identify the identity of the protein retention mechanism in weak cation-ex-change chromatography.