Iron changes in natural and Fe(III) loaded montmorillonite during carbon nanotube growth

A detailed elaboration of the transformations of iron species, present in natural and Fe(NO(3))(3) loaded montmorillonite, during carbon deposition and carbon nanotube growth is described. According to transmission electron microscopy results, deposited carbon atoms form fibres in the case of pristine montmorillonite and multiwalled carbon nanotubes in the case of Fe(III) loaded montmorillonite. M?ssbauer and x-ray diffraction analysis results point to an extensive reduction of structural and intercalated Fe(III) cations to Fe(II) with the latter migrating from the interlayer space to the vacant octahedral sites of the mineral's lattice. Such migration of the non-structural iron catalyst prohibits extensive contamination of the final composite with various metal catalyst impurities. The crucial role of the active catalytic centres in the formation of carbon nanotubes is ascribed to a minor quantity of iron, found entrapped in the carbon nanostructures, which, at the end of the reaction, is identified as iron carbide. The interesting formation of a nanometric γ-iron precipitate is also detected, which is probably stabilized through strong interactions with the lattice of montmorillonite. Finally, it is demonstrated that iron-rich natural clay minerals can serve as direct catalysts for carbon nanotube growth.     

Adsorption characteristics of Fe(III) and Fe(III)-NTA complex on granular activated carbon

The adsorption of Fe(3+) ion on granular activated carbon has been studied in kinetic and equilibrium conditions taking into account the adsorbate concentration, temperature and solution pH as major influential factors. In addition, the effect of nitrilotriacetic acid on adsorption reaction as a complexing agent has been examined. Kinetic studies showed that the adsorption rate was increased as the initial Fe(3+) concentration was raised. The adsorption reaction was estimated to be first-order at room temperature. The adsorption rate and equilibrium adsorption of Fe(3+) increased as the temperature rose. The activation energy for adsorption was approximately 2.23 kJ mol(-1), which implied that Fe(3+) mainly physically adsorbed on activated carbon. Coexistence of nitrilotriacetic acid with Fe(3+) resulted in a decrease of equilibrium adsorption and the extent of decrease was proportional to the concentration of nitrilotriacetic acid. In the presence of nitrilotriacetic acid, the adsorbability of Fe(3+) decreased with pH. However, the trend was reversed in the absence of nitrilotriacetic acid. When activated carbon was swelled by acetic acid, the specific surface area was increased and maximum swelling was achieved at approximately 48 h of swelling time. Thermodynamic parameters such as DeltaG(o), DeltaH(o) and DeltaS(o) for adsorption reaction were estimated based on equilibrium data and in connection with these results the thermodynamic aspects of adsorption reaction were discussed.     

Photodegradation mechanism and kinetics of methyl orange catalyzed by Fe(III) and citric acid

In this study, the photodegradation process of methyl orange (MO) catalyzed by Fe(III) and citric acid and the reaction kinetics were investigated in detail at pHs from 2 to 8. The results show that the photodegradation of MO is slow in the presence of Fe(III) or citric acid alone. However, it is markedly enhanced when Fe(III) and citric acid coexist. High initial citric acid or initial Fe(III) concentrations lead to increased photodegradation of MO. And Fe(III) citrate mediated photodegradation of MO is optimized at pH 6. The photoproduction of hydroxyl radicals (·OH) in different catalytic systems was determined by HPLC. And the concentrations of Fe(II) and citric acid concentration in the process of the reaction were analyzed. The photodegradation of MO obeys to pseudo-zero order kinetics with respect to MO and the degradation reaction occurs in two phases. At the initial initiation stage, degradation rate is relatively slow, and significantly increases at a later acceleration stage.     

TOF-SARS study of hydrogen adsorption and desorption kinetics on Si(1 0 0)

The kinetics of atomic hydrogen isothermal adsorption and desorption on a Si(1 0 0) surface was studied using the time-of-flight scattering and recoiling spectrometry technique at temperatures below and above the thermal desorption threshold. A continuous decrease in saturation coverage with temperature under constant atomic hydrogen exposure has been observed in both regions for temperatures in the range 325-820 K. For T_S=500-650 K, the decrease is described by a kinetic model where Eley-Rideal (ER) abstraction is responsible for hydrogen removal from the surface and hydrogen coverage depends on the temperature due to the changing rate of migration from precursor to primary monohydride sites. For T_S=650 K and higher, in addition to the ER abstraction, the thermal desorption from primary monohydride sites leads to a further decrease of the saturation coverage. The first-order desorption rates after source shut-off have been measured and an activation barrier of 1.89 eV has been obtained.     

Arsenic removal by adsorption on iron(III) phosphate

Under natural conditions, arsenic is often associated with iron oxides and iron(III) oxidative capacity towards As(III) is well known. In this study, As(III) and As(V) removal was performed using synthesised iron(III) phosphate, either amorphous or crystalline. This solid can combine (i) As(III) oxidation by iron(III) and (ii) phosphate substitution by As(V) due to their similar properties. Results showed that adsorption capacities were higher towards As(III), leading to Fe2+ and HAsO4(2-) leaching. Solid dissolution and phosphate/arsenate exchange led to the presence of Fe3+ and PO4(3-) in solution, therefore various precipitates involving As(V) can be produced: with Fe2+ as Fe3(AsO4)2.8H2O(s) and with Fe3+ as FeAsO4.2H2O(s). Such formations have been assessed by thermodynamic calculations. This sorbent can be a potential candidate for industrial waste treatment, although the high release of phosphate and iron will exclude its application in drinking water plants.     

Characterization of Fe(III)-Zr(IV) mixed and Sn(III)-doped hydrous oxides

Surface and structural properties of iron-zirconium mixed and Sn(II)-doped hydrous oxide gels have been compared with ferric oxide hydrate gel using thermal analysis, infrared spectroscopy, X-ray diffraction, electron microscopy and magnetic measurements. The mixed and doped oxide gels were found to consist of a hexagonal close packed arrangement of oxygen sublattices similar to those present in -FeOOH and -Fe₂O₃, with the iron ion quite randomly distributed in the gels. The gels were found to be composed of hexagonal to rounded and thin rod-like particles and their agglomerates. The particles in the superparamagnetic state have an incompletely compensated antiferromagnetic character.     

Thermodynamics and kinetics of Zn(II) adsorption on crosslinked starch phosphates

Crosslinked starch phosphates (CSP) with different contents of phosphate groups were used to adsorb Zn(II) from aqueous solution. Effects of adsorption time, initial concentration of Zn(II) ion, and temperature on the adsorption of Zn(II) by CSP were studied, and the equilibrium, thermodynamics and kinetics of the adsorption process were further investigated. It showed that crosslinked starch phosphates can effectively remove Zn(II) from the solution. The adsorption equilibrium data correlate well with the Langmuir isotherm model with a maximum adsorption capacity of 2.00mmolg(-1). The adsorption of Zn(II) on CSP is endothermic in nature. The pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data. The pseudo-second-order kinetic model provided a better correlation of the experimental data in comparison with the pseudo-first-order model.     

Equilibrium studies for trimethoprim adsorption on montmorillonite KSF

In this study, the adsorption of trimethoprim (TMP) on montmorillonite KSF was studied under different conditions (pH, ionic strength, temperature). The results indicate that a pH value of 5.04 is optimum value for the adsorption of TMP on KSF. The adsorption kinetics was interpreted using pseudo-first-order kinetic model, pseudo-second-order kinetic model and intraparticle diffusion model. The pseudo-second-order model provides the best correlation with the experimental data of KSF adsorption. The adsorption data could be fitted with Freundlich, Langmuir and Dubinin-Radushkevich equation to find the characteristic parameters of each model. It was found that linear form of Langmuir isotherm seems to produce a better model than linear form of Freundlich equation. From the Langmuir and Freundlich equation, the adsorption capacity values raised as the solution temperature decreased. From DR isotherm, it was also determined that the type of adsorption can be considered as ion-exchange mechanism. Determination of the thermodynamic parameters DeltaH(0), DeltaS(0) and DeltaG(0) showed that adsorption was spontaneous and exothermic in nature. It was also added that adsorption of TMP by KSF may involve physical adsorption.     

非剥离型聚苯胺/蒙脱土碳纳米复合吸附材料的研究

采用原位插层聚合法制备非剥离型聚苯胺/蒙脱土纳米复合吸附材料,研究了过氧化环己酮、异辛酸钴的用量和反应时间,以及碳化温度对复合材料性能的影响。结果表明:引发剂的用量为3%,促进剂的用量为5%,聚合反应时间为1.5h,所得的聚苯胺/蒙脱土复合材料的层间距最大,达21.54;碳化温度为500℃,所得的碳纳米复合材料的比表面积最大,达52.39m2/g。利用XRD、FT-IR、TG和BET等手段对该条件下制备的纳米复合材料进行了表征。     

Kinetics and equilibrium isotherms of adsorption of Pb(II) and Cu(II) onto raw and arginine-modified montmorillonite

Arg-Mt, was fabricated by modifying sodium montmorillonite (Na-Mt) with Arginine monohydrochloride (Arg salt), to adsorb Pb(II) and Cu(II) in aqueous solution. The X-ray powder diffraction (XRD), Fourier transform infrared (FTIR) spectrum, thermal analysis (TG/DTG), Brunauer-Emmett-Teller (BET) and Scanning electron microscope (SEM) were employed to investigate the properties of Na-Mt and Arg-Mt. The effects of the amount of modifier, pH value, the initial concentration of M(II), temperature and contact time were tested in a single adsorption system. The isotherm model was well matched with the Langmuir curve and the kinetic adsorption fitted well with the pseudo-second-order rate equation. The saturated adsorption of Pb(II) and Cu(II) by Arg-Mt were 124.69 and 29.15?mg/g, respectively, which were higher than that of Na-Mt (89.08 and 23.93?mg/g). The thermodynamic equation indicated that the adsorption process was spontaneous, endothermic, and the randomness of the samples changed a little after adsorption. The adsorption capacity of heavy metal ions in the binary co-adsorption system was poor than single adsorption system. Furthermore, the adsorbed M(II) onto Arg-Mt can hardly be dissolved under weak acidic condition (pH?>?4) according to the desorption experiments. High-efficiency and low-cost make Arg-Mt to be used in the removal of heavy ions in aqueous solution.     

蒙脱土/海藻酸钠接枝丙烯酸高吸水性复合物的制备及吸附性能研究

以过硫酸胺(APS)为引发剂,N,N-亚甲基双丙烯酰胺(MBA)为交联剂,采用插层聚合法制备了蒙脱土/海藻酸钠接枝丙烯酸(MMT/SA-g-PAA)高吸水性复合物。通过红外光谱(FT-IR)、扫描电镜(SEM)、热重分析(TGA)对MMT/SA-g-PAA的结构和性能进行了表征。研究了MMT/SA-g-PAA对重金属离子的吸附性能,结果表明室温下MMT/SA-g-PAA对Pb2+、Cu2+、Ni 2+的最大吸附量分别为968.9、231.0及236.0mg/g,其中对Pb2+和Cu2+的吸附符合Langmuir吸附模型,而对Ni 2+的吸附符合Freundlich吸附模型。     

Detection of phosphopeptides using Fe(III)-nitrilotriacetate complexes immobilized on a MALDI plate

Metal affinity complexes were chemically grafted onto the surface of gold matrix-assisted laser desorption/ionization (MALDI) plates by coupling a derivative of nitrilotriacetate (NTA) to immobilized poly(acrylic acid) (PAA) and subsequently forming the Fe(III)-NTA complex. The immobilized complexes can adsorb phosphorylated peptides preferentially from protein digests; deposition of digests on these surface-modified plates, followed by rinsing with an acetic acid solution, addition of matrix, and subsequent analysis by MALDI MS, resulted in mass spectra dominated by peaks corresponding to phosphopeptides. In the case of analyzing a tryptic digest of beta-casein, conventional MALDI MS revealed only one monophosphopeptide, while use of the Fe(III)-NTA-PAA-modified plate resulted in strong signals due to two additional tetraphosphorylated species. The diminution or elimination of signals due to nonphosphorylated species also greatly simplified the identification of phosphopeptides during analysis of ovalbumin digests and myoglobin digests spiked with an equimolar mixture of angiotensin and phosphoangiotensin. The matrix 2',4',6'-trihydroxyacetophenone mixed with diammonium hydrogen citrate proved to be much better than alpha-cyano-4-hydroxycinnamic acid for the detection of phosphorylated peptides from digests of beta-casein and ovalbumin.     

Synthesis and characterization of Fe(III)-silicate precipitation tubes

Fe(III)-silicate precipitation tubes synthesized through “silica garden” route have been characterized using a number of analytical techniques including X-ray diffraction, infrared spectroscopy, atomic force microscopy, scanning and transmission electron microscopy. These tubes are brittle and amorphous and are hierarchically built from smaller tubes of 5-10 nm diameters. They remain amorphous at least up to 650 °C. Crystobalite and hematite are the major phases present in Fe(III)-silicate tubes heated at 850 °C. Morphology and chemical compositions at the external and internal walls of these tubes are remarkably different. These tubes are porous with high BET surface area of 291.2 m²/g. Fe(III)-silicate tubes contain significant amount of physically and chemically bound moisture. They show promise as an adsorbent for Pb(II), Zn(II), and Cr(III) in aqueous medium.     

Triplet-state photoexcitation dipole-jump relaxation method to observe adsorption/desorption kinetics at a reversed-phase silica/solution interface

Electronic excitation of a probe chromophore can lead to a change in dipole moment that influences its activity or solubility in solution and changes its relative affinity for partitioning between two phases. Photoexcitation of a probe molecule can, therefore, perturb a sorption equilibrium, and the relaxation kinetics of the probe to the new equilibrium conditions can be monitored in a time-resolved luminescence experiment. The adsorption/desorption kinetics of rose bengal, distributed between a C-18 derivatized porous-silica surface and a liquid mobile-phase solution, were investigated. These kinetics were determined by observing their effect on the phosphorescence decay of the triplet state of rose bengal and its quenching by ferricyanide. The methanol/water solvent compositions were varied to alter the fraction of adsorbed rose bengal. The adsorption rate constant for the triplet state was determined from the dependence of the phosphorescence relaxation rate on dye concentration in solution. The results indicate that the adsorption kinetics are diffusion controlled and that the relaxation is influenced by efficient triplet-energy transfer between excited- and ground-state rose bengal at the C-18 silica/solution interface.     

Enhanced sorption of radiocobalt from water by Bi(III) modified montmorillonite: a novel adsorbent

In this study, Ca-montmorillonite (Ca-Mt) modified with Bi³⁺ was used as a novel adsorbent for the sorption of Co(II) from aqueous solutions. The sorption of Co(II) on Bi-montmorillonite (Bi-Mt) was investigated as a function of contact time, pH, ionic strength, adsorbent content, Co(II) concentrations, fulvic acid (FA) and temperature. Compared to Ca-Mt, Bi-Mt showed a higher affinity to bind Co(II) ions. The sorption percentage of Co(II) on Bi-Mt increased with increasing pH at pH 3.0-8.5, and then maintained the high level at pH 8.5-12. The sorption of Co(II) on Bi-Mt was dependent on ionic strength at low pH, and independent of ionic strength at high pH. The presence of FA enhanced Co(II) sorption at low pH, but suppressed Co(II) sorption at high pH. The thermodynamic data derived from temperature dependent sorption isotherms suggested that the sorption of Co(II) on Bi-Mt was spontaneous and endothermic process. Outer-sphere surface complexation and/or ion exchange were the main mechanisms of Co(II) sorption on Bi-Mt at low pH, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. From the experimental results, it is possible to conclude that Bi-Mt is suitable for application of Co(II) removal from aqueous solutions.     

Speciation of Fe(III) Radionuclides in Aqueous Solutions

Fe(III) radionuclide speciation in aqueous solutions at pH ranging from 1 to 12 and Fe(III) concentration, from 1 ×10^{- 7} to 1 ×10^{- 2} M was studied. At trace Fe(III) concentrations (1 ×10^{- 7} M), the sorption colloids, so-called pseudocolloids, are formed within pH range 3-12. At pH within 0.7-1.5, Fe(III) exists in the form of hydrated cations Fe(H₂O)₆ ^{3 +}, which are hydrolyzed at pH > 1.5 (K _h = 3.7 ×10^{- 3}) to form mononuclear Fe(OH)^{2 +} hydroxo complexes. At Fe(III) concentration exceeding 1 ×10^{- 4} M, Fe₂(OH)5.70.3+ binuclear hydroxo complexes are formed.     

Nitric oxide adsorption and desorption on alumina supported palladium

The adsorption properties of nitric oxide (NO) on alumina supported palladium were studied by a simultaneous thermogravimetric-analysis and differential-scanning-calorimetry (TGA-DSC) in a temperature ranges between 220 and 470 K. Upon adsorption, NO molecules on both Pd/Al2O3 and Pd/NaOH-Al2O3 samples were molecularly adsorbed between 220 and 300 K. Some NO molecules were strongly adsorbed on Pd/NaOH-Al2O3 and possessed a higher enthalpy of adsorption [approximately 140 kJ (mol NO)(-1)] than Pd/Al2O3 [approximately 114 kJ (mol NO)(-1)]. Upon heating above 320 K, the adsorbed NO molecule on these palladium surface was dissociated. In addition, a temperature programmed desorption and mass spectrometer (TPD-MS) study in a temperature range between 300 and 1100 K further indicated that some strongly adsorbed NO molecules may stay on basic sites (*b) and Pd-NaOH interface sites (*i) to enhance the decomposition of NO.     

Synthesis and characterization of Fe3+-modified PLZT ferroelectrics

Fe³⁺-modified nanocrystalline PLZT, i.e., Pb_0.92[La_1–z Fe _z ]_0.08[Zr_0.60Ti_0.40]_0.98O₃ (PLFZT) (z=0.0, 0.3, 0.6, 0.9, 1) materials were synthesized by a high-temperature solid-state reaction technique. X-ray studies of the compounds confirmed the formation of single-phase, ultrafine (nano-sized) and homogeneous materials. Microstructural scanning electron microscopy (SEM) study shows the uniform distribution of smaller grains on the surface of the samples. Detailed dielectric studies of the compounds as a function of temperature (30–450 °C) show that the broadening of the permittivity peak and transition temperature depends on Fe³⁺-ion concentration. Analysis of diffuseness () of the broadened dielectric peaks of the materials gave its value between 1 and 2, indicating the different degrees of substitutional disorder in the system. The increase in Fe³⁺-substitution at the La-site of PLZT shows many interesting and unusual dielectric relaxor behaviors of the compounds. The transition temperature T _c of PLZT (8/60/40) ferroelectric shifts towards a higher temperature region on increasing Fe³⁺ concentration. The variation of d.c. and a.c. electrical conductivity of the material with temperature shows its semiconducting behavior; and hence the materials can be used for some electronic devices.     

An adsorption study of Al(III) ions onto chitosan

The adsorption of Al(III) from aqueous solutions onto chitosan was studied in a batch system. The isotherms and the kinetics of adsorption with respect to the initial Al(III) concentration and temperature were investigated. Langmuir and Freundlich adsorption models were applied to describe the experimental isotherms. Equilibrium data fitted very well to the Langmuir model in the entire concentration range (5-40 mg/L). The negative values of free energy (DeltaG degrees ) and enthalpy (DeltaH degrees ) for the adsorption of Al(III) onto chitosan indicated that the adsorption process is a spontaneous and exothermic one. Two simplified kinetic models, based on pseudo first-order and pseudo second-order equations, were tested to describe the adsorption mechanism. The pseudo second-order kinetic model resulted in an activation energy of 56.4 kJ/mol. It is suggested that the overall rate of Al(III) ion adsorption is likely to be controlled by the chemical process. The values of the enthalpy (DeltaH(#)) and entropy (DeltaS(#)) of activation were 53.7 kJ/mol and -164.4 J/molK, respectively. The free energy of activation (DeltaG(#)) at 30 degrees C was 103.5 kJ/mol.