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1.
高岭石水溶液的界面反应特征 总被引：2，自引：1，他引：1
高岭石的表面荷电性、溶解及其对 Cu2 、 Pb2 的吸附等实验结果表明, 高岭石的零净质子电荷点 pHPZNPC=5.2,但端面 >AlOH的 pHPZNPC在 6.5～ 7.0之间,而 >SiOH的 pHPZNPC < 2.3;然而,在 pH 2～ 10范围,ζ电位均为负值,即电动电荷等于零对应的 pH (pHIEP) < 2;且在 pH < 4溶解时, Al溶出率比 Si高,表明高岭石表层形成富 Si贫 Al层.随着溶液 pH由酸性往碱性的变化,重金属离子的吸附表现为离子交换与表面配位模式并存,并发生规律性的变化:在 pH < 6.5时主要表现为离子交换吸附,在 pH < 4时由于受到高岭石 Al的高溶出及较高的离子强度影响,高岭石对 Cu2 、 Pb2 的吸附率较低,但在 pH 5～ 6附近吸附率有明显的提升,并且有个吸附平台;在 pH > 6.5时,主要表现为离子交换和表面配位均为重要的吸附机制,若 pH再升高或重金属离子浓度过高时甚至发生表面沉淀.研究还表明,溶液 pH与离子强度影响高岭石水界面反应过程,表面溶解与质子化反应改变高岭石的表面性质,包括表面荷电性和表面位化合形态,因而调控 Cu2 、 Pb2 的界面吸附行为. 相似文献
2.
高岭石和蒙脱石分别是暖湿和冷干气候带内典型土壤的代表性矿物,对二者吸附胡敏酸特点的对比研究可以为探索不同地带土壤中重金属的环境行为提供重要的依据。笔者通过一系列实验研究了pH值、离子强度和胡敏酸初始浓度对胡敏酸在高岭石和蒙脱石上吸附量的影响,重点剖析了引起高岭石和蒙脱石在吸附胡敏酸方面表现出的共性和差异的原因。研究结果表明:1)在pH=5条件下,胡敏酸在高岭石和蒙脱石上的吸附量均随着胡敏酸初始浓度和离子强度的升高而逐渐增加;2)胡敏酸在高岭石和蒙脱石上的吸附量均随着pH值的升高而降低;3)pH<6时,高岭石吸附的胡敏酸量多于蒙脱石,pH>6时则相反。这是由高岭石和蒙脱石在不同pH条件下吸附胡敏酸的机制不同造成的。在pH<6时,高岭石与胡敏酸之间的静电引力起主导作用,其次是配位交换作用和氢键作用。此时,蒙脱石以氢键作用为主要吸附机制。在pH>6时,高岭石和蒙脱石的主要吸附机制分别是疏水性作用和阳离子键桥。 相似文献
3.
考察酸性条件特别是在近中性 pH范围内胡敏酸对高岭石吸附铜离子的强化作用。研究表明 ,胡敏酸的加入可以提高高岭石对铜离子的吸附率 ,甚至在pH 5～ 6附近高岭石对铜离子的吸附率也从约 5 0 %提高到约 6 5 %。当 pH <4时 ,由于高岭石表面铝的高溶出或胡敏酸阴离子基团离解程度降低等因素 ,使其表面对胡敏酸的吸附率有所降低 ,但与高岭石样品相比 ,胡敏酸高岭石复合体对铜离子的吸附仍然有明显的增加。胡敏酸对高岭石吸附铜离子的强化机制是 ,高岭石端面形成了Al—HA—Cu三元配合物 (B型 ) ,与传统的诸如pH、离子强度与离子初始浓度等介质条件影响不同。在 pH >7时高岭石端面及腐殖质基团去质子化增强 ,因而静电排斥降低了高岭石对胡敏酸的吸附 ,从而使得胡敏酸对铜离子在高岭石表面上的吸附作用有所减弱 ,此时可能出现胡敏酸铜及氢氧化铜的沉淀 ,铜离子的表观吸附率可能不会有明显变化 相似文献
4.
针铁矿/水界面反应性的实验研究 总被引：1，自引：0，他引：1
选择针铁矿对Pb2+、Cu2+、Cd2+等3种重金属离子的吸附实验,开展矿物/水界面反应性研究.金属离子(M2+)在矿物-水溶液间分配有多种表面反应机制,这些表面反应发生作用的条件主要取决于吸附质水化学性质和矿物表面荷电性,因此,溶液pH值是影响矿物/水界面反应性的关键因素.在不同pH值条件下, 表面羟基可通过发生质子化或去质子化反应而使得矿物表面产生荷电性并发生改变,而金属离子的水解则可显著加快金属羟基配合物的形成,从而进一步增强了矿物/水界面反应.本实验条件下针铁矿表面对重金属离子的吸着量随pH值升高而升高,在一个较窄的pH值范围内吸附率急剧升高,呈S形分布.针铁矿对3种不同的重金属离子的吸附能力的强弱顺序是Cu2+＞Pb2+＞Cd2+.无论是Langmuir方程还是Freundlich方程,都能较好拟合针铁矿对重金属离子的等温吸附过程.Freundlich方程的n值均在0.1～0.5之间,说明重金属离子在针铁矿表面的吸附并不能简单地归结为单配位或双配位模式,可能存在着多种吸附结合形态.表观吸附常数KM值的变化规律,说明重金属离子与针铁矿表面反应模式及其表面吸附形态发生了变化,具体的吸附形态还有待谱学研究进一步证实. 相似文献
5.
介微孔复合沸石分子筛对重金属离子吸附性能的实验研究 总被引：12，自引：0，他引：12
以介微孔复合沸石分子筛MCM-41／ZSM-3为吸附剂，采用静态吸附方法初步研究了其对重金属离子Cu^2 、Zn^2 、Pb^2 、Cd^2 的吸附性能。结果表明：对于配置的60mg／dm^3重金属离子溶液，使用分子筛用量为10g／dm^3时，在较宽的pH范围内MCM-41／ZSM-3对Cu^2 、Zn^2 、Pb^2 、Cd^2 的吸附率可达90％以上；对等温吸附曲线的回归分析得出Cu^2 、Zn^2 、Pb^2 、Cd^2 在实验浓度范围内符合Langmuir单吸附位吸附曲线且具有较大的吸附容量。 相似文献
6.
7.
采用表面酸碱电位滴定法探讨高岭石表面酸碱性质,基于多位模式(即假定高岭石表面存在3种基团Al2 OH 、AlOH 和SiOH ) ,根据实验所得数据对高岭石表面的质子化和去质子化过程的相关参数进行拟合,讨论各个位点所发生的反应,并探讨了支持电解质浓度、高岭石溶解过程对表面酸碱电位滴定结果的影响。高岭石的表面零净质子电荷点(pHPZNPC,5 .2 )不等同于零电荷点,当pH <5 .2时,高岭石表面荷正电荷,主要由于表面富硅贫铝层的形成和Al位的质子化所致;当pH >5 .2时,高岭石表面荷负电荷,以Si位和Al的去质子化反应为主。 相似文献
8.
国内矿物治理重金属废水研究进展与展望 总被引：7，自引：4，他引：3
综述了我国利用天然矿物治理重金属废水方面的研究新成果。天然铁的硫化物、天然铁锰的氧化物、方解石与磷灰石等具有良好的表面吸附与氧化还原化学活性;不同介质中它们能不同程度地表现出对Cr^6 、Pb^2 、Hg^2 、Cd^2 等重金属离子的吸附作用,可广泛用于重金属废水处理。矿物吸附重金属离子机理的研究表明,矿物对重金属的吸附是矿物表面与无机重金属离子之间的表面作用过程,包括矿物表面功能基与重金属离子的配位反应、矿物表面氧化还原反应和沉淀转化作用,以及矿物表面离子交换吸附作用等。 相似文献
9.
重金属离子在胡敏酸-高岭石复合体上的吸附 总被引：6，自引：0，他引：6
本文研究了胡敏酸存在下高岭石对重金属离子的吸附行为。实验结果表明:①胡敏酸和Cu2 溶液按先后顺序或同时加入高岭石中反应,在Cu2 平衡浓度<10mg/L时,3种加入顺序对Cu2 的吸附量基本相同,当Cu2 平衡浓度>10mg/L时,(K Cu) HA和(K Cu HA)两种加入顺序对Cu2 的吸附量比(K HA) Cu的略大。②在pH=5时,胡敏酸-高岭石复合体对Cu2 的吸附量明显大于纯高岭石。这是由于胡敏酸含有大量的羧基和酚羟基等活性基团,吸附在高岭石上的胡敏酸增加了其表面吸附位,在复合体表面形成了S—HA—Cu三元配合物,且Cu2 的吸附量与复合体中胡敏酸的含量在一定范围内成正相关;③溶液pH值在4～7之间变化可调控复合体对Cu2 的吸附机制。④在Cu2 和Cd2 共存时,随着金属离子初始浓度的增大,Cu2 的吸附量呈直线上升,而Cd2 的吸附量增加缓慢,表明复合体对Cu2 的吸附能力比对Cd2 强。 相似文献
10.
借助原位液槽原子力显微镜（in situ AFM）的观察,通过Cd2+,Pb2+替代方解石最外层晶格Ca2+生长模式的实验研究,
探讨了Cd2+与Pb2+作用下方解石表面溶解与结晶行为。在液体反应槽中,分别将含不饱和Cd2+与Pb2+溶液流经方解石{101 _
4}解理面,结果发现:（1）Cd2+的存在不影响方解石沿<4_41> 晶向台阶的溶解,而Pb2+的存在则强烈阻碍了方解石沿<441>+晶向台阶的溶解;（2）停止输入溶液含Cd2+,Pb2+溶液后,随着方解石表面与溶液达到平衡,溶解过程逐渐转变为结晶过程。结果显示在Cd2+存在时,单分子生长层具有方解石原有的定向性,而在Pb2+存在时的生长则不具任何定向性。尽管有此差异,
但（Ca,Cd）CO3 和（Ca,Pb）CO3 固溶体都受控于单分子层外延生长这一结晶机理。
含Cd2+和Pb2+溶液对方解石溶解动力学的作用与选择性吸附的阳离子半径大小、吸附复合体的几何形状及其结晶学取
向有关。Cd2+离子倾向于优先进入更狭小的<4_41>- 晶向的微台阶上,而Pb2+则倾向于形成扭曲的八面体络合物吸附在更开
阔的<4_41>+ 晶向台阶上。因此,Pb2+存在下方解石表面生长方向无序可认为是白铅矿和方解石结构差异的原因。 相似文献
11.
The adsorption behavior of Zn2+ ions onto the surface of amorphous aluminosilicates was studied using both potentiometric and spectroscopic methods (XANES: X-ray Absorption Near-Edge Structure). The aluminosilicates were prepared with different Al/Si ratios in order to compare the reactivities of surface aluminol and silanol groups toward Zn2+ ions. Potentiometric experiments were performed by maintaining the reacting suspensions at constant pH, ionic strength, and solid concentration, while Zn concentration was increased by stepwise addition. Our results showed that the surface aluminol and silanol groups possess significantly different reactivities toward Zn2+ ions. The reaction of Zn2+ ions with aluminol groups occurs through three processes: (i) surface complexation, (ii) dissolution, and (iii) re-sorption. A stoichiometric relationship was confirmed for the surface complexation between the aluminol groups and Zn2+ ions: two moles of H+ ions were released for one mole of Zn2+ ion adsorption. Following the surface complexation process, measurable amounts of zinc and aluminum ions were found to be mobilized from the surface of the solid to the liquid phase; subsequently, these ions precipitated on the solid surface, and possibly formed a co-precipitate with the hydrotalcite-type structure. On the other hand, a stoichiometric relationship was not obtained for the sorption of Zn2+ ions on silanol groups, and therefore, it was concluded that Zn2+ ions are retained on the surface of amorphous aluminosilicates by two different reactions. One reaction involves the surface complexation between Zn2+ ions and surface aluminol groups, which proceeds rapidly. The other reaction is the slow retention of Zn2+ ions onto silanol and/or aluminol groups, which could be the surface precipitation of Zn(OH)2 or the co-precipitation of Zn2+-Al3+ hydroxides. It can be suggested that the total sorption behavior of Zn2+ ions on amorphous aluminosilicates with different Al/Si ratios can be represented as the sum of the individual reactions of Zn2+ ions toward the aluminol and silanol groups. The potentiometric results were confirmed by XANES data. It was clearly evident that only the aluminol groups were responsible for surface complexation of Zn2+ ions. An equilibrium constant was calculated for this reaction. 相似文献
12.
Batch experiments were conducted to study the sorption of uranium on selected clay minerals (KGa-1b and KGa-2 reference kaolinite,
SWy-2 and STx-1b reference montmorillonite, and IBECO natural bentonite) as a function of pH (4–9) and 0.001, 0.01, and 0.025 M
NaCl in equilibrium with the CO2 partial pressure of the atmosphere. Uranium concentrations were kept below 100 μg L−1 to avoid precipitation of amorphous Uranium-hydroxides. Solely PTFE containers and materials were used, because experiments
showed significant sorption at higher pH on glass ware. All batch experiments were performed over a period of 24 h, since
kinetic experiments proved that the common 10 or 15 min are in many cases by far not sufficient to reach equilibrium. Kaolinite
showed much greater uranium sorption than the other clay minerals due to the more aluminol sites available. Sorption on the
poorly crystallized KGa-2 was higher than on the well-crystallized KGa-1b. Uranium sorption on STx-1b and IBECO exhibited
parabolic behavior with a sorption maximum around pH 6.5. Sorption of uranium on montmorillonites showed a distinct dependency
on sodium concentrations because of the effective competition between uranyl and sodium ions, whereas less significant differences
in sorption were found for kaolinite. The presence of anatase as impurity in kaolinite enhanced the binding of uranyl-carbonate
complexes with surface sites. The kinetic of uranium sorption behavior was primarily dependent on the clay minerals and pH.
A multisite surface complexation model without assuming exchange is based on the binding of the most dominant uranium species
to aluminol and silanol edge sites of montmorillonite, respectively to aluminol and titanol surface sites of kaolinite. For
eight surface species, the log_k was determined from the experimental data using the parameter estimation code PEST together
with PHREEQC. 相似文献
13.
Sorption of Cu and Pb to kaolinite-fulvic acid colloids: Assessment of sorbent interactions 总被引：2，自引：0，他引：2
Ilona Heidmann 《Geochimica et cosmochimica acta》2005,69(7):1675-1686
The sorption of Cu(II) and Pb(II) to kaolinite-fulvic acid colloids was investigated by potentiometric titrations. To assess the possible interactions between kaolinite and fulvic acid during metal sorption, experimental sorption isotherms were compared with predictions based on a linear additivity model (LAM). Suspensions of 5 g L−1 kaolinite and 0.03 g L−1 fulvic acid in 0.01 M NaNO3 were titrated with Cu and Pb solutions, respectively. The suspension pH was kept constant at pH 4, 6, or 8. The free ion activities of Cu2+ and Pb2+ were monitored in the titration vessel using ion selective electrodes. Total dissolved concentrations of metals (by ICP-MS) and fulvic acid (by UV-absorption) were determined in samples taken after each titration step. The amounts of metals sorbed to the solid phase, comprised of kaolinite plus surface-bound fulvic acid, were calculated by difference. Compared to pure kaolinite, addition of fulvic acid to the clay strongly increased metal sorption to the solid phase. This effect was more pronounced at pH 4 and 6 than at pH 8, because more fulvic acid was sorbed to the kaolinite surface under acidic conditions. Addition of Pb enhanced the sorption of fulvic acid onto kaolinite at pH 6 and 8, but not at pH 4. Addition of Cu had no effect on the sorption of fulvic acid onto kaolinite. In the LAM, metal sorption to the kaolinite surface was predicted by a two-site, 1-pK basic Stern model and metal sorption to the fulvic acid was calculated with the NICA-Donnan model, respectively. The LAM provided good predictions of Cu sorption to the kaolinite-fulvic acid colloids over the entire range in pH and free Cu2+ ion activity (10−12 to 10−5). The sorption of Pb was slightly underestimated by the LAM under most conditions. A fractionation of the fulvic acid during sorption to kaolinite was observed, but this could not explain the observed deviations of the LAM predictions from the experimental Pb sorption isotherms. 相似文献
14.
15.
由于重金属镉离子的吸附性能较差、毒性大,因此,寻找镉离子的高效吸附材料具有重要现实意义。本文开展巯基硅烷对高岭石的嫁接改性研究,经红外光谱测试证实,成功将巯基引入到高岭石表面。同时,硅烷改性对高岭石晶体结构没有产生影响。通过批量实验考察了高岭石和巯基硅烷改性高岭石(K-SH)对Cd(Ⅱ)的吸附特征,主要探讨了p H值、时间对吸附效率的影响。矿物对Cd2+的吸附动力学符合准二级动力学模型,吸附等温方程更符合Langmuir模型,并估算的K-SH的最大吸附量是4.375 mg/g,比高岭石的大近20倍。改性高岭石表面嫁接了巯基后,可为高岭石吸附Cd(Ⅱ)提供大量的新吸附位点,通过配位复合作用显著提高对镉离子的吸附固定能力。因此,巯基硅烷改性高岭石是一种有应用前景的土壤修复材料。 相似文献
16.
C. Zhu X. Dong Z. Chen R. Naidu 《International Journal of Environmental Science and Technology》2016,13(5):1257-1268
Amorphous tin(VI) hydrogen phosphate (ATHP) was synthesized using the liquid phase precipitation method and served as an adsorbent to remove Pb(II), Cu(II), and Zn(II) from aqueous solutions. The ATHP was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption–desorption techniques. Adsorption properties were evaluated as a function of pH, reaction time, concentration of reactants, and salinity. Their equilibrium adsorption data were modeled using Freundlich, Langmuir, and Dubinin–Kaganer–Radushkevich isotherms, respectively. The results revealed that adsorption equilibrium reached within 180 min. ATHP indicated good adsorption even below the pHZPC, and best adsorption at pH 5 for Pb(II) and Cu(II) and at pH 5.5 for Zn(II) was observed. Equilibrium data fitted better to the Langmuir model for Pb(II) and Cu(II) and fitted better to the Freundlich model for Zn(II). The saturated adsorption capacities deduced from the Langmuir model were 2.425, 1.801, and 0.600 mmol/g for Cu(II), Pb(II), and Zn(II), respectively, indicating an adsorption affinity order of Cu > Pb > Zn. There is a negative correlation between the concentration of NaCl and adsorption capacity of ATHP, yet ATHP still exhibited excellent adsorption having an adsorption capacity of 19.35, 15.16, 6.425 mg/g when the concentration of NaCl was 0.6 mol/L. The free energy (E) was 12.33, 10.70, and 14.74 kJ/mol for Pb(II), Cu(II), and Zn(II), respectively. An adsorption mechanism based on ion exchange between heavy metal ions and H+ in the ATHP is proposed. Furthermore, the used ATHP was regenerated by HCl solution and the adsorbent was used repeatedly. 相似文献
17.
Caroline L. Peacock 《Geochimica et cosmochimica acta》2005,69(15):3733-3745
We measured the adsorption of Cu(II) onto kaolinite from pH 3-7 at constant ionic strength. EXAFS spectra show that Cu(II) adsorbs as (CuO4Hn)n−6 and binuclear (Cu2O6Hn)n−8 inner-sphere complexes on variable-charge ≡AlOH sites and as Cu2+ on ion exchangeable ≡X--H+ sites. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed at least up to pH 6.5. Inner-sphere complexes are bound to the kaolinite surface by corner-sharing with two or three edge-sharing Al(O,OH)6 polyhedra. Our interpretation of the EXAFS data are supported by ab initio (density functional theory) geometries of analog clusters simulating Cu complexes on the {110} and {010} crystal edges and at the ditrigonal cavity sites on the {001}. Having identified the bidentate (≡AlOH)2Cu(OH)20, tridentate (≡Al3O(OH)2)Cu2(OH)30 and ≡X--Cu2+ surface complexes, the experimental copper(II) adsorption data can be fit to the reactions
18.
Proton binding constants for the edge and basal surface sites of kaolinite were determined by batch titration experiments at 25 °C in the presence of 0.1 M, 0.01 M and 0.001 M solutions of NaNO3 and in the pH range 3-9. By optimizing the results of the titration experiments, the ratio of the edge sites to the basal surface sites was found to be 6:1. The adsorption of Cd(II), Cu(II), Ni(II), Zn(II) and Pb(II) onto kaolinite suspensions was investigated using batch adsorption experiments and results suggested that in the lower pH range the metallic cations were bound through non-specific ion exchange reactions on the permanently charged basal surface sites (X−). Adsorption on these sites was greatly affected by ionic strength. With increasing pH, the variable charged edge sites (SOH) became the major adsorption sites and inner-sphere specifically adsorbed monodentate complexes were believed to be formed. The effect of ionic strength on the extent of adsorption of the metals on the variable charged edge sites was much less than those on the permanently charged sites. Two binding constants, log K(X2Me) and log K(SOMe), were calculated by optimizing these constants in the computer program FITEQL. A model combining non-specific ion exchange reactions and inner-sphere specific surface complexations was developed to predict the adsorption of heavy metals onto kaolinite in the studied pH range. Linear free energy relationships were found between the edge site binding constants and the first hydrolysis constants of the metals. 相似文献
19.
Uranium U(VI) adsorption was measured as function of pH (3–10) on goethite, kaolinite, quartz, two binary mixtures of goethite and kaolinite, and a vadose zone sediment collected on The Department of Energy’s Savannah River Site (SRS), the clay mineral fraction of which is composed largely of kaolinite and goethite. Diffuse-layer surface complexation models were parameterized using the code PEST together with PHREEQC to fit U(VI) sorption data for the pure goethite, kaolinite, and quartz. U(VI) adsorption on kaolinite and goethite was modeled as the formation of two bidentate U(VI) complexes at mineral edge sites on a variable charge site. U(VI) adsorption on quartz was described using a one-site diffuse-layer with the formation of bidentate complex on a variable charge site. These models were used to predict U(VI) adsorption on the binary sorbent mixtures and the SRS sediment using a simple component-additivity approach. In general, the predicted adsorption edges were in good agreement with measured data, with statistically similar goodness of fit compared to that obtained for the pure mineral systems. 相似文献
20.
WU Daqing DIAO Guiyi YUAN Peng PENG Jinlian 《《地质学报》英文版》2006,80(2):192-199
The adsorption of pentachlorophenol （PCP） onto quartz, kaolinite, illite, montmorillonite and iron oxides has been investigated by batch equilibrium techniques. The pH-dependent isotherms are curves with peak values, the position of which is at about pH = 5-6 depending on the mineral species. Based on distribution of both speciation of surface hydroxyls on minerals and PCP in solution a surface reaction model involving surface complexation and surface electrostatic attraction is presented to fit the pH-dependent isotherms, and both reaction constants are calculated. The results show that on quartz and phyllosilicate minerals the predominant adsorption reaction is surface complexation, meanwhile both of surface electrostatic attraction and surface complexation are involved on the iron oxide minerals. The reaction constants of surface electrostatic adsorption are usually one to three orders in magnitude, larger than that of surface complexation. The concentration-dependent isotherms can be well fitted by Langmnir equation with the correlation coefficient R〉0.93 for kaolinite and iron oxides. The maximum adsorption is found in the order： hematite 〉 lepidocrocite 〉 goethite 〉 kaolinite 〉 quartz 〉 montmorillonite ≈ illite, which can be interpreted by consideration of both reaction mechanism and surface hydroxyl density. The significant adsorption of PCP onto mineral surfaces suggests that clay and iron oxide minerals will play an important role as HIOCs are adsorbed in laterite or latertoid soil, which is widespread in South China. 相似文献