用于染料吸附的改性沸石吸附剂:机理及功能表征

以十六烷基三甲基溴化铵(CTAB)改性沸石作为吸附剂,研究了其对水溶液中甲基橙(MO)的吸附行为。用红外光谱(FT-IR)和BET方法对沸石进行了表征。研究表明,CTAB改性沸石对MO的吸附符合Langmuir模型,在pH值为7、温度为298.15K、振荡速度为160r/min时,CTAB改性沸石对MO的最大吸附量为82mg/g。动态吸附实验表明,CTAB改性沸石对MO的吸附动力学可以用准二级动力学方程描述,说明它的吸附机理是一个物理与化学吸附过程。     

改性累托石的制备及其对水中磷的吸附研究

利用有机改性法对累托石(REC)进行改性,制得季铵盐改性累托石(REC-1631),再对碱性条件下的REC-1631用FeCl_3·6H_2O和FeSO_4·7H_2O进行磁性处理,制得磁性累托石(Fe_3O_4/REC-1631),并对水中磷的吸附性能进行研究。结果表明,REC对废水中磷的最大吸附量由改性前的61.60 mg/g提高到改性后117.00mg/g,吸附效果明显增大,同时还具有稳定的磁性,便于回收再利用,其吸附过程符合准二级动力学方程和Langmuir等温吸附曲线。     

Mg/Fe类水滑石的磷酸根吸附性能及吸附机理

采用共沉淀法成功制备了Mg/Fe类水滑石(Mg/Fe-hlc),并研究了其对废水中磷酸根的吸附性能及吸附机理。研究结果表明:制备的Mg/Fe-hlc具有典型的类水滑石结构和较大的比表面积(156.7 m~2·g~(-1));Mg/Fe-hlc对磷酸根的吸附动力学过程符合准二级动力学模型;Langmuir和Tempkin方程都可以很好地拟合Mg/Fe-hlc对磷酸根的等温吸附数据,Langmuir方程拟合得到的最大吸附量可达47.38 mg·g~(-1);共存阴离子NO_3~-、Cl~-和SO_4~(2-)对磷吸附性能的影响很小;通过分析吸附磷酸根前后的Mg/Fe-hlc的结构和织构性质以及表面官能团变化,并结合溶液pH对磷酸根吸附影响实验结果,发现静电相互作用、配体交换和阴离子交换是Mg/Fe-htl吸附磷酸根的三种主要机制。     

新型螯合树脂聚苯乙烯负载葡糖胺对Pt(Ⅳ)吸附性能

合成了新型螯合树脂聚苯乙烯负载葡糖胺(PS-GA)。研究了树脂对Pt(Ⅳ)的吸附容量、吸附动力学、等温吸附等静态吸附性能及影响吸附的因素。结果表明,该树脂对Pt(Ⅳ)的吸附量较高;吸附动力学研究证明树脂对Pt(Ⅳ)的吸附为液膜扩散控制,吸附的活化能通过计算得10.31kJ/mol;树脂对Pt(Ⅳ)的等温吸附,与Freundlich方程相比,更加符合Langmuir方程;计算了等温吸附过程的热力学参数ΔG,ΔH,ΔS值;升高温度有利于吸附;树脂可用2%硫脲～0.1mol/LHCl溶液清洗再生,5次再生后仍保持良好的吸附能力,适合重复使用。     

（英）二氧化钛/石墨烯复合材料对水溶液中钯离子的吸附性能研究

本文合成了一种新型二氧化钛/石墨烯(TiO2-Gr)复合材料吸附剂,研究了其对水溶液中Pd(II)的吸附作用,并与TiO2的吸附性能进行了比较。制得的TiO2-Gr吸附剂分别进行了透射电子显微镜(TEM)表征及X射线衍射(XRD)分析,考察了吸附过程中时间、溶液p H、吸附剂用量、离子强度、Pd(II)浓度和温度等参数对吸附量的影响。研究了吸附过程中动力学、热力学及吸附等温线。结果表明吸附过程符合假二级动力学模型,吸附等温线符合Langmuir和Freundlich等温吸附方程。对热力学函数(吉布斯函数变、焓变、熵变)测定表明,本文合成的TiO2-Gr吸附剂对Pd(II)的吸附属于自发吸热反应。     

二氧化钛/石墨烯复合材料对水溶液中钯离子的吸附性能研究(英文)

本文合成了一种新型二氧化钛/石墨烯(TiO2-Gr)复合材料吸附剂,研究了其对水溶液中Pd(II)的吸附作用,并与TiO2的吸附性能进行了比较。制得的TiO2-Gr吸附剂分别进行了透射电子显微镜(TEM)表征及X射线衍射(XRD)分析,考察了吸附过程中时间、溶液p H、吸附剂用量、离子强度、Pd(II)浓度和温度等参数对吸附量的影响。研究了吸附过程中动力学、热力学及吸附等温线。结果表明吸附过程符合假二级动力学模型,吸附等温线符合Langmuir和Freundlich等温吸附方程。对热力学函数(吉布斯函数变、焓变、熵变)测定表明,本文合成的TiO2-Gr吸附剂对Pd(II)的吸附属于自发吸热反应。     

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.     

N-乙烯吡咯烷酮/甲基丙烯酸-β-羟乙酯无规共聚物凝胶对蛋白质吸附机理的研究

用紫外分光光度法研究了牛血清白蛋白(BSA)在N-乙烯吡咯烷酮(NVP)/甲基丙烯酸-β-羟乙酯(HEMA)共聚物水凝胶上的吸附量.结果表明,BSA在凝胶上的吸附关系既可用Langmuir方程描述,又可用计量置换吸附Freundlich方程描述,且用Langmuir方程描述更为优越.研究了凝胶对BSA的吸附动力学行为,建立牛血清白蛋白的吸附动力学模型,发现用Bangharm方程对BSA吸附动力学曲线拟合程度较好,Bangharm方程可以较好地描述BSA在NVP/HEMA凝胶上的吸附动力学行为.     

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。     

复合改性膨润土对2,4,6-三氯苯酚和Pb~(2+)的吸附行为研究

本文主要以钠基膨润土为原料,用十六烷基二甲基苄基氯化铵和乙二胺四乙酸二钠盐对膨润土进行复合改性,制得改性膨润土,用XRD对其结构进行表征,研究了改性后的膨润土对2,4,6-三氯苯酚和Pb~(2+)的吸附行为,结果表明,改性后的膨润土对2,4,6-三氯苯酚和Pb~(2+)的吸附性能明显提高,吸附等温线较好地符合Langmuir模型,改性膨润土对2,4,6-三氯苯酚和Pb~(2+)的最大吸附量分别为238.1mg/g和191.20mg/g,吸附动力学符合准二级反应动力学方程,其二级反应速率常数为分别为8.34×10~(-5)g/mgámin和5.62×110~(-5)g/mgámin,改性膨润土对2,4,6-三氯苯酚的吸附为吸热反应,而对Pb~(2+)的吸附为放热反应。     

Kinetics and thermodynamics of bromophenol blue adsorption by a mesoporous hybrid gel derived from tetraethoxysilane and bis(trimethoxysilyl)hexane

A mesoporous hybrid gel is prepared with tetraethoxysilane (TEOS) and bis(trimethoxysilyl)hexane (TSH) as precursors without using any templating agent. Nitrogen sorption, TG-DTA, FTIR, and point of zero charge (PZC) measurement are used to characterize the gel. The gel has a specific surface area of 695 m(2) g(-1) with a pore size of 3.5 nm, a pore volume of 0.564 cm(3) g(-1), and a point of zero charge (PZC) of 6.2. The kinetics and thermodynamics of bromophenol blue (BPB) adsorption by the gel in aqueous solution are investigated comprehensively. The effects of initial BPB concentration, pH, ionic strength, and temperature on the adsorption are investigated. Kinetic studies show that the kinetic data are well described by the pseudo-second-order kinetic model. Initial adsorption rate increases with the increase in initial BPB concentration and temperature. Adsorption activation energy is found to be 62.5-67.5 kJ mol(-1) depending on the initial BPB concentration. Internal diffusion appears to be the rate-limiting step for the adsorption process. The equilibrium adsorption amount increases with the increase in the initial BPB concentration, solution acidity, and ionic strength, but decreases with the increase in temperature. The thermodynamic analysis indicates that the adsorption is spontaneous and exothermic. The adsorption isotherms can be well described with Freundlich equation indicating the heterogeneity of the hybrid gel surface. Electrostatic and hydrophobic interactions are suggested to be the dominant mechanism for adsorption.     

分子筛对葡萄糖淀粉酶的吸附性能研究

测定了黑曲霉葡萄糖淀粉酶(E.C.3.2.1.3)在三种改性的、具有中孔和大孔的分子筛上的吸附等温线并将吸附量和吸附等温线的形状与分子筛的等电点、孔容、孔径及酸性相关联。讨论了孔结构和不同酶吸附量对分子筛固定化葡萄糖淀粉酶活力的影响。发现葡萄糖淀粉酶在再造孔分子筛上的单层饱和吸附量与再造孔的方法密切有关,三种不同再造孔方法制得的分子筛具有不同的骨架Si/Al比、不同的孔分布和比表面积。不同的Si/Al比导致不同的酸性质和等电点。酶吸附量与载体的表面酸性、等电点以及吸附时溶液的pH有关。分子筛对酶的吸附以静电作用为主。其次,当中孔孔径和孔容越大时,单层饱和吸附量亦越大。随着分子筛对葡萄糖淀粉酶的吸附量增加,固定化酶的活力增大,但固定化酶的比活力随吸附量的增加、中孔孔容和孔径的减小而下降。     

Comparison of dye adsorption by mesoporous hybrid gels: understanding the interactions between dyes and gel surfaces

Without using any templating agents, mesoporous hybrid gels were prepared using mixtures of tetraethoxysilane (TEOS) with n-propyltriethoxysilane (PTES), bis(trimethoxysilyl)hexane (TSH), or bis(trimethoxysilylpropyl)amine (TSPA) as precursors. Fourier transform infrared (FTIR), N2 adsorption/desorption, thermogravimetry (TG), point of zero charge (PZC), and water vapor adsorption measurements were used to characterize the gels. The adsorption of methyl orange (MO), methyl red (MR), bromocresol purple (BP), phenol red (PR), neutral red (NR), and brilliant blue FCF (BBF) by the gels in both 0.01 M HCl and 0.01 M NaOH solutions was compared comprehensively. The gel derived from TEOS/TSH (with -(CH2)6- groups, Gel 2) has the largest specific surface area (695 m2 g(-1)), the smallest pore volume (0.564 cm3 g(-1)), and the smallest average pore size (3.7 nm). The gels derived form TEOS/PTES (with -(CH2)2CH3 groups, Gel 1), and TEOS/TSPA (with -(CH2)3NH(CH2)3- groups, Gel 3) have similar textual properties. The PZC of Gels 1, 2, and 3 was estimated to be 6.28, 6.20, and 6.88, respectively. Gel 3 has the highest PZC due to the presence of -NH- groups. In general, Gel 2 shows the highest dye adsorption among all the gels in both acidic and basic solutions. All the dyes except NR have much lower adsorption in basic solutions than in acidic solutions. In acidic solutions Gels 1 and 2 have similar adsorption trends for the dyes, except for BP, with NR having the highest adsorption, and PR the lowest adsorption. Gel 3 presents a different trend from Gels 1 and 2, with BBF having the highest adsorption, and MR the lowest adsorption. In basic solutions the order of dye adsorption by all the gels is shown to follow the sequence NR>MR approximately BBF>MO>BP approximately PR. The adsorption results can be explained by considering the textural properties of the gels and the interactions between the gel surfaces and the dyes, which include hydrogen bonding, electrostatic, and hydrophobic interactions.     

Interface chemistry of nanostructured materials: ion adsorption on mesoporous alumina

This paper presents a part of our work on understanding the effect of nanoscale pore space confinement on ion sorption by mesoporous materials. Acid-base titration experiments were performed on both mesoporous alumina and alumina particles under various ionic strengths. The point of zero charge (PZC) for mesoporous alumina was measured to be approximately 9.1, similar to that for nonmesoporous alumina materials, indicating that nanoscale pore space confinement does not have a significant effect on the PZC of pore surfaces. However, for a given pH deviation from the PZC, (pH-PZC), the surface charge per mass on mesoporous alumina was as much as 45 times higher than that on alumina particles. This difference cannot be fully explained by the surface area difference between the two materials. Our titration data have demonstrated that nanoscale confinement has a significant effect, most likely via the overlap of the electric double layer (EDL), on ion sorption onto mesopore surfaces. This effect cannot be adequately modeled by existing surface complexation models, which were developed mostly for an unconfined solid-water interface. Our titration data have also indicated that the rate of ion uptake by mesoporous alumina is relatively slow, probably due to diffusion into mesopores, and complete equilibration for sorption could take 4-5 min. A molecular simulation using a density functional theory was performed to calculate ion adsorption coefficients as a function of pore size. The calculation has shown that as pore size is reduced to nanoscales (<10 nm), the adsorption coefficients of ions can vary by more than two orders of magnitude relative to those for unconfined interfaces. The prediction is supported by our experimental data on Zn sorption onto mesoporous alumina. Owing to their unique surface chemistry, mesoporous materials can potentially be used as effective ion adsorbents for separation processes and environmental cleanup.     

Influence of PZC (Point of Zero Charge) on the Static Adsorption of Anionic Surfactants on a Malaysian Sandstone

Static adsorption studies of two anionic surfactants produced in our lab are reported. The adsorption of surfactants on the rock samples was investigated with and without the presence of alkali. The point of zero charge (PZC) values were determined for the sandstone samples employing three titrimetric methods and it was found to be at pH 7.98. The relationship between the adsorption degree and pH value of brine below and above the PZC is discussed. It was found that at the pH of solution exceeds the PZC of the rock, the adsorption was 0.43 and 0.86mg/g of rock for the two surfactants. However, at pH values below PZC, the adsorption as high as 3.66 and 4.49mg/g for the two surfactants. The synthesized surfactants are found to be suitable for the EOR applications at pH values higher than the PZC of the rock sample.     

Removal of lead(II) and zinc(II) ions from aqueous solutions by adsorption onto activated carbon synthesized from watermelon shell and walnut shell

Activated carbons from watermelon shell (GACW) and walnut shell (GACN) were synthesized through chemical activation with phosphoric acid 40 % w/w, as an alternative low-cost adsorbent for the removal of lead(II) and zinc(II) ions from aqueous solutions. The yield of production was 85 and 80 % for GACW and GACN respectively. To compare the differences and similarities between the two activated carbons the following tests were performed: surface and pore width with SEM, nitrogen adsorption isotherms at ?196 °C (77 K), IR spectroscopy, TGA, point of zero charge (PZC) and Boehm titration. The GACN has 10 % more surface area (789 m² g^?1 for GACN and 710 m² g^?1 for GACW) and 13 % more pore volume than GACW. Also, GACN has a better resistance to high temperatures than GACW (the loss of mass at 900 °C was 20 % for GACN, while for GACW was 31 %). The effect of the initial concentration of lead(II) and zinc(II) ions on the adsorption process was studied in a batch process mode. To quantify the adsorption of lead and zinc adsorption isotherms of both metals in aqueous solution were performed for each carbon using analytic technique of atomic absorption. The adsorption isotherm data were better fitted by Langmuir model. Experimental results suggests that one gram of GACW adsorbs more milligrams of lead(II) and zinc(II) than one gram of GACN; it is suggest that the pore distribution is a significant variable in the adsorption process because GACW present mesopores and micropores, while GACN has only micropores. Also, the surface chemistry is an important variable in the adsorption process because GACW presents a lower pH_PZC than GACN (3.05 for GACW and 4.5 for GACN) and the solution’s pH of each metal was adjusted in 4.5, for that it could be suggested that the electrostatic interactions were increased between the ion and the carbon surface.     

Temperature effects on the point of zero charge and isoelectric point of a red soil rich in kaolinite and iron minerals

The effects of temperature (373–1373 K) on the point of zero charge (PZC) and isoelectric point (IEP) of a red soil rich in kaolinite and iron minerals were studied. PZC values of the soil treated at 373 and 573 K indicated the presence of iron oxide. The soil calcined between 773 and 1173 K shows a PZC almost coincident with the respective values of kaolinite. At 1373 K, the PZC of the soil is nearer to the value of iron oxide. In the entire temperature range studied the PZC values were lower than the IEP values. An approach of PZC and IEP values was observed after a partial removal of iron oxide by the dithionite-citrate-bicarbonate (DCB) method. The analyses of the PZC and IEP values, of electron probe micro analysis (EPMA) data and of specific surface areas evidence a specific adsorption of iron oxide on kaolinite. Finally, the dissolution sequence of iron and aluminium contained in soil was determined using hydrochloric acid.     

Monte Carlo modeling of ion adsorption at the energetically heterogeneous metal oxide/electrolyte interface: Micro- and macroscopic correlations between adsorption energies

Grand canonical Monte Carlo simulations are carried out for the basic Stern model of the electrical double layer formed at the energetically heterogeneous metal oxide/electrolyte interface. The effect of the global (macroscopic) and local (microscopic) adsorption energies correlations as well as the influence of the model parameter on the surface charge density curves were investigated. The linear dependence of point of zero charge (PZC) as a function of H+ ion adsorption energy proves that the acidic/basic properties of the system are mainly governed by proton uptake/release. Two kinds of systems were taken into account: one neglecting lateral interactions and the other one including them. The effect of electrolyte concentrations as well as the surface heterogeneity on the surface charge density curves were shown too. The presented simulation algorithm allows to model two experimentally observed instances of the metal oxide/electrolyte interface: one possessing a common intersection point (CIP) at pH = PZC and the other one with CIP not equal PZC.     

Sorption of atrazine on conventional and surface modified activated carbons

The sorption of atrazine from water has been studied using a conventional activated carbon, F400, an annealed carbon sample, F400AN, and an aminated carbon sample, F400NH(2). Characterisation of the carbon samples showed that sample F400NH(2) had the highest proportion of micropores, but had the lowest values of point of zero charge (PZC) and iso-electric point (IEP). This was attributed to the existence of a high proportion of oxygen containing functional groups. Sorption data showed that sample F400AN was superior in the sorption of atrazine to samples F400 and F400NH(2). It was noted that pore size distribution alone was not the only contributing factor for the uptake of atrazine onto the activated carbons. The sorption data were fitted well using the Freundlich isotherm. The free energy change showed that sorption of atrazine on activated carbons is a spontaneous process. A pseudo-second order kinetic model was used for analysing the kinetic data, and it was concluded that adsorption of atrazine was controlled by a film diffusion mechanism.     

Formal Mathematical Analysis of the Existence of the Common Intersection Point in Relation to Determining the Parameters Describing Ion Adsorption at the Oxide/Electrolyte Interface: Comparison of the Triple and Four-Layer Models

For most oxide/electrolyte systems potentiometric titration curves measured for different ionic strengths have a Common Intersection Point (CIP) which corresponds to the Point of Zero Charge (PZC). However, there are systems where a CIP exists but the surface charge at this point does not equal zero (PZC CIP). In this paper theoretical analysis of the systems in which the PZC and CIP do not coincide is presented. It is based on the well-known 2-pK surface charging approach and Triple Layer Model (TLM) as well as the Four Layer Model (FLM) of the electric double layer. The appropriate mathematical criterion for CIP existence was applied with detailed derivations, both for TLM and FLM. Having determined in this manner the parameter values, one can draw proper conclusions about the features of oxide/electrolyte adsorption systems, in which PZC and CIP do not coincide. The values of adsorption parameters are found by fitting simultaneously the obtained theoretical expressions to both of the experimental titration isotherms, and to the individual isotherms of electrolyte cation adsorption measured using radiometric methods.