Hongping He

Montmorillonite-supported magnetite nanoparticles for the removal of hexavalent chromium [Cr(VI)] from aqueous solutions.

Montmorillonite-supported magnetite nanoparticles were prepared by co-precipitation and hydrosol method. The obtained materials were characterized by X-ray diffraction, nitrogen adsorption, elemental analysis, differential scanning calorimetry, transmission electron microscopy and X-ray photoelectron spectroscopy. The average sizes of the magnetite nanoparticles without and with montmorillonite support are around 25 and 15 nm, respectively. The montmorillonite-supported magnetite nanoparticles exist on the surface or inside the interparticle pores of clays, with better dispersing and less coaggregation than the ones without montmorillonite support. Batch tests were carried out to investigate the removal mechanism of hexavalent chromium [Cr(VI)] by these synthesized magnetite nanoparticles. The Cr(VI) uptake was mainly governed by a physico-chemical process, which included an electrostatic attraction followed by a redox process in which Cr(VI) was reduced into trivalent chromium. The adsorption of Cr(VI) was highly pH-dependent and the kinetics of the adsorption followed the Pseudo-second-order model. The adsorption data of unsupported and clay-supported magnetite nanoparticles fit well with the Langmuir and Freundlich isotherm equations. The montmorillonite-supported magnetite nanoparticles showed a much better adsorption capacity per unit mass of magnetite (15.3mg/g) than unsupported magnetite (10.6 mg/g), and were more thermally stable than their unsupported counterparts. These fundamental results demonstrate that the montmorillonite-supported magnetite nanoparticles are readily prepared, enabling promising applications for the removal of Cr(VI) from aqueous solution.

Removal of hexavalent chromium (Cr(VI)) from aqueous solutions by the diatomite-supported/unsupported magnetite nanoparticles

Diatomite-supported/unsupported magnetite nanoparticles were prepared by co-precipitation and hydrosol methods, and characterized by X-ray diffraction, nitrogen adsorption, elemental analysis, differential scanning calorimetry, transmission electron microscopy and X-ray photoelectron spectroscopy. The average sizes of the unsupported and supported magnetite nanoparticles are around 25 and 15 nm, respectively. The supported magnetite nanoparticles exist on the surface or inside the pores of diatom shells, with better dispersing and less coaggregation than the unsupported ones. The uptake of hexavalent chromium [Cr(VI)] on the synthesized magnetite nanoparticles was mainly governed by a physico-chemical process, which included an electrostatic attraction followed by a redox process in which Cr(VI) was reduced into trivalent chromium [Cr(III)]. The adsorption of Cr(VI) was highly pH-dependent and the kinetics of the adsorption followed a pseudo-second-order model. The adsorption data of diatomite-supported/unsupported magnetite fit well with the Langmuir isotherm equation. The supported magnetite showed a better adsorption capacity per unit mass of magnetite than unsupported magnetite, and was more thermally stable than their unsupported counterparts. These results indicate that the diatomite-supported/unsupported magnetite nanoparticles are readily prepared, enabling promising applications for the removal of Cr(VI) from aqueous solution.

THERMAL CHARACTERIZATION OF SURFACTANT-MODIFIED MONTMORILLONITES

The thermal stability of surfactant-modified clays plays a key role in the synthesis and processing of organoclay-based nanocomposites. Differential thermal analysis (DTA), thermogravimetric measurement and differential scanning calorimetry (DSC) were used in this study to characterize the thermal stability of hexadecyltrimethylammonium bromide-modified montmorillonites prepared at different surfactant concentrations. Analysis by DSC shows that the molecular environment of the surfactant within the montmorillonite galleries is different from that in the bulk state. The endothermic peak at 70–100°C in the DTA curves of the modified montmorillonites is attributed to both the surfactant phase transformation and the loss of free and interlayer water. With an increase of surfactant-packing density, the amount of water residing in the modified montmorillonite decreases gradually, reflecting the improvement of the hydrophobic property for the organoclay. However, the increase in the surfactant packing density within the galleries leads to a decrease in the thermal stability of the organoclays.With an increase of initial surfactant concentration for the preparation of organoclays, the surfactant- packing density increases gradually to a ‘saturated’ state. It was found that the cationic surfactant was introduced into the montmorillonite interlayer not only by cation exchange but also by physical adsorption.

Arrangement models of alkylammonium cations in the interlayer of HDTMA~+ pillared montmorillonites

The orientation of HDTMA+ in the interlayer of organic pillared montmorillonites prepared at different concentrations of HDTMA+ have been studied using X-ray powder diffraction (XRD) and theoretical calculation. A series of arrangement models of HDTMA+ in the interlayer of montmorillonite have been proposed as lateral-monolayer (LM), lateral-bilayer (LB), pseudotrilayer (PT), paraffin-type-monolayer (PM), paraffin-type-bilayer (PB). With the increase of the concentration of HDTMA+, the arrangement model of HDTMA+ in the interlayer of montmorillonites changes as lateral-monolayer→lateral-bilayer→paraffin-type monolayer→pseudotrilayer→paraffin-type-bilayer and the packing density of HDTMA+ in the interlayer increases gradually. In the intermediate stages, different models may coexist.

Synthesis, characterization of palygorskite supported zero-valent iron and its application for methylene blue adsorption

In this work, natural palygorskite impregnated with zero-valent iron (ZVI) was prepared and characterized. The combination of ZVI particles on surface of fibrous palygorskite can help to overcome the disadvantage of ultra-fine powders which may have strong tendency to agglomerate into larger particles, resulting in an adverse effect on both effective surface area and catalyst performance. There is a significant increase of methylene blue (MB) decolourized efficiency on acid treated palygorskite with ZVI grafted, within 5 min, the concentration of MB in the solution was decreased from 94 mg/L to around 20 mg/L and the equilibration was reached at about 30-60 min with only around 10 mg/L MB remained in solution. Changes in the surface and structure of prepared materials were characterized using X-ray diffraction (XRD), infrared (IR) spectroscopy, surface analysing and scanning electron microscopy (SEM) with element analysis and mapping. Comparing with zero-valent iron and palygorskite, the presence of zero-valent iron reactive species on the palygorskite surface strongly increases the decolourization capacity for methylene blue, and it is significant for providing novel modified clay catalyst materials for the removal of organic contaminants from waste water.

Microstructure of HDTMA+-Modified Montmorillonite and its Influence on Sorption Characteristics

A series of organoclays with monolayers, bilayers, pseudotrilayers, paraffin monolayers and paraffin bilayers were prepared from montmorillonite by ion exchange with hexadecyltrimethylammonium bromide (HDTMAB). The HDTMAB concentrations used for preparing the organoclays were 0.5, 0.7, 1.0, 1.5, 2.0 and 2.5 times the montmorillonite cation exchange capacity (CEC). The microstructural parameters, including the BET-N2 surface area, pore volume, pore size, and surfactant loading and distribution, were determined by X-ray diffraction, N2 adsorption-desorption and high-resolution thermogravimetric analysis (HRTG). The BET-N2 surface area decreased from 55 to 1 m2/g and the pore volume decreased from 0.11 to 0.01 cm3/g as surfactant loading was increased from Na-Mt to 2.5CEC-Mt. The average pore diameter increased from 6.8 to 16.3 nm as surfactant loading was increased. After modifying montmorillonite with HDTMAB, two basic organoclay models were proposed on the basis of HRTG results: (1) the surfactant mainly occupied the clay interlayer space (0.5CEC-Mt, 0.7CEC-Mt, 1.0CEC-Mt); and (2) both the clay interlayer space and external surface (1.5CEC-Mt, 2.0CEC-Mt, 2.5CEC-Mt) were modified by surfactant. In model 1, the sorption mechanism of p-nitrophenol to the organoclay at a relatively low concentration involved both surface adsorption and partitioning, whereas, in model 2 it mainly involved only partitioning. This study demonstrates that the distribution of adsorbed surfactant and the arrangement of adsorbed HDTMA+ within the clay interlayer space control the efficiency and mechanism of sorption by the organoclay rather than BET-N2 surface area, pore volume, and pore diameter.

A combined study by XRD, FTIR, TG and HRTEM on the structure of delaminated Fe-intercalated/pillared clay

Fe-PILC samples were synthesized by the reaction between Na(+)- and/or Ca(2+)-montmorillonite (Mt) and base-hydrolyzed solutions of Fe(III) nitrate. Different from the known usual microporous pillared structure, a meso-microporous delaminated structure containing intercalated or pillared fragments was found in the respective resulting Fe-intercalated or -pillared clays. XRD patterns of Na(+)-Mt-based Fe-intercalated/pillared clays show one large d-spacing above 6.4 nm corresponding to the mesoporous delaminated part, whereas another d-spacing of ca. 1.5 nm was indicative of the microporous pillared part. Fe-intercalated/pillared clays based on Ca(2+)-Mt lead to similar results, but with a d-spacing less than 6 nm and a second low intense d-spacing less than 1.5 nm. In the delaminated Fe-intercalated clays, NO(-)(3) anions were retained even after thorough washing process. They play as counterions to neutralize the positive-charged iron aggregates in the delaminated structure, and can be exchanged by heteropolyanions as [PW(12)O(40)](3-). The delaminated Fe-pillared clays show good thermal stability at 500 degrees C and exhibit at this temperature dramatically higher specific surface area and porosity than the starting montmorillonites. However, calcination at a higher temperature leads to the formation of nanocrystalline hematite. Air-drying after ethanol extraction (EAD) method has an advantage over air-drying (AD) method in preserving the delaminated structure.

CONFORMATION OF SURFACTANT MOLECULES IN THE INTERLAYER OF MONTMORILLONITE STUDIED BY 13C MAS NMR

The ordering conformation of surfactant molecules in intercalated montmorillonite prepared at various concentrations was investigated by 13C MAS NMR. The 13C MAS NMR study demonstrates the coexistence of ordered and disordered chain conformations. Two main resonance peaks are associated with the backbone alkyl chains: the resonance at 33 ppm corresponds to the ordered conformation (all-trans), and the resonance at 30 ppm corresponds to the disordered conformation (mixture of trans and gauche). Deconvolution of 13C MAS NMR spectra indicates that the ordering conformation of surfactant molecules within the gallery of montmorillonite depends very much on their orientation and packing density. When amine chains are oriented parallel to the silicate layers, the amount of all-trans conformer decreases with the increase of amine concentration. However, the amount of all-trans conformer increases with the increase of amine concentration when amine chains radiate from the silicate layers. Furthermore, 13C MAS NMR spectra show that the intercalated surfactant molecules in the clay minerals never attained the complete liquidlike or solidlike behavior.

The decolorization of Acid Orange II in non-homogeneous Fenton reaction catalyzed by natural vanadium-titanium magnetite

The catalytic activity of natural vanadium-titanium magnetite was investigated in the decolorization of Acid Orange II by non-homogeneous Fenton process. The natural catalysts purified by magnetic separation were characterized using X-ray diffraction (XRD), polarizing microscope, X-ray absorption fine structure (XAFS) analysis and Mössbauer spectroscopy. The obtained results show that the natural samples after magnetic separation mainly contain titanomagnetite, with a small amount of ilmenite and chlorite. Titanomagnetite is doped with vanadium, whose the valency is mainly +3 and occupies the octahedral site. Batch decolorization studies were performed to evaluate the influences of various experimental parameters like initial pH, the amount of catalyst and initial concentration of hydrogen peroxide on the decolorization efficiency of Acid Orange II. The decolorization of the dye mainly relied on degradation. The degradation efficiency was strongly dependent on pH of the medium where it increased as the pH decreased in acid range. The increase of catalyst and hydrogen peroxide could accelerate the degradation. The catalytic property of natural vanadium-titanium magnetite in the degradation of Acid Orange II was stronger than that of synthetic magnetite (Fe(3)O(4)). The catalytic activity of the natural samples was greatly related to the titanomagnetite content. The degradation process was dominated by heterogeneous Fenton reaction, complying with pseudo-first-order rate law. The natural catalyst has a good catalytic stability.

Heterogeneous UV/Fenton degradation of TBBPA catalyzed by titanomagnetite: Catalyst characterization, performance and degradation products

Tetrabromobisphenol A (TBBPA), a widely used brominated flame retardant, could negatively affect various aspects of mammalian and human physiology, which triggers effective techniques for its removal. In this work, the degradation characteristics of TBBPA in heterogeneous UV/Fenton reaction catalyzed by titanomagnetite (Fe(3-x)Ti(x)O₄) were studied. Batch tests were conducted to evaluate the effects of titanomagnetite dosage, H₂O₂ concentration and titanium content in magnetite on TBBPA degradation. In the system with 0.125 g L⁻¹ of Fe₂.₀₂Ti₀.₉₈O₄ and 10 mmol L⁻¹) of H₂O₂, almost complete degradation of TBBPA (20 mg L⁻¹) was accomplished within 240 min UV irradiation at pH 6.5. The titanium incorporation obviously enhanced the catalytic activity of magnetite. As shown by the XRD and XANES results, titanomagnetite had a spinel structure with Ti⁴⁺ occupying the octahedral sites. On the basis of the degradation products identified by GC-MS, the degradation pathways of TBBPA were proposed. TBBPA possibly underwent the sequential debromination to form TriBBPA, DiBBPA, MonoBBPA and BPA, and β-scission to generate seven brominated compounds. All of these products were finally completely removed from reaction solution. In addition, the reused catalyst Fe₂.₀₂Ti₀.₉₈O₄ still retained the catalytic activity after three cycles, indicating that titanomagnetite had good stability and reusability. These results demonstrated that heterogeneous UV/Fenton reaction catalyzed by titanomagnetite is a promising advanced oxidation technology for the treatment of wastewater containing TBBPA.