Adsorption Capacities of Iron Hydroxide for Arsenate and Arsenite Removal from Water by Chemical Coagulation: Kinetics,Thermodynamics and Equilibrium Studies

Arsenic (As)-laden wastewater may pose a threat to biodiversity when released into soil and water bodies without treatment. The current study investigated the sorption properties of both As(III, V) oxyanions onto iron hydroxide (FHO) by chemical coagulation. The potential mechanisms were identified using the adsorption models, ζ-potential, X-ray diffraction (XRD) and Fourier Transform Infrared Spectrometry (FT-IR) analysis. The results indicate that the sorption kinetics of pentavalent and trivalent As species closely followed the pseudo-second-order model, and the adsorption rates of both toxicants were remarkably governed by pH as well as the quantity of FHO in suspension. Notably, the FHO formation was directly related to the amount of ferric chloride (FC) coagulant added in the solution. The sorption isotherm results show a better maximum sorption capacity for pentavalent As ions than trivalent species, with the same amount of FHO in the suspensions. The thermodynamic study suggests that the sorption process was spontaneously exothermic with increased randomness. The ζ-potential, FT-IR and XRD analyses confirm that a strong Fe-O bond with As(V) and the closeness of the surface potential of the bonded complex to the point of zero charge (pH_zpc) resulted in the higher adsorption affinity of pentavalent As species than trivalent ions in most aquatic conditions. Moreover, the presence of sulfates, phosphates, and humic and salicylic acid significantly affected the As(III, V) sorption performance by altering the surface properties of Fe precipitates. The combined effect of charge neutralization, complexation, oxidation and multilayer chemisorption was identified as a major removal mechanism. These findings may provide some understanding regarding the fate, transport and adsorption properties onto FHO of As oxyanions in a complex water environment.     

稀土取代的复合氧化物Eu_（0．5）RE_（0．5）Fe_（0．5）Mn_（0．

利用固相反应合成了稀土取代的复合氧化物Ｅｕ_（０．５）ＲＥ_（０．５）Ｆｅ_（０．５）Ｍｎ_（０．５）Ｏ_３（ＲＥ＝Ｌａ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ）．测量了这些化合物的ＸＲＤ和ＸＰＳ谱。在ＸＰＳ研究中发现，稀土取代而使稀土元素本身的结合能相对于其倍半氧化物中的有所降低；在取代的复合氧化物中，随着ＲＥ离子半径的减小，Ｆｅ、Ｍｎ的结合能随之增加。     

Equilibrium properties of charged spherical colloidal particles suspended in aqueous electrolytes: finite ion size and effective ion permittivity effects

The adsorption behaviour and mechanism of As(III) and Se(IV) oxyanion uptake using a mixed inorganic adsorbent were studied. The novel adsorbent, based on Fe(III)-Mn(III) hydrous oxides and manganese(II) carbonate, was synthesised using a hydrothermal precipitation approach in the presence of urea. The inorganic ion exchanger exhibited a high selectivity and adsorptive capacity towards As(III) (up to 47.6 mg/g) and Se(IV) (up to 29.0 mg/g), even at low equilibrium concentration. Although pH effects were typical for anionic species (i.e., the adsorption decreased upon pH increase), Se(IV) was more sensitive to pH changes than As(III). The rates of adsorption of both oxyanions were high. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) studies showed that the ion exchange adsorption of both anions took place via OH(-) groups, mainly from Fe(III) but also Mn(III) hydrous oxides. MnCO(3) did not contribute directly to As(III) and Se(IV) removal. A higher adsorptive capacity of the developed material towards As(III) was partly due to partial As(III) oxidation during adsorption.     

Effects of toluene on thiophene adsorption over NaY and Ce(IV)Y zeolites

Zeolites NaY and Ce(IV)Y were employed as adsorbents to remove organic sulfur compounds from model gasoline(MG) solutions with and without toluene in static adsorption experiments at room temperature(RT) and atmospheric pressure.The adsorbents were characterized by XRD,XRF and pyridine infrared spectrum(IR).The adsorption experiments show that the desulfurization performance of Ce(IV)Y is much better than that of NaY.The sulfur removal over both NaY and Ce(IV)Y decreases with the increase of toluene concentration in MG,however,the decline tendency on Ce(IV)Y is smooth,and it is steep on NaY.FT-IR spectra of thiophene adsorption indicate that thiophene molecules are mainly adsorbed on NaY via π electron interaction,but on Ce(IV)Y,in addition to the π electron interaction,both Ce4+-S direct interaction and protonation of thiophene also play important roles.Toluene molecules are adsorbed on NaY also via π electron interaction.Although the amount of Brnsted acid sites is increased due to the introduction of Ce4+ ions into NaY zeolite,it is not found to influence the adsorption mode of toluene over Ce(IV)Y.Compared with NaY zeolite,the improved desulfurization performance over Ce(IV)Y for removing organic sulfur compounds from MG solution,especially those containing large amount of aromatics,may be ascribed to the direct Ce(IV)-S interaction,which is much resistant to the influence resulted from toluene adsorption.     

Ce改性对Y型分子筛酸性及其催化转化性能的调变机制

采用液相离子交换(LPIE)法制备了不同离子交换度的CeY分子筛. 运用电感耦合等离子发射光谱(ICPAES)、X射线衍射(XRD)、N₂吸附等温线和氨气程序升温脱附(NH₃-TPD)等方法对其进行表征, 采用原位傅里叶变换红外(in situ FTIR)光谱技术分别以吡啶和噻吩作为探针分子研究了Ce改性对Y型分子筛酸性能和催化转化性能的影响规律. 结果表明, Ce离子改性不改变Y 型分子筛晶体的基本骨架, 但改变其精细结构. 分子筛改性过程中Ce物种优先定位于方钠石(SOD)笼, 随着稀土离子含量增大, 逐渐出现在超笼中. Ce离子交换过程中产生一定量的Brönsted (B)酸中心, 且其量与强度随着Ce含量的增大均呈现先增加后平稳的趋势. 同时, Ce离子交换产生与非骨架铝物种和铈物种有关的两种强度不同的Lewis (L)酸中心, 且两者均随着Ce含量的增大而增大. 噻吩吸附红外光谱表明, 由于Ce离子改性产生的强B酸中心可导致噻吩在室温条件下即可发生质子化反应, 质子化的噻吩分子可进一步发生低聚反应. 而稀土物种与B酸中心的协同作用有利于低聚反应的发生.     

Preparation of unsaturated polyester Ce(IV) phosphate by plastic waste bottles and its application for removal of Malachite green dye from water samples

In this paper, recycling of polyethyleneterephthalate (PET), a non-biodegradable plastic, was carried out by preparing unsaturated polyester Ce(IV) phosphate (USPECe(IV)P) composite cation exchanger. Various samples of USPECe(IV)P was prepared by mixing different volume ratios of unsaturated polyester in an inorganic Ce(IV) phosphate gel and characterized by TGA/DTA, XRD, SEM, Fourier transform infra-red spectroscopy (FTIR) instrumental methods. The composite has been employed as adsorbents for the removal of Malachite green dye from waste water. The nature of possible adsorbent and dye interaction was examined by the FTIR technique. The adsorption of MG was found to be maximum (98%) at pH 8. The extent of removal of MG was found to be dependent on adsorbent dose, temperature and time. The equilibrium data for adsorption was best represented by the Friendlich isotherm. Thermodynamic parameters (ΔH⁰ and ΔG⁰) suggest an endothermic and spontaneous process. Kinetic studies show better applicability of an intraparticle diffusion kinetic model.     

Behaviors and mechanisms of copper adsorption on hydrolyzed polyacrylonitrile fibers

Polyacrylonitrile fiber (PANF) was hydrolyzed in a solution of sodium hydroxide and the hydrolyzed polyacrylonitrile fiber (HPANF) was used as an adsorbent to remove copper ions from aqueous solution. Scanning electron microscopy (SEM) showed that the hydrolysis process made the surface of HPANF rougher than that of PANF. Fourier transform infrared (FTIR) spectroscopy revealed that the HPANF contained conjugated imine (-Cz=Nz-) sequences. Batch adsorption results indicated that the HPANF was very effective in adsorbing copper, and the adsorption equilibrium could be reached within 10-20 min. Atomic force microscopy (AFM) showed that some aggregates formed on the surface of the HPANF after copper ion adsorption and the average surface roughness (R(a)) value of the HPANF changed from 0.363 to 3.763 nm due to copper adsorption. FTIR analysis indicated that copper adsorption caused a decrease of the light adsorption intensity of the imine (-Cz=Nz-) groups at 1573 and 1406 cm(-1) wavenumbers, and X-ray photoelectron spectroscopy (XPS) showed that the binding energy (BE) of some of the nitrogen atoms in the HPANF increased to a greater value due to copper adsorption. The FTIR and XPS results suggest that the adsorption of copper ions to the HPANF is attributed to the imine groups on the surface of the HPANF.     

稀土铈掺杂对甲烷高温燃烧催化剂LaFeAl11O19结构和性能的影响

六铝酸盐甲烷高温燃烧催化剂研究目前主要集中在BaMnA l11O19基和LaMnA l11O19基的催化剂上[1-4],关于LaFeA l11O19催化剂研究相对较少,而据文献报道[5]在沉淀法制备取代型的六铝酸钡催化剂中铁和锰活性相近,但铁比锰具有更高的耐高温和抗水热冲击的能力,因此本工作选择LaFeA l     

The mechanism of antimony(III) removal and its reactions on the surfaces of Fe-Mn binary oxide

Antimony is a regulated pollutant to be well controlled. This study compared the removal capability and mechanisms involved in the removal of Sb(III) by Fe-Mn Binary Oxide (FMBO), ferric hydroxide (FeOOH), and manganese dioxide (MnO(2)). FMBO shows a maximum Sb removal capacity of 1.76 mmol/g and was much higher than that of both FeOOH (0.83 mmol/g) and MnO(2) (0.81 mmol/g). Characterization techniques of FTIR and XPS indicated the different variation trends of functional groups, surface elemental composition, and chemical valence of Fe, Mn, and Sb after the adsorption of Sb(III) on these three adsorbents. As for FMBO, results indicated that the manganese oxide dominated in oxidation of Sb(III) to Sb(V) whereas the iron oxide adsorbed the Sb(III) and Sb(V). The oxidation and sorption mechanism was proposed to involve in the removal of Sb(III) by FMBO. FMBO may be promisingly used to remove Sb from drinking water and wastewater.     

Supramolecular sequential assembly of polymer thin films based on dimeric, dendrimeric, and polymeric Schiff-base ligands and metal ions

New metal-Schiff-base coordination polymer films were prepared using multiple sequential adsorption of metal ions and salen-based ligand molecules. As the ligands, bis-bidentate 5,5'-methylene-bis(N-methylsalicylidenamine) (MBSA), tetra-bidentate N,N',N' ',N' '-tetrasalicylidene-polyamidoamine (TSPA), and multi-bidentate poly(N-salicylidenevinylamine) (PSVA) were used. The metal ions were Cu(II), Zn(II), Fe(II), Fe(III), and Ce(IV). The resulting films are deeply colored due to the formation of coordinative bonds between the metal ions and the salen groups. Our study indicates that film formation becomes progressively easier, if the number of salen groups per ligand molecule increases. While Cu(II), Ni(II), Fe, and Ce(IV) are well suited for complex formation, Zn(II) is less suited. Possible structures of the polymers are discussed. Cyclic voltammetric studies of the films are also presented.     

In situ and ex situ study of the enhanced modification with iron of clinoptilolite-rich zeolitic tuff for arsenic sorption from aqueous solutions

Adsorption methods have been developed for the removal of arsenic from solution motivated by the adverse health effects of this naturally occurring element. Iron exchanged natural zeolites are promising materials for this application. In this study we introduced iron species into a clinoptilolite-rich zeolitic tuff by the liquid exchange method using different organic and inorganic iron salts after pretreatment with NaCl and quantified the iron content in all trials by XRF spectroscopy. The materials were characterized by XRD, FTIR, FTIR-DR, UV-vis, cyclic voltammetry, ESR and M?ssbauer spectroscopies before and after adsorption of arsenite and arsenate. The reached iron load in the sample T+Fe was %Fe(2)O(3)-2.462, n(Fe)/n(Al)=0.19, n(Si)/n(Fe)=30.9 using FeCl(3), whereby the iron leachability was 0.1-0.2%. The introduced iron corresponded to four coordinated species with tetrahedral geometry, primarily low spin ferric iron adsorbing almost 12 mug g(-1) arsenite (99% removal) from a 360 mug(As(III)) L(-1) and 6 mug g(-1) arsenate from a 230 mug(As(V)) L(-1). Adsorption of arsenite and arsenate reached practically a plateau at n(Fe)/n(Si)=0.1 in the series of exchanged tuffs. The oxidation of arsenite to arsenate in the solution in contact with iron modified tuff during adsorption was observed by speciation. The reduction of ferric iron to ferrous iron could be detected in the electrochemical system comprising an iron-clinoptilolite impregnated electrode and was not observed in the dried tuff after adsorption.     

镨和铈对低温还原法制备的Ni2P催化剂加氢脱硫活性的影响

采用低温热解次磷酸盐法制备了Ni₂P-L、Pr-Ni₂P-L和Ce-Ni₂P-L催化剂,并采用XRD、H₂-TPR、BET、CO吸附、XPS等手段对制备得到的催化剂进行了表征。以二苯并噻吩(DBT)为模型化合物,研究了Pr、Ce稀土元素对低温还原法制备的Ni₂P-L催化剂加氢脱硫(HDS)性能的影响。结果表明,催化剂添加稀土Pr和Ce能够抑制Ni₅P₄和其他杂晶的生成,从而促进活性相Ni₂P的生成;添加稀土能提高催化剂对联苯(BP)的选择性,但催化剂的总HDS活性略有降低。     

Spectrophotometric determination of copper(II) using oximidobenzotetronic acid

Summary Oximidobenzotetronic acid (OBTA) is proposed as a sensitive spectrophotometric reagent for the estimation of 0.5–3.0 ppm of copper(II) at 427 nm in 50% dioxan at p_H 5.3–7.5. For the estimation of 2 ppm Cu(II), 1.3 ppm Ni(II), 1.3 ppm Co(II), 3.2 ppm Fe(II), 10.3 ppm Fe(III), 9.7 ppm Ce(IV), 300 ppm acetate, 160 ppm oxalate, 95 ppm tartrate, 50 ppm citrate, as well as Zn(II), Cd(II), Hg(II)) Pb(II), Mn(II), As(III) as well as (V), Th(IV), Be(II), Ce(III), La(III), V(V) and Mo(VI), even when present in large quantities, do not interfere. The interference due to 25 ppm Bi(III), 20 ppm Sb(III), 20 ppm Sn(II), 25 ppm Sn(IV) and 30 ppm W(VI) can be removed by the addition of 95 ppm tartrate ions.

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Zusammenfassung Oximidobenzotetronsäure wurde als empfindliches Reagens zur spektrophotometrischen Bestimmung von 0,5 bis 3,0 ppm Kupfer(II) bei 427 nm in 50%iger Dioxanlösung bei p_H 5,3 bis 7,5 vorgeschlagen. Die Anwesenheit von 1,3 ppm Ni(II), 1,3 ppm Co(II), 3,2 ppm Fe(II), 10,3 ppm Fe(III), 9,7 ppm Ce(IV), 300 ppm Acetat, 160 ppm Oxalat, 95 ppm Tartrat, 50 ppm Citrat sowie die Anwesenheit auch großer Mengen Zn(II), Cd(II), Hg(II), Pb(II), Mn(II), As(III) bzw. (V), Th(IV), Be(II), Ce(III), La(III), V(V) und Mo(VI) stören die Bestimmung von 2 ppm Cu(II) nicht. Der störende Einfluß von 25 ppm Bi(III), 20 ppm Sb(III), 20 ppm Sn(II), 25 ppm Sn(IV) und 30 ppm W(VI) kann durch Zusatz von 95 ppm Tartrat beseitigt werden.

     

FT-IR、XPS和DFT研究水杨酸钠在针铁矿或赤铁矿上的吸附机理

采用傅里叶变换红外(FT-IR)光谱、X射线光电子能谱(XPS)以及基于周期平面波的密度泛函理论(DFT)分别研究了水杨酸钠在针铁矿或赤铁矿表面上的吸附结构,并将计算得到的光电子能谱移动(CLS)和电荷转移与实验得到的XPS结果进行对比。FT-IR结果表明,水杨酸钠可能以双齿双核(V)和双齿单核(IV)的形式分别吸附于针铁矿或赤铁矿表面。由DFT计算结果可知,水杨酸钠在针铁矿(101)晶面上形成双齿双核化合物(V)的吸附能为-5.46 eV。而水杨酸钠在针铁矿(101)晶面上形成双齿单核化合物(IV)的吸附能为3.80 eV,因此水杨酸钠在针铁矿上基本不以双齿单核化合物(IV)构型存在。水杨酸钠在赤铁矿(001)晶面上形成双齿单核化合物(IV)时吸附能为-4.07 eV,说明水杨酸钠在赤铁矿(001)晶面上形成了双齿单核化合物(IV)。另外,理论计算的针铁矿(101)晶面上吸附位点铁原子的Fe 2p的CLS值(-0.68 eV)与实验观察到的Fe 2p的CLS值(-0.5 eV)吻合。理论计算的赤铁矿(001)晶面上吸附位点铁原子的Fe 2p的CLS值(-0.80 eV)与实验观察到的Fe 2p的CLS值(-0.8 eV)吻合。因此,水杨酸钠吸附在针铁矿表面时能够通过羧酸基团上一个氧原子和酚羟基上的氧原子与针铁矿(101)表面上的两个铁原子形成双齿双核(V)结构,而在赤铁矿(001)表面上,水杨酸钠中羧酸基团上一个氧原子和酚羟基上的氧原子与赤铁矿(001)表面上的一个铁原子形成了双齿单核(IV)结构。     

原位水热合成Ce(Ⅳ)-X分子筛及对噻吩的吸附性能

通过原位水热合成方法直接制备出不同载Ce量的Ce(Ⅳ)-X分子筛,并考察了其对模拟汽油中噻吩的吸附性能。采用粉末X射线衍射(XRD)、傅里叶变换红外(FT-IR)、紫外-可见漫反射(UV-vis DRS)、全谱直读等离子体原子发射光谱(ICP-AES)、氮气吸附和NH₃程序升温热脱附(NH₃-TPD)等方法对分子筛进行表征。结果表明,合成分子筛均具备典型的X型分子筛结构,同时Ce(Ⅳ)被较好地引入到分子筛的骨架结构中;载Ce分子筛的酸性大于X分子筛,而且Ce(Ⅳ)-X分子筛的酸性随着Ce掺杂量的增加而增强。吸附实验表明,载Ce分子筛对噻吩的吸附性能明显好于X分子筛。其中,n(Ce)/n(Si)=0.05的分子筛脱硫效果最佳,饱和吸附容量达到52.541 9 mg/g。再生实验表明,加热再生的Ce(Ⅳ)-X分子筛对噻吩仍具有理想的吸附效果。n(Ce)/n(Si)=0.05的分子筛再生后饱和吸附容量为47.512 1 mg/g,约为新鲜吸附剂的90.43％。     

Investigation of removal of Ag(I) from aqueous solution by a novel chelating resin containing acyl and thiourea groups

This work aimed at investigating a novel chelating resin (PTDTR) containing acyl and thiourea groups for the removal of Ag(I) from aqueous solution by adsorption tests, FTIR, scanning electron microcopy (SEM), BET and XPS analyses. The maximum adsorption capacity of Ag(I) ions obtained from Langmuir model was 6.078?mmol/g at 30?°C. The uptake of Ag(I) on resin was found to follow liquid film diffusion and pseudo-second-order model. Thermodynamic parameters showed that the adsorption process of Ag(I) ions onto PTDTR resin was spontaneous and endothermic under nature conditions. The regeneration test indicated that PTDTR resin have good stability and the adsorption capacity decreased 2.7% after five cycles of adsorption-desorption. In addition, PTDTR resin showed good selectivity for Ag(I) ions in Ag(I)-Cu(II) binary system. The results of SEM suggested that Ag(I) adsorbed on the surface of PTDTR. The FTIR and XPS analyses further confirmed Ag(I) ions might chemisorb onto PTDTR surfaces through its acyl and thiourea groups.     

Optimization of adsorption parameters for Fe (III) ions removal from aqueous solutions by transition metal oxide nanocomposite

Manganese oxide nanocomposite (Mn₂O₃/Mn₃O₄) was prepared by sol-gel technique and used as an adsorbent. Fourier Transform Infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and Field Emission Scanning Electron Microscopy (FE-SEM) were used to characterize the adsorbent. The response surface methodology (RSM) was employed to evaluate the effects of solution pH, initial Fe (III) ions concentration, adsorbent weight, and contact time on the removal ratio of the Fe (III) ions. A total of 27 adsorption experimental runs were carried out employing the detailed conditions designed based on the Box-Behnken design (BBD). Results showed that the pH of the solution and initial Fe (III) ions concentration were the most significant parameters for Fe (III) ions removal. In process optimization, the maximal value of the removal ratio of Fe (III) was achieved as 95.80%. Moreover, the corresponding optimal parameters of adsorption process were as: contact time?=?62.5?min, initial Fe (III) concentration?=?50?mg/L, adsorbent weight?=?0.5?g, and pH?=?5. The experimental confirmation tests showed a strong correlation between the predicted and experimental responses (R²?=?0.9803). The fitness of equilibrium data to common isotherm equations such as Langmuir, Freundlich, and Temkin were also tested. The sorption isotherm of adsorbent was best described by the Langmuir model. The kinetic data were analyzed using pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Elovich kinetic models. The adsorption kinetics of Fe (III) ions were well fitted with the pseudo-second-order kinetic model.     

Catalytic application of K2Ce(PO4)2 in Knoevenagel condensation -A green protocol

A framework connected phosphate material K₂Ce(PO₄)₂, explored for the first time for the Knoevenagel condensation of aldehydes with malononitrile in water. The catalyst was prepared by newly developed solid-state method and characterized using XRD, RAMAN, FTIR, BET surface area, TPD, XPS, SEM and HRTEM. The developed protocol showed the substrate compatibility along with the catalyst reusability. Moreover, the catalyst was scaled up to 30 g and also showed reusability. The role of predominant Ce(IV) species was also discussed apart from phosphate basic sites.     

Determination of surface properties of iron hydroxide-coated alumina adsorbent prepared for removal of arsenic from drinking water

A novel type adsorbent was prepared by in situ precipitation of Fe(OH)3 on the surface of activated Al2O3 as a support material. The iron content of the adsorbent was 0.31+/-0.003% m/m (56.1 mmol/g); its mechanical and chemical stability proved to be appropriate in solutions. The total capacity of the adsorbent was 0.12 mmol/g, and the pH of zero point of charge, pH(zpc) = 6.9+/-0.3. Depending on the pH of solutions, the adsorbent can be used for binding of both anions and cations, if pH(eq) < pH(zpc) anions are sorbed on the surface of adsorbent (S) through [SOH2+] and [SOH] groups. A graphical method was used for the determination of pH(iep) (isoelectric points) of the adsorbent and values of pH(iep) = 6.1+/-0.3 for As(III) and pH(iep) = 8.0+/-0.3 for As(V) ions were found. The amount of surface charged groups (Q) was about zero within the a pH range of 6.5-8.6, due to the practically neutral surface formed on the adsorption of As(V) ions. At acidic pH (pH 4.7), Q = 0.19 mol/kg was obtained. The adsorption of arsenate and arsenite ions from solutions of 0.1-0.4 mmol/L was represented by Langmuir-type isotherms. A great advantage of the adsorbent is that it can be used in adsorption columns, and low waste technology for removal of arsenic from drinking water can be developed.     

稀土水滑石的合成与表征（Ⅰ）

合成了稀土镧在层晶格骨架中的水滑石,经粉末X射线衍射、红外光谱、X射线光电子能谱及离子交换法进行了表征.通过催化苯酐与正己醇的酯化反应,表明样品具有催化活性.