Zirconium doped nano-dispersed oxides of Fe,Al and Zn for destruction of warfare agents

Zirconium doped nano dispersive oxides of Fe, Al and Zn were prepared by a homogeneous hydrolysis of the respective sulfate salts with urea in aqueous solutions. Synthesized metal oxide hydroxides were characterized using Brunauer–Emmett–Teller (BET) surface area and Barrett–Joiner–Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDX). These oxides were taken for an experimental evaluation of their reactivity with sulfur mustard (HD or bis(2-chloroethyl)sulfide), soman (GD or (3,3′-Dimethylbutan-2-yl)-methylphosphonofluoridate) and VX agent (S-[2-(diisopropylamino)ethyl]-O-ethyl-methylphosphonothionate). The presence of Zr⁴⁺ dopant can increase both the surface area and the surface hydroxylation of the resulting doped oxides, decreases their crystallites' sizes thereby it may contribute in enabling the substrate adsorption at the oxide surface thus it can accelerate the rate of degradation of warfare agents. Addition of Zr⁴⁺ converts the product of the reaction of ferric sulphate with urea from ferrihydrite to goethite. We found out that doped oxo-hydroxides Zr–FeO(OH) — being prepared by a homogeneous hydrolysis of ferric and zirconium oxo-sulfates mixture in aqueous solutions — exhibit a comparatively higher degradation activity towards chemical warfare agents (CWAs). Degradation of soman or VX agent on Zr-doped FeO(OH) containing ca. 8.3 wt.% of zirconium proceeded to completion within 30 min.     

Detoxification reactions of sulphur mustard on the surface of zinc oxide nanosized rods

Detoxification reactions of sulphur mustard, a deadliest chemical warfare agent were studied on the surface of zinc oxide nanorods at room temperature (32+/-2 degrees C) and the data was compared with that of the bulk ZnO. Prior to the reaction, the nanorods of zinc oxide were synthesized by the hydrothermal method and subsequently characterized by XRD, SEM, TG, N(2) BET, FT-IR. The data revealed the formation of nanorods with diameter ranging from 100 nm to 500 nm with length in microns. Obtained nanomaterial along with bulk ZnO were tested as reactive sorbent for the detoxification of sulphur mustard. Reaction was monitored by GC-FID technique and the reaction products were characterized by GC-MS. Data explores the role of hydrolysis and elimination reactions in the detoxification of sulphur mustard and it also reveals that zinc oxide nanorods and bulk ZnO show the half lives of 8.48 h, 24.75 h in the first 12h and 122.47 h, 177.29 h from 12h to 48 h of the reaction.     

Mesoporous titanium–manganese dioxide for sulphur mustard and soman decontamination

Titanium(IV)–manganese(IV) nano-dispersed oxides were prepared by a homogeneous hydrolysis of potassium permanganate and titanium(IV) oxo-sulphate with 2-chloroacetamide. Synthesised samples were characterised using Brunauer–Emmett–Teller (BET) surface area and Barrett–Joiner–Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), and scanning electron microscopy (SEM). These oxides were taken for an experimental evaluation of their reactivity with sulphur mustard (HD or bis(2-chloroethyl)sulphide) and soman (GD or (3,3′-dimethylbutan-2-yl)-methylphosphonofluoridate). Mn⁴⁺ content affects the decontamination activity; with increasing Mn⁴⁺ content the activity increases for sulphur mustard and decreases for soman. The best decontamination activities for sulphur mustard and soman were observed for samples TiMn_37 with 18.6 wt.% Mn and TiMn_5 with 2.1 wt.% Mn, respectively.     

Impregnated silica nanoparticles for the reactive removal of sulphur mustard from solutions

High surface area (887.3m(2)/g) silica nanoparticles were synthesized using aerogel route and thereafter, characterized by N(2)-Brunauer-Emmet-Teller (BET), SEM and TEM techniques. The data indicated the formation of nanoparticles of silica in the size range of 24-75 nm with mesoporous characteristics. Later, these were impregnated with reactive chemicals such as N-chloro compounds, oxaziridines, polyoxometalates, etc., which have already been proven to be effective against sulphur mustard (HD). Thus, developed novel mesoporous reactive sorbents were tested for their self-decontaminating feature by conducting studies on kinetics of adsorptive removal of HD from solution. Trichloroisocyanuric acid impregnated silica nanoparticles (10%, w/w)-based system was found to be the best with least half-life value (t(1/2)=2.8 min) among prepared systems to remove and detoxify HD into nontoxic degradation products. Hydrolysis, dehydrohalogenation and oxidation reactions were found to be the route of degradation of HD over prepared sorbents. The study also inferred that 10% loading of impregnants over high surface area and low density silica nanoparticles enhances the rate of reaction kinetics and seems to be useful in the field of heterogeneous reaction kinetics.     

Development of chemically engineered porous metal oxides for phosphate removal

In this study, the application of ordered mesoporous silica (OMS) doped with various metal oxides (Zr, Ti, Fe and Al) were studied for the removal of (ortho) phosphate ions from water by adsorption. The materials were characterized by means of N₂ physisorption (BET), powder X-ray diffraction (PXRD) and transmission electron microscopy (TEM). The doped materials had surface areas between 600 and 700 m² g⁻¹ and exhibited pore sizes of 44–64 Å. Phosphate adsorption was determined by measurement of the aqueous concentration of orthophosphate using ultraviolet–visible (UV–vis) spectroscopy before and after extraction. The effects of different metal oxide loading ratios, initial concentration of phosphate solution, temperature and pH effects on the efficiency of phosphate removal were investigated. The doped mesoporous materials were effective adsorbents of orthophosphate and up to 100% removal was observed under appropriate conditions. ‘Back extracting’ the phosphate from the doped silica (following water treatment) was also investigated and shown to have little adverse effect on the adsorbent.     

Preparation of spherical zirconium salt particles by homogeneous precipitation

Spherical basic zirconium sulphate particles were prepared by homogeneous precipitation in mixed solutions of zirconium sulphate and urea. Values of [SO ₄ ^2– ]/[Zr⁴⁺] and [urea]/[Zr⁴⁺] in starting mixed solutions and cooling rate may affect the formation of spherical particles. Complexes such as [Zr(OH)_n]^4–n could prevent the formation and thus lead to gel precipitation. In addition, spherical particles could only be obtained in the presence of SO ₄ ^2– ; for NO^3– and Cl^–, only gel precipitation occurred.     

Synthesis, characterization and re-activation of a Fe0/Ti system for the reduction of aqueous Cr(VI)

The conventionally employed zero-valent iron (Fe0) particles suffer a formation of surface oxides to lower their activity prior to use. During their using process for contaminant remediation, such oxide formation is also encountered, while the cumbersome handling of particles impedes the Fe0 recovery. To conquer the drawbacks, a Fe0 film was synthesized by electrodepositing ferrous ion cathodically on titanium (Ti) substrate to form a new Fe0/Ti system. X-ray diffraction (XRD) revealed that the freshly electrodeposited (FED) Fe0 film was free of oxides, which was attributed to the particularity of electrodeposition procedure. Reduction results of 10.0 mg/L chromium [Cr(VI)] indicated that the FED Fe0 film had higher activity than the oxide-covered counterpart. Further analysis of the pH-dependent Cr(VI) reduction reaction indicated that the Fe0/Ti system kept its activity and could be reused for further Cr(VI) reduction at pH 3.0 and 4.0, while it was inactivated at pH 5.0 and 7.0. Due to the easy handling of Fe0/Ti system, the inactivated Fe0 was recovered significantly through a cathodic reduction.     

The sensitization of SrTiO3 photoanodes by doping with various transition metal ions

The influence that various dopants exert on the behaviour of single crystalline SrTiO₃ electrodes in a photoelectrochemical cell for water decomposition has been investigated. The electrodes were surface doped with Sr₃MeNb₂O₉ (Me₂₊ = Mn, Fe, Co, Ni) and LaMeO₃ (Me³⁺ = V, Cr, Mn, Fe, Co, Rh). The results have been compared with those for the sensitization of single crystalline SrTiO₃ photoanodes homogeneously doped with LaCrO₃ or the oxides of the transition metals Cr, Mn, Fe, Co, Ni, Nb, Mo, Ta and W. The response to visible light is greatest for Cr³⁺ and decreases in the sequence Co²⁺, Ni²⁺, Mn²⁺, Rh³⁺. The dopant ions V³⁺, Mn³⁺, Fe²⁺, Fe³⁺, Co³⁺ and the oxides of Nb, Mo, Ta and W reveal hardly any or no photosensitization. This is discussed in terms of a simple model proposed recently by members of our group.     

Photocatalytic activity of a new composite material of Fe (III) oxide nanoparticles wrapped by a matrix of polymeric carbon nitride and amorphous carbon

Polymeric carbon nitride was synthesized from urea and doped with Cu and Fe to act as co-catalysts. The material doped with Fe was a new composite material composed of Fe(III) oxides (acting as a co-catalyst) wrapped by the polymer layers and amorphous carbon. Furthermore, the copper doped material was described in a previous report. The photocatalytic degradation of the azo dye direct blue 1 (DB) was studied using as photocatalysts: pure carbon nitride (CN), carbon nitride doped with Cu (CN-Cu) and carbon nitride doped with Fe (CN-Fe). The catalysts were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), by X-ray photoelectron spectroscopy (XPS) and Brunauer–Emmett–Teller method (BET), etc. The adsorption phenomenon was studied using the Langmuir and Freundlich models. For the kinetic study, a solution of 500 mg L^?1 of DB1 was treated with each catalyst, visible light and H₂O₂. The dye concentration was measured by spectrophotometry at the wavelength of 565 nm, and the removal of the total organic content (TOC) was quantified. BET analysis yielded surface areas of 60.029, 20.116 and 70.662 m²g^?1 for CN, CN-Cu and CN-Fe, respectively. The kinetics of degradation were pseudo-first order, whose constants were 0.093, 0.039 and 0.110 min^?1 for CN, CN-Cu and CN-Fe, respectively. The total organic carbon (TOC) removal reached the highest value of 14.46% with CN-Fe.     

Corrosion behaviour and magnetic properties of melt-spun Nd-(Fe·Co·Ni)-B-(Al·Ti) ribbons

The corrosion behaviour of melt-spun Nd-Fe-B alloy ribbons in which Fe was replaced with Co and Ni and small quantities of Al and Ti added was investigated from the viewpoint of anodic corrosion, Although the addition of Ni degraded the magnetic properties of melt-spun ribbons, it improved corrosion resistance. According to EDXS and AES analyses, the corrosion products on the surface of Ni-free ribbons consisted of Nd and Fe oxides, but the Nd oxide corrosion product almost disappeared in the Ni-added samples. Also, the degradation of magnetic properties after the corrosion test was suppressed by the addition of Ni.From these results, it was thought that the improvement of corrosion resistance and the smaller degradation of magnetic properties of Nd-(Fe·Co·Ni)-B-(Al·Ti) ribbons after the corrosion test were associated with the suppressed dissolution of the Nd-rich phase at the grain boundaries.The oxidation of Ni-added melt-spun ribbons also showed similar characteristics and behaviour to the corrosion test in the morphologies of the ribbon surface and magnetic properties after the oxidation test.     

Effect of calcinations temperature of CuO nanoparticle on the kinetics of decontamination and decontamination products of sulphur mustard

Present study investigates the potential of CuO nanoparticles calcined at different temperature for the decontamination of persistent chemical warfare agent sulphur mustard (HD) at room temperature (30 ± 2 °C). Nanoparticles were synthesized by precipitation method and characterized by using SEM, EDAX, XRD, and Raman Spectroscopy. Synthesized nanoparticles were tested as destructive adsorbents for the degradation of HD. Reactions were monitored by GC-FID technique and the reaction products characterized by GC-MS. It was observed that the rate of degradation of HD decreases with the increase in calcination temperature and there is a change in the percentage of product of HD degradation. GC-MS data indicated that the elimination product increases with increase in calcination temperature whereas the hydrolysis product decreases.     

Synthesis and photocatalytic activity of cobalt oxide doped ZnFe2O4-Fe2O3-ZnO mixed oxides

Novel cobalt oxide doped ZnFe₂O₄-Fe₂O₃-ZnO mixed oxides with the Zn/Fe molar ratio of 1/2 were synthesized with a citric acid complex method. The effects of cobalt oxide and calcination temperature on phase composition and photocatalytic activity of the mixed oxides were investigated. X-ray diffraction (XRD) analysis revealed that there were mainly ZnFe₂O₄, α-Fe₂O₃, amorphous ZnO and Fe₂O₃ in the 6 mol% cobalt oxide doped products calcined at 500 °C. 5-10 mol% cobalt oxide doping could significantly enhance the formation of ZnFe₂O₄ and altered the phase composition of the mixed oxides. Experimental results showed that cobalt oxide doping could remarkably improve the photocatalytic activity of the mixed oxides for phenol degradation. The 6 mol% cobalt oxide doped mixed oxides calcined at 500 °C exhibited better photocatalytic activity as compared with other samples.     

Reactions of sulphur mustard on impregnated carbons

Activated carbon of surface area 1100 m2/gm is impregnated with 4% sodium hydroxide plus 3% Cr(VI) as CrO3 with and without 5% ethylene diamine (EDA), 4% magnesium nitrate and 5% ruthenium chloride by using their aqueous solutions. These carbons are characterized for surface area analysis by BET conventional method and exposed to the vapours of sulphur mustard (HD) at room temperature (30 degrees C). After 24 h, the reaction products are extracted in dichloromethane and analyzed using gas chromatography and mass spectrometry (GC-MS). Hemisulphur mustard, thiodiglycol, 1,4-oxathiane are observed to be the products of reaction between sulphur mustard and NaOH/CrO3/C system, whereas on NaOH/CrO3/EDA/C system HD reacted to give 1,4-thiazane. On Mg(NO3)2/C system it gave hemisulphur mustard and thiodiglycol. On RuCl3/C system it degraded to divinyl sulphone. Residual sulphur mustard is observed along with reaction products in all systems studied. Reaction mechanisms are also proposed for these interesting surface reactions. Above-mentioned carbons can be used in filtration systems for protection against hazardous gases such as sulphur mustard.     

Synthesis of titania-silica xerogels by co-solvent induced gelation at ambient temperature

A series of binary titania-silica mixed oxides was prepared by sol-gel synthesis at room temperature. The hydrolysis of titanium isopropoxide (Ti(ⁱOPr)₄) and tetraethylorthosilicate (TEOS) was facilitated by co-solvent induced gelation in acidic media. The resulting gels were dried, calcined, and then characterized by powder X-ray diffraction analysis, nitrogen sorption studies (at 77 K), diffuse reflectance spectroscopy, Raman microscopy, and transmission electron microscopy. The nitrogen sorption studies indicate that the porosities could be tuned when simple aromatic solvents such as toluene, p-xylene, or mesitylene were added as a co-solvent to the synthesis gel. The binary mixed metal oxide materials obtained in this study showed high activity towards the degradation of phenol, and possessed high surface areas, and large pore volumes with narrow pore size distribution without the need for additional hydrothermal synthesis or supercritical drying.     

Surface reaction and deoxidation mechanism of titanium powder deoxidized by calcium in atmospheric pressure argon

A new deoxidation in solid-state (DOSS) process was carried out in atmospheric-pressure argon to solve various difficulties associated with high-vacuum conditions, and the surface reaction and contact deoxidation mechanism were examined. The oxygen concentration of the Ti powder was decreased to 750 ppm at 800 °C by DOSS in atmospheric-pressure argon. Craters were formed on the surface of the deoxidized Ti powder, and the surface roughness increased. The craters were formed of Ca-Ti-O intermediate compounds during the reduction process and deoxidation. As the surface oxides of the Ti powder were reduced by deoxidation, the oxidation state decreased. When the deoxidation reaction reached equilibrium, the surface oxide was completely deoxidized, and the surface oxides were minimized upon re-passivation after pickling. As a result, the surface deoxidation reaction of the Ti powder was caused by the formation and decomposition of the Ca-Ti-O ternary compound on the surface.     

Development of self-assembled 3D Fe(x)Oy micro/nano materials for application in hexachlorobenzene degradation

Self-assembled three dimensional (3D) hierarchical, flower-like iron oxide micro/nano materials, including pure Fe3O4, alpha-Fe2O3/Fe3O4 composite and pure alpha-Fe2O3, were developed to degrade hexachlorobenzene (HCB) at 300 degrees C. It was found that pure Fe3O4 exhibited the highest activity with the reaction rate constant at 0.959 min(-1). Identified degradation products with lower chlorinated benzenes suggest a stepwise hydrodechlorination was occurring for the degradation of HCB on the synthesized Fe3O4. The characterization of the synthesized iron oxides after reaction indicates the Fe3O4 phase was partially transformed into alpha-Fe2O3 phase and in return accelerated progress of hydrodechlorination of HCB. The superior performance of as-prepared Fe3O4 could be attributed to its structural feature such as surface area and pore structure, as well as its phase transformation during HCB degradation.     

Oxide microstructure and deuterium ingress in Zr-2.5Nb CANDU® pressure tubes

Abstract

The microstructures of oxides grown on the inside surface (water-side) of Zr–2.5Nb pressure tubes removed from CANDU® reactors were characterised by TEM and correlated with deuterium ingress. Oxide cross-sections consisted of two structurally distinct regions: a columnar oxide region next to the metal/oxide interface, and an outer coarse equiaxed oxide region. Near the metal/oxide interface, the microstructure consisted of columnar grains without overt porosity. Away from the interface, the oxide consisted of coarsened equiaxed grains with (100)_m twins, grain-boundary cracks and nanopores. The oxide microstructures on various pressure tubes differ in the proportion of equiaxed grains. Electron micrographs suggest that a larger proportion of equiaxed grains is associated with higher deuterium uptake. The predominance of grain-boundary cracks in equiaxed oxides indicates that they are likely more permeable to water than columnar oxides.

Energy dispersive X-ray analyses revealed substantial amounts of Fe–K_α (and Mn–K_α) in the equiaxed oxide grains at the outermost surface. Energy Dispersive X-ray mapping of Fe–K_α and detection of the Mn-K_α (produced by neutron activation of ⁵⁴Fe and subsequent decay of ⁵⁵Fe) in the absence of external excitation, unequivocally demonstrated that the iron had accumulated in the oxide during reactor operation. The Fe concentration was highest near the outermost region, and decreased inwards towards the metal/oxide interface. These results are consistent with permeable equiaxed oxides picking up considerable amounts of Fe at the outermost region from the heavy water coolant.     

Photocatalytic activity of TiO2 doped with Zn2+ and V5+ transition metal ions: Influence of crystallite size and dopant electronic configuration on photocatalytic activity

Anatase TiO₂ was prepared by sol–gel method through the hydrolysis of titanium tetrachloride and doped with transition metal ions like V⁵⁺ and Zn²⁺. The photocatalysts were characterized by various analytical techniques. Powder X-ray diffraction studies revealed only anatase phase for the doped samples. The band gap absorption for the doped samples showed red shift to the visible region (～456 nm) as confirmed by UV–vis absorption spectroscopy and diffuse reflectance spectral studies. The surface area of the Zn²⁺ doped samples were higher than the V⁵⁺ doped samples as observed by BET surface area measurements due to their smaller crystallite size. Scanning electron microscopy showed almost similar morphology, while energy dispersive X-ray analysis confirmed the presence of dopant in the TiO₂ matrix. The photocatalytic activities of these catalysts were tested for the degradation of Congo Red under solar light. Although both the doped samples showed similar red shift in the band gap, Zn²⁺ (0.06 at.%) doped TiO₂ showed enhanced activity and its efficiency was five fold higher compared to Degussa P-25 TiO₂. This enhanced activity was attributed to smaller crystallite size and larger surface area. Further completely filled stable electronic configuration (d¹⁰) of Zn²⁺ shallowly traps the charge carriers and detraps the same to the surface adsorbed species thereby accelerating the interfacial charge transfer process.     

Charge transfer reactions on oxide-covered Ti Electrodes: Effect of dielectric constant variation and oxide stabilization

The electron transfer kinetics of the Fe³⁺/Fe²⁺ redox couple on the oxide covered Ti electrodes were investigated as a function of the film thickness, film stabilization, and concentration of the redox species. The oxides were formed potentiodynamically in acidic solution of pH=3 (Na₂SO₄+H₂SO₄) at a scan rate of 1 mV s⁻¹. The cathodic and anodic Tafel lines were also measured at the same scan rate. The logarithm of the exchange current density i₀ shows an exponential decrease with the oxide film thickness. Direct tunnelling may explain the kinetics of the reaction across thin Ti0₂ (oxide formed at the potential region before the O₂-evolution). Values of the cathodic and anodic transfer coefficients are tabulated. It was found that, the stabilization of the oxide could possibly increase its conductivity. The electron transfer reaction showed a first order dependence on the redox species concentration, independent of the conditions of oxide film formation.     

Bulk and surface structures of iron doped zirconium oxide systems: Influence of preparation method

Three different Fe-Zr oxide systems were prepared using firstly classical impregnation of iron nitrates on calcined ZrO₂ (Fe_x/ZrO₂, x represents Fe/Zr ratio = 0.01 and 0.11), secondly impregnation of iron nitrates on dried zirconium hydroxide ZrO(OH)₂ (Fe_x/ZrO(OH)₂) and finally hydrolysis of aqueous suspension of iron and zirconium salts to coprecipitate iron and zirconium hydroxides (Fe_x-Zr). Thermal decomposition study of dried samples evidenced a delay in the temperature crystallization of zirconia for Fe_x-Zr and Fe_x/ZrO(OH)₂, the more the iron content in the sample, the more important the delay. For these samples, the formation and the stabilization of different phases were evidenced by several characterization techniques : X-Ray Diffraction (XRD), Raman spectroscopy and Electron Paramagnetic Resonance (EPR).The interaction of iron species with zirconia was different in accordance with different preparations. A bulk dispersion of the coprecipitated sample was observed and as a consequence Zr^{3 +} defects in the solid were not produced. In the case of Fe_x/ZrO₂ sample, production of surface Zr^{3 +} ions was established at low temperature of calcination (up to 600^∘C) and explained by the reaction of NO₃⁻ with Zr^{4 +} on the zirconia surface. However such interaction did not occur for Fe_x/ZrO(OH)₂ since a low dispersion of iron species was observed by X-ray Photoelectron Spectroscopy (XPS), deposited phase (Fe₂O₃) forming preferentially blocks. Temperature Programmed Reduction (TPR) showed that the reduction of small particles of Fe₂O₃ and bulk Fe₂O₃ present in the impregnated samples was easier than that of iron species well dispersed in the bulk of the coprecipitated solid.