十六烷基三甲基溴化铵修饰P型沸石吸附水中直链烷基苯磺酸钠的研究

通过使用碱液对天然斜发沸石(Z)进行处理制得P型沸石(PZ), 再用十六烷基三甲基溴化铵(CTMAB)对Z和PZ进行修饰, 制得有机改性沸石ZC和PZC, 对比考察了ZC和PZC对直链烷基苯磺酸钠(LAS)的吸附性能. 实验结果表明, 制得的PZ硅/铝比为2, 比Z(4.85)降低58.8%; PZ的零净电荷点、 比表面积、 孔径和孔容均高于Z; 吸附平衡时间为4 h. 当pH=2时, ZC和PZC对LAS吸附量达到最高, 吸附数据符合Langmuir准二级动力学方程和Langmuir等温吸附方程, 饱和吸附量(q_m)分别为12.658和27.100 mg/g, 吸附过程主要为单分子层的化学吸附, PZC的吸附速率常数大于ZC, 具有更好的动力学性能.     

Adsorption kinetics of an organic dye by wet hybrid gel monoliths

Wet hybrid gel monoliths are prepared with bis(trimethoxysilylpropyl)amine (TSPA) or the mixture of TSPA with n-propyltriethoxysilane (PTES) or bis(trimethoxysilyl)hexane (TSH) or tetraethoxysilane (TEOS) as precursors. The adsorption kinetics of an organic dye (erioglaucine disodium salt, EDS) by the gel monoliths in aqueous solutions is studied comprehensively. The effects of temperature, pH, and ionic strength on the adsorption kinetics are investigated. Kinetic studies show that in general the kinetic data are well described by the pseudo second-order kinetic model. Initial adsorption rate increases with the increase in temperature, but decreases with the increase in solution pH and ionic strength. The adsorption activation energy is found to be 17–51 kJ mol⁻¹ under our experimental conditions. The internal diffusion of the dye into the hybrid gels appears to be the rate-limiting step of the overall adsorption process. The adsorption is promoted by hydrogen bonding, hydrophobic and electrostatic attractions in acidic or neutral solutions, suppressed by the electrostatic repulsion in basic solutions and by the ionic exchange competition of Cl⁻ with the dye anions in solutions with a high NaCl concentration. After adsorption for 165 h, all the gel monoliths present a linear shrinkage less than 10%.     

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.     

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。     

缓蚀剂吸附行为的电化学及AFM力曲线研究

结合极化曲线,微分电容曲线测试和AFM力曲线技术研究了直链十二胺对氯化钠溶液中铜镍合金的缓蚀行为以及吸附机理。结果表明:十二胺在合金表面形成单分子层吸附膜而起到缓蚀作用。十二胺浓度越大,吸附膜越致密,缓蚀率越高,力曲线上测得的粘附力值也越大。质子化的十二胺在荷负电的合金表面的吸附使电极零电荷电位正移,电荷屏蔽作用使得AFM力曲线上探针与试样之间的长程静电斥力减小。     

Synthesis and characterization of goethite and goethite-hematite composite: experimental study and literature survey

Aging of synthetic goethite at 140 degrees C overnight leads to a composite material in which hematite is detectable by M?ssbauer spectroscopy, but X-ray diffraction does not reveal any hematite peaks. The pristine point of zero charge (PZC) of synthetic goethite was found at pH 9.4 as the common intersection point of potentiometric titration curves at different ionic strengths and the isoelectric point (IEP). For the goethite-hematite composite, the common intersection point (pH 9.4), and the IEP (pH 8.8) do not match. The electrokinetic potential of goethite at ionic strengths up to 1 mol dm(-3) was determined. Unlike metal oxides, for which the electrokinetic potential is reversed to positive over the entire pH range at sufficiently high ionic strength, the IEP of goethite is rather insensitive to the ionic strength. A literature survey of published PZC/IEP values of iron oxides and hydroxides indicated that the average PZC/IEP does not depend on the degree of hydration (oxide or hydroxide). Our material showed a higher PZC and IEP than most published results. The present results confirm the allegation that electroacoustic measurements produce a higher IEP than the average IEP obtained by means of classical electrokinetic methods.     

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.     

硫酸溶液中1,1’-硫代羰基二咪唑在碳钢上的吸附及缓蚀影响和碘离子的增强效应

The inhibition effect of 1,1’-thiocarbonyldiimidazole (TCDI) on the corrosion behaviors of mild steel (MS) in 0.5 mol·L -1 H2SO4 solution was studied with the help of potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and linear polarization resistance (LPR) techniques. The effect of immersion time on the inhibition effect of TCDI was also investigated over 72 h. For the long-term tests, hydrogen evolution with immersion time (VH2-t) was measured in addition to the three techniques already mentioned. The thermodynamic parameters, such as adsorption equilibrium constant (Kads) and adsorption free energy (⊿Gads) values, were calculated and discussed. To clarify inhibition mechanism, the synergistic effect of iodide ion was also investigated. The potential of zero charge (PZC) of the MS was studied by electrochemical impedance spectroscopy method, and a mechanism of adsorption process was proposed. It was demonstrated that inhibition efficiency increased with the increase in TCDI concentration and synergistically increased in the presence of KI. The inhibition efficiency was discussed in terms of adsorption of inhibitor molecules on the metal surface and protective filmformation.     

硫酸溶液中1,1'-硫代羰基二咪唑在碳钢上的吸附及缓蚀影响和碘离子的增强应

The inhibition effect of 1,1'-thiocarbonyldiimidazole (TCDI) on the corrosion behaviors of mild steel impedance spectroscopy(EIS),and linear polarization resistance(LPR)techniques.The effect of immersion time on the inhibition effect of TCDI was also investigated over 72 h.For the long.term tests.hydrogen evolution with immersion time(VH2-t)was measured in addition to the three techniques already mentioned.The thermodynamic parameters.such as adsorption equilibrium constant(Kads) and adsorption free energy(△Gads)values,were calculated and discussed.To clarify inhibition mechanism,the synergistic effect of iodide ion was also investigated.The potential of zero charge (PZC)of the MS was studied by electrochemical impedance spectroscopy method.and a mechanism of adsorption process was proposed.It was demonstrated that inhibition efficiency increased with the increase in TCDI concentration and synergistically increased in the presence of KI.The inhibition efficiency was discussed in terms ofadsorption of inhibitormolecules on the metal surface and protective film formation.     

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.     

Effective sequestration of Congo red dye with ZnO/cotton stalks biochar nanocomposite: MODELING,reusability and stability

Widespread application of dyes and disposal of their untreated effluents into water bodies adversely affect the ecosystem due to their complex aromatic structures and persistent nature. The present study aims to utilize the cotton stalks biochar (CSB) and its composite with zinc oxide nanoparticles (CSB/ZnONPs) to evaluate for the decontamination their batch scale potential of Congo red dye from wastewater. The characterization of CSB and CSB/ZnONPs was performed with Fourier-transform infra-red (FTIR) spectroscopy, scanning electron microscopy, energy-dispersive X-ray (EDX) and point of zero charge (PZC) to get insight of their potential for the decontamination of CR. The effects of initial CR concentration (25–500 mg/L), dosage of CSB and CSB/ZnONPs (0.5–2 g/L), solution pH (2–10) and contact time (0–180 min) were evaluated on CR removal at temperature (25 ± 1.5 °C). The results disclosed that CSB/ZnONPs showed excellent adsorption potential (556.6 mg/g) in comparison with CSB (250 mg/g) and most of the other adsorbents previously studies in the literature. The equilibrium experimental data were equally explained with Freundlich and Langmuir isotherm models (R² > 0.98) while kinetic data demonstrated the best fit with pseudo second order model. The CSB/ZnONPs composite exhibited excellent reusability (89.65%) after five adsorption/desorption cycles for the sequestration of CR from contaminated systems. The present study demonstrated that metallic nanocomposite of CSB (CSB/ZnONPs) is an excellent candidate for the cost effective and environment friendly decontamination of CR from industrial wastewater and is suggested to be considered for the decontamination of other pollutants from the wastewater.     

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.     

Surface charge properties of Fe2O3 in aqueous and alcoholic mixed solvents

Iron oxide (Fe2O3) was identified and characterized by surface area, X-ray diffractometry, and FTIR analyses. Surface charge densities, point of zero charge (PZC), and surface ionization constants were determined from the potentiometric titration data in various aqueous and aqueous organic mixed solvents in the temperature range 293-313 K. The surface charge densities were observed to decrease with the increase in temperature and concentration of metal ions in both the aqueous and aqueous organic mixed solvents. The absolute values of the surface charge density were found to change in the order aqueous > aqueous/methanol > aqueous/ethanol. Further, the PZC of the iron oxide was observed to shift to the higher pH values in the order ethanol > methanol > aqueous solution, which indicated a decrease in the acidity of the surface -OH groups. The pKa1 and pKa2 values of iron oxide were also determined and then used for determination of the surface potential (psi0) of the solid in aqueous and aqueous organic mixed solvents. The surface potential-surface charge curves generally supplemented the results derived from psi0-pH curves.     

The significance of the difference in the point of zero charge between rutile and anatase

The points of zero charge (PZC) of titanium dioxide reported in the literature range from 2 to 8.9. A set of 138 PZC of titanium dioxide was used to explore the effect of the crystalline structure on the PZC. The average and median PZC at pH 5.6 and 5.8, respectively, was found when the entire data set was taken into account. The PZC of anatase (31 entries, average and median 5.9 and 6, respectively) is slightly higher than that of rutile (49 entries, average and median 5.4 and 5.5, respectively), and the difference between the polymorphs corresponds to half of a standard deviation in each set of PZC.     

The effect of external stimuli on the Bovine Serum Albumin adsorption capacity of poly(acrylamide/maleic acid) hydrogels prepared by gamma rays

The effects of external stimuli such as pH of the buffer solution, ionic strength, temperature and the amount of poly-electrolyte monomer in the hydrogel system on the Bovine Serum Albumin (BSA) adsorption capacity of poly(acrylamide/maleic acid) [P(AAm/MA)] hydrogels were investigated. Poly-electrolyte P(AAm/MA) hydrogels with varying compositions were prepared by irradiating acrylamide/maleic acid/water mixtures with γ rays at ambient temperature. Langmuir type adsorption isotherms were observed for all prepared hydrogels. Increase of ionic strength of the buffer solution from 0.01 to 0.1 mol dm⁻³ decreased the adsorption capacity of hydrogels and zero adsorption was observed in the presence of 0.1 mol dm⁻³ Na⁺ and Ca²⁺ ion in the adsorption medium. The adsorption capacity of hydrogels was found to increase from 0 to 120 mg BSA/g dry gel, by changing external stimuli and hydrogel composition.     

Oxide-dependent adsorption of a model membrane phospholipid, dipalmitoylphosphatidylcholine: bulk adsorption isotherms

The importance of substrate chemistry and structure on supported phospholipid bilayer design and functionality is only recently being recognized. Our goal is to investigate systematically the substrate-dependence of phospholipid adsorption with an emphasis on oxide surface chemistry and to determine the dominant controlling forces. We obtained bulk adsorption isotherms at 55 degrees C for dipalmitoylphosphatidylcholine (DPPC) at pH values of 5.0, 7.2, and 9.0 and at two ionic strengths with and without Ca(2+), on quartz (alpha-SiO(2)), rutile (alpha-TiO(2)), and corundum (alpha-Al(2)O(3)), which represent a wide a range of points of zero charge (PZC). Adsorption was strongly oxide- and pH-dependent. At pH 5.0, adsorption increased as quartz < rutile approximately corundum, while at pH 7.2 and 9.0, the trend was quartz approximately rutile < corundum. Adsorption decreased with increasing pH (increasing negative surface charge), although adsorption occurred even at pH > or = PZC of the oxides. These trends indicate that adsorption is controlled by attractive van der Waals forces and further modified by electrostatic interactions of oxide surface sites with the negatively charged phosphate ester (-R(PO(4)-)R'-) portion of the DPPC headgroup. Also, the maximum observed adsorption on negatively charged oxide surfaces corresponded to roughly two bilayers, whereas significantly higher adsorption of up to four bilayers occurred on positively charged surfaces. Calcium ions promote adsorption beyond a second bilayer, regardless of the sign of oxide surface charge. We develop a conceptual model for the structure of the electric double layer to explain these observations.     

壳聚糖插层蒙脱土复合材料吸附酸性染料的动力学和热力学研究

通过离子交换的方法将天然大分子壳聚糖引入蒙脱土的层间,利用XRD和TG对得到的复合材料进行表征。将该复合材料用于酸性黑10B的吸附,考查了pH值、染料起始浓度、吸附时间以及温度对吸附性能的影响。结果表明,吸附动力学实验数据符合准二级动力学模型。应用Langmuir和Freundlich两种模型描述吸附等温线,结果显示Langmuir模型的拟合效果更好。计算得到吸附过程的热力学参数△Go、△Ho和△So的值分别为-27.16kJ/mol(20℃)、-14.18kJ/mol和44.0J/mol.K,说明复合材料对酸性染料的吸附是一个自发进行的放热过程。     

Probing electric fields at the ionic liquid-electrode interface using sum frequency generation spectroscopy and electrochemistry

The arrangement of ions at the platinum electrode in the room-temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate has been determined using sum frequency generation vibrational spectroscopy (SFG), electrochemical impedance spectroscopy (EIS), and the vibrational Stark effect. The results indicate that CO adsorbed on the Pt electrode has a Stark shift of 30-35 cm(-1)/V in the ionic liquid. The potential of zero charge (PZC) of the ionic liquid-Pt system is approximately -500 mV (vs Ag wire), with a capacitance of 0.12 F/m2. Further, polarization-dependent SFG experiments suggest the ions reorganize at the surface depending on the electrode charge. In combination, all these results indicate that the ions of a neat ionic liquid are organized in a Helmholtz layer at the electrified metal electrode interface.     

1pK and 2pK protonation models in the theoretical description of simple ion adsorption at the oxide/electrolyte interface: the analysis of temperature dependence of potentiometric titration curves

Two models of oxide surface charging (1pK and 2pK) were used to describe the potentiometric titration curves measured by Blesa et al. (J. Colloid Interface Sci.101, 410 (1984)) at three temperatures and at three concentrations of electrolyte. Rudzinski et al. (Langmuir13, 483 (1997)) have applied the 2pK Triple Layer Model to analyze the above system earlier. Two calculation procedures based on the 1pK Basic Stern Model were developed to described Blesa's data. Since the experimental curves have the CIP (common intersection point) it was assumed that heat of electrolyte ion adsorption was equal to zero. We assumed two different values of the double layer innermost capacitance on both sides of PZC (point of zero charge), which was followed from asymmetry of surface charge curves relative to PZC. Moreover, it was necessary to take into consideration the dependence of capacitance on ionic strength and temperature. The quality of fit given by two models was comparable. Since the 1pK BSM is simpler than the 2pK TLM and includes not so many best-fit parameters it seems to be a better choice in this case. Discussion of the results obtained by other authors concerning the subject under consideration is also presented.