Determination of specific surface area of uranium oxide powders using differential thermal analysis technique

The two step oxidation of UO_2+x and reduction of U₃O₈ powders observed during Differential Thermal Analysis (DTA) has been exploited to determine their Specific Surface Areas (SSAs). The results obtained by this method have been compared with the Braunauer, Emmett and Teller (BET) method and are found to be in good agreement in the SSA range of 2–4 m²/gm in the case of UO_2+x obtained from ADU route and 4–8 m²/gm in the case of AUC route. A precision of ±0.1 m²/gm is obtained. The maximum temperature of oxidation and reduction of these oxides are dependent upon their preparative routes such as Ammonium Diuranate (ADU) and Ammonium Uranyl Carbonate (AUC).     

Thermoanalytical study on the oxidation of uranium dioxides derived from uranyl nitrate,uranyl acetate and ammonium diuranate

The oxidation of UO₂ was investigated by TG, DSC and X-ray diffraction . UO₂ samples were prepared by the reduction of UO₃ at P_H2 + P_N2 = 100 + 50 mm Hg and 5°C min^?1 up to 800°C. In order to obtain six UO₂ samples with different preparative histories, UNH, UAH and ADU were used as starting materials and their thermal decomposition was carried out at 450–625°C for 0–9 h at an air flow rate of 100 ml min^?1. α-UO₃, γ-UO₃, UO₃ - 2 H₂O, and their mixtures were obtained. The reduction of UO₃ gave β-UO_2+x with different x values from 0.030 to 0.055. The oxidation carried out at P_O2 = 150 mm Hg was found to consist of oxygen uptake at room temperature. UO₂ - U₃O₇ (Step I) and U₃O₇ → U₃O₈ (Step II). TG and DSC curves of the oxidation showed two plateaus and two exothermic peaks corresponding to Steps I and II. In the case of two of the samples, the DSC peak of Step II split into two substeps, which were assumed to be due to the different reactivities of U₃O- formed from α-CO₃ and that from other types of UO₃. The increase in O/U ratio due to the oxygen uptake at room temperature changed from 0.010 to 0.042 except for a sample prepared from ADU which showed an extraordinarily large value of 0.445. TG curves showed an increase in O/U from room temperature to near 250°C for Step I and the plateau at 250–350°C where O/U was about 2.42, and showed a sharp increase in O/U above 350°C for Step II and the plateau above 100°C where O/U was 2.72–2.75. It is thought that the prepared UO₂ had a defective structure with a large interstitial volume to accommodate the excess oxygen.     

Reduction of U<Subscript>3</Subscript>O<Subscript>8</Subscript> to U by a metallic reductant,Li

Reduction of U₃O₈ was investigated for the recycling of spent oxide fuel from a commercial nuclear power plant. The possible reduction methods were proposed and compared. Based on the thermodynamic analysis, Li metal was selected as a reductant. The optimum reaction temperature for the reduction of U₃O₈ was investigated at the wider reaction temperature range. The adverse oxidation of U metal by Li₂O at 1,000 °C was experimentally verified. Ellingham diagram was constructed to investigate the extent of the uranium oxides reduction when the reaction was carried out above melting point of U metal.     

Study of Fe-doped V<Subscript>2</Subscript>O<Subscript>5</Subscript>/TiO<Subscript>2</Subscript> catalyst for an enhanced NH<Subscript>3</Subscript>-SCR in diesel exhaust aftertreatment

Selective catalytic reduction (SCR) with ammonia has been considered as the most promising technology, as its effect deals with the NO_X. Novel Fe-doped V₂O₅/TiO₂ catalysts were prepared by sol–gel and impregnation methods. The effects of iron content and reaction temperature on the catalyst SCR reaction activity were explored by a test device, the results of which revealed that catalysts could exhibit the best catalytic activity when the iron mass ratio was 0.05%. It further proved that the VTiFe (0.05%) catalyst performed the best in denitration and its NO_X conversion reached 99.5% at 270 °C. The outcome of experimental procedures: Brunauer–Emmett–Teller surface area, X-ray powder diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction and adsorption (H₂-TPR, NH₃-TPD) techniques showed that the iron existed in the form of Fe³⁺ and Fe²⁺ and the superior catalytic performance was attributed to the highly dispersed active species, lots of surface acid sites and absorbed oxygen. The modified Fe-doped catalysts do not only have terrific SCR activities, but also a rather broad range of active temperature which also enhances the resistance to SO₂ and H₂O.     

Photo-fenton refreshable Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@HCS adsorbent for the elimination of tetracycline hydrochloride

A yolk–shell-structured sphere composed of a superparamagnetic Fe₃O₄ core and a carbon shell (Fe₃O₄@HCS) was etched from Fe₃O₄@SiO₂@carbon by NaOH, which was synthesized through the layer-by-layer coating of Fe₃O₄. This yolk–shell composite has a shell thickness of ca. 27 nm and a high specific surface area of 213.2 m² g^?1. Its performance for the magnetic removal of tetracycline hydrochloride from water was systematically examined. A high equilibrium adsorption capacity of ca. 49.0 mg g^?1 was determined. Moreover, the adsorbent can be regenerated within 10 min through a photo-Fenton reaction. A stable adsorption capacity of 44.3 mg g^?1 with a fluctuation <10% is preserved after 5 consecutive adsorption–degradation cycles, demonstrating its promising application potential in the decontamination of sewage water polluted by antibiotics.     

Thermodynamic investigations of BaUF<Subscript>6</Subscript>(s)

The calcium fluoride solid electrolyte Galvanic cell: (-) Pt, U₃O₈(s) + UO₂F₂(s) + BaUF₆(s) + BaF₂(s) | CaF₂(s) | NiO(s) + NiF₂(s), Pt (+) was used to measure the standard molar Gibbs energy of formation of BaUF₆(s). From the measured emf values of the cell and required Gibbs energy values from the literature, Δ_f G _m° (T) of BaUF₆(s) has been calculated. The pseudo-binary phase diagram of BaF₂–UF₄ system was calculated by minimization of Gibbs energies of the phases present in the system. The stability domain of BaUF₆(s) has been calculated from the chemical potential diagram of Ba–U–F–O system at 800 K.     

Steam pre-reforming of natural gas over nanostructured Ni/12CaO–7Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst for hydrogen production: effect of support preparation method

Calcium aluminate (12CaO–7Al₂O₃) powder was synthesized using three methods, viz. Pechini, coprecipitation, and a new novel facile decomposition route starting from activated alumina and calcium nitrate precursors, then used as a support to prepare a series of 31 wt%Ni/12CaO–7Al₂O₃ catalysts by deposition–precipitation method. The resultant catalysts were tested in steam pre-reforming of natural gas at 400–550 °C, low steam-to-carbon (S/C) molar ratio of 1.5, and atmospheric pressure. The obtained samples were characterized by Brunauer–Emmett–Teller (BET) analysis, scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis, temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), hydrogen chemisorption, and CO₂–temperature-programmed desorption (TPD). Experimental results showed that the basicity and morphology of the supports depended significantly on the synthesis method. Calcium aluminate synthesized using the new decomposition procedure showed surface area of 6.23 m² g^?1, while the surface area of those prepared by the Pechini and coprecipitation method were 1.38 and 3.76 m² g^?1, respectively. The catalytic properties of the 31 wt%Ni/12CaO–7Al₂O₃ catalysts were strongly influenced by the support preparation approach. The highest specific surface area (about 230 m² g^?1), smallest Ni particle size (8.86 nm), and highest nickel dispersion (7.48%) were observed for the catalyst whose support was synthesized by the decomposition method. Even at high gas hourly space velocity (GHSV) of 2 × 10⁵ mL \({\text{g}}^{ - 1}_{\text{catalyst}}\) h^?1, this catalyst exhibited around 100% C₂H₆ and C₃H₈ conversion at temperature above 500 °C. High catalytic stability during 60 h time on-stream was also shown. The TPO profiles of the spent catalyst demonstrated high resistance to carbon formation.     

Preparation and characterization of H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript>/ZrO<Subscript>2</Subscript> catalyst for carbonation of methanol into dimethyl carbonate

A H₃PW₁₂O₄₀/ZrO₂ catalyst for effective dimethyl carbonate (DMC) formation via methanol carbonation was prepared using the sol–gel method. X-ray photoelectron spectra showed that reactive and dominant (63%) W(VI) species, in WO₃ or H₂WO₄, enhanced the catalytic performances of the supported ZrO₂. The mesoporous structure of H₃PW₁₂O₄₀/ZrO₂ was identified by nitrogen adsorption–desorption isotherms. In particular, partial sintering of catalyst particles in the duration of methanol carbonation caused a decrease in the Brunauer–Emmett–Teller surface area of the catalyst from 39 to 19 m²/g. The strong acidity of H₃PW₁₂O₄₀/ZrO₂ was confirmed by the desorption peak observed at 415 °C in NH₃ temperature-programmed desorption curve. At various reaction temperatures (T?=?110, 170, and 220 °C) and CO₂/N₂ volumetric flow rate ratios (CO₂/N₂?=?1/4, 1/7, and 1/9), the calculated catalytic performances showed that the optimal methanol conversion, DMC selectivity, and DMC yield were 4.45, 89.93, and 4.00%, respectively, when T?=?170 °C and CO₂/N₂?=?1/7. Furthermore, linear regression of the pseudo-first-order model and Arrhenius equation deduced the optimal rate constant (4.24?×?10^?3 min^?1) and activation energy (E_a?=?15.54 kJ/mol) at 170 °C with CO₂/N₂?=?1/7 which were favorable for DMC formation.     

Promotional effect of cobalt addition on catalytic performance of Ce<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>O<Subscript>2</Subscript> mixed oxide for diesel soot combustion

A series of Co-modified Ce_0.5Zr_0.5O₂ catalysts with different concentrations of Co (mass %: 0, 2, 4, 6, 8, 10) was investigated for diesel soot combustion. Ce_0.5Zr_0.5O₂ was prepared using the coprecipitation method and Co was loaded onto the oxide using the incipient wetness impregnation method. The activities of the catalysts were evaluated by thermogravimetric (TG) analysis and temperature-programmed oxidation (TPO) experiments. The results showed the soot combustion activities of the catalysts to be effectively improved by the addition of Co, 6 % Co/Ce_0.5Zr_0.5O₂ and that the 8 % Co/Ce_0.5Zr_0.5O₂ catalysts exhibited the best catalytic performance in terms of lower soot ignition temperature (T_i at 349°C) and maximal soot oxidation rate temperature (T_m at 358°C). The reasons for the improved activity were investigated by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), H₂ temperature-programmed reduction (H₂-TPR), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). These results revealed that the presence of Co could lower the reduction temperature due to the synergistic effect between Co and Ce, thereby improving the activity of the catalysts in soot combustion. The 6 % Co catalyst exhibited the best catalytic performance, which could be attributed to the greater amounts of Co³⁺ and surface oxygen species on the catalyst.     

UO2, NpO2 and PuO2 preparation in aqueous nitrate solutions in the presence of hydrazine hydrate

It was established that heating to 90 °C of nitrate solutions of U, Np and Pu in the presence of hydrazine hydrate results in the formation of hydrated dioxides of these elements. On ignition under inert or reducing conditions in the temperature range of 280–800 °C hydrated uranium dioxide transmogrify into crystalline UO₂. On ignition in air atmosphere UO₂·nH₂O turns into UO₃ at 440 °C and into U₃O₈ at 570–800 °C. It was shown that thermolysis of the solution containing a mixture of uranium, neptunium and plutonium nitrates at 90 °C in the presence of hydrazine hydrate allows one to prepare hydrated dioxides (U, Np, Pu)O₂·nH₂O which on heating to ~300 °C transmogrify into crystalline product of UO₂, NpO₂ and PuO₂ solid solution. The technique of preparation of solid solutions of U and Pu dioxides is very promising as simple and effective method of production of MOX-fuel for.     

Synthesis of high surface area transitional alumina from Al(OPh)<Subscript>3</Subscript>

Al(OPh)₃ involving sterically hindered phenyl groups on ultrasonic assisted micro hydrolysis yielded a mixture of boehmite and bayerite as deduced from the FTIR and powder X-ray diffraction pattern. In the thermogravimetric trace, the complete removal of decomposable moieties of the hydrolyzed gel occurred around 530 °C. Calcining the gel at temperatures 600, 700, 800 and 900 °C showed crystalline tetragonal δ-Al₂O₃ to be the product at 900 °C as deduced from FTIR, ²⁷Al NMR and PXRD techniques. δ-Al₂O₃ showed a surface area of 135 m²/g with rectangular bar like morphology with the sizes below 50 nm in the TEM images.     

Nano particles of iron oxides in SiO<Subscript>2</Subscript> glass prepared by ion implantation

Quartz (SiO₂) glass was implanted with 5 × 10^{16 57}Fe ions/cm² at a substrate temperature of 500 °C, and annealed at temperatures between 700 and 950 °C. The implanted and annealed plates were characterized by conversion electron Mössbauer spectroscopy (CEMS), and measured by a Kerr effect magnetometer or a vibration sample magnetometer. Kerr effect measurement of as-implanted SiO₂ glass showed ferromagnetism at room temperature. CEM spectrum of the as-implanted glass consisted of magnetic relaxation peaks of finely dispersed metallic Fe species, and paramagnetic doublets of Fe³⁺ and Fe²⁺ species. The sample heated at 700 °C contained large grains of metallic Fe and a lot of oxidation products of Fe²⁺ species. After oxidation at temperatures higher than 800 °C, the samples showed also ferromagnetism, which was attributed mainly to ferromagnetic ε-Fe₂O₃ precipitated in SiO₂ matrix. Small amounts of α-Fe₂O₃ were produced at 950 °C. The results suggest that ion implantation and oxidation make a transparent ferromagnetic glass possible.     

Studies on the synthesis of higher alcohol over modified Cu/ZnO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst

Higher alcohol has been considered as a potential fuel additive. Higher alcohol, including C₂–C₄ alcohol was synthesized by catalytic conversion of syngas (with a ratio of CO/H₂?=?1) derived from natural gas over modified Cu/ZnO/Al₂O₃ catalyst. Modified Cu/ZnO/Al₂O₃ catalysts promoted by alkali metal (Li) for higher alcohol synthesis (HAS) were prepared at different pH (6, 6.5, 7, 8, and 9) by co-precipitation to control Cu surface area and characterized by N₂ physisorption, XRD, SEM, H₂-TPR and TPD. The HAS reaction was carried out under a pressure of 45 bar, GHSV of 4000 h^?1, ratio of H₂/CO?=?1, and temperature ranges of 240 and 280 °C. It was found that the malachite phase of copper causes the size of copper to be small, which is suitable for methanol synthesis. Methanol and HAS share a common catalytic active site and intermediate. It was also found that the productivity to higher alcohol was correlated with Cu surface area.     

Synthesis of Na<Subscript>2</Subscript>Ti<Subscript>3</Subscript>O<Subscript>7</Subscript> nanoparticles by sonochemical method for solid state electrolyte applications

Na₂Ti₃O₇ ceramic materials have been widely used in sodium-ion battery applications with relative good results; however, there are still several studies that might be carried out in the improvement of the Na₂Ti₃O₇ properties and the overall batteries’ performance. In this direction, we used sonochemical method following a thermal treatment in order to synthetized pure phase Na₂Ti₃O₇ nanopowders. X-ray diffraction characterization revealed that Na₂Ti₃O₇ is the primary phase in nanopowders and ceramic sample; although, a high level of amorphization was observed in the sonicated nanopowder without heat treatment process. Nanopowder-prepared ceramic sample showed a crystallite size of 50 nm after sintering at 900 °C for 1 h. The specific surface area, pore volume, and pore size were obtained from the B.E.T. measurements, being 51 m² g^?1, 0.07 cm³ g^?1, and 55 Å, respectively. The capacitance values of the nanopowder-prepared ceramic sample were in the order of microfarad. The total energy of the system was used to determine relaxation time of the sample (τ ₀ = 31 ms).     

The effects of the nanostructure of mesoporous TiO<Subscript>2</Subscript> on optical band gap energy

Mesoporous TiO₂ is prepared by sol–gel process with a triblock copolymer as an organic template and aqueous TiOCl₂ solution as inorganic precursor. The XRD patterns reveal that only the anatase phase can be observed in mesoporous TiO₂, regardless of the different calcining temperatures, and with increasing calcining temperature the grain size gradually increases. The grain sizes of TiO₂ increased from 4.7 to 11.9 nm with calcining temperature increasing from 300 to 400 °C. The pore size and the surface area evaluated from the Barrett–Joyner–Halenda model and Brunauer–Emmett–Teller method indicated that the average pore sizes increased from 87 to 153 Å and specific surface areas decreased from 179.71 to 74.31 m²/g for 300–400 °C calcination. The relationship between the optical band gap (E _g) and microstructure of anatase has been determined and discussed. The quantum confinement effect is observed at grain sizes lower than 10 nm, and the estimated E _g shifts from 3.32 to 3.46 eV. These results suggest that there are potential applications of mesostructured TiO₂ with nanocrystals in the design of optical devices and photocatalysts.     

Preparation and characterization of high specific surface area Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> from electrolytic manganese residue

Mn₃O₄ powders have been produced from Electrolytic Manganese Residue (EMR). After leaching of EMR in sulfuric acid, MnSO₄ solution containing various ions was obtained. Purifying the solution obtained and then adding aqueous alkali to the purified MnSO₄ solution, Mn(OH)₂ was prepared. Two methods were employed to produce Mn₃O₄. One way was oxidation of Mn(OH)₂ in aqueous phase under atmosphere pressure to obtain Mn₃O₄. The other way was roasting Mn(OH)₂ precursors in the range of 500°C to 700°C. The prepared samples were investigated by using several techniques including X-ray powder diffraction (XRD), Fourier Transformation Infra-Red (FTIR) spectra, and Brunauer-Emmett-Teller (BET) specific surface area instrument. Particle distribution and magnetic measurements were carried out on laser particle size analyzer, vibrating sample magnetometer (VSM). Through XRD, FTIR and determination of total Mn content (TMC), the products prepared were confirmed to be a single phase Mn₃O₄. BET specific surface areas can reach to 32 m² g⁻¹. The results indicated that products synthesized by aqueous solution oxidation method had higher specific surface areas and smaller particle size than those prepared by means of roasting. However the products prepared using the above two methods showed no obvious differences in magnetic property.      

Facile synthesis of Fe@Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> core-shell nanowires as O<Subscript>2</Subscript> electrode for high-energy Li-O<Subscript>2</Subscript> batteries

Fe@Fe₂O₃ core-shell nanowires were synthesized via the reduction of Fe³⁺ ions by sodium borohydride in an aqueous solution with a subsequent heat treatment to form Fe₂O₃ shell and employed as a cathode catalyst for non aqueous Li-air batteries. The synthesized core-shell nanowires with an average diameter of 50–100 nm manifest superior catalytic activity for oxygen evolution reaction (OER) in Li-O₂ batteries with the charge voltage plateau reduced to ～3.8 V. An outstanding performance of cycling stability was also achieved with a cutoff specific capacity of 1000 milliampere hour per gram over 40 cycles at a current density of 100 mA g^?1. The excellent electrochemical properties of Fe@Fe₂O₃ as an O₂ electrode are ascribed to the high surface area of the nanowires’ structure and high electron conductivity. This study indicates that the resulting iron-containing nanostructures are promising catalyst in Li-O₂ batteries.     

Synthesis and thermal decomposition of neodymium(III) peroxotitanate to Nd<Subscript>2</Subscript>TiO<Subscript>5</Subscript>

Neodymium(III) peroxotitanate is used as a precursor for obtaining Nd₂TiO₅. The last one possesses numerous valuable electrophysical properties. TiCl₄, Nd(NO₃)₃·6H₂O and H₂O₂ in mol ratio 1:2:10 were used as starting materials. The reaction ambience was alkalized to pH = 9 with a solution of NH₃. The obtained neodymium(III) peroxotitanate and intermediate compounds of the isothermal heating were proved by the help of quantitative analysis and infrared spectroscopy (IRS). It has Nd₄[Ti₂(O₂)₄(OH)₁₂]·7H₂O composition. The absorption band observed in IRS at 831 cm^?1 relates to a triangular bonding of the peroxo group of Ti, at 1062 cm^?1—terminal groups Ti–OH and at 1491 and 1384 cm^?1—the bridging OH^?-groups Ti–O(H)–Ti. Nd₂TiO₅ was obtained by thermal decomposition of neodymium(III) peroxotitanate. The isothermal conditions for decomposition were determined on the base of differential thermal analysis, thermogravimetric and differential scanning calorimetry results in the temperature range of 20–1000 °C. The mechanism of thermal decomposition of Nd₄[Ti₂(O₂)₄(OH)₁₂]·7H₂O to Nd₂TiO₅ was studied. In the temperature range of 20–208 °C, a simultaneous decomposition of the peroxo groups by the separation of oxygen and hydrate water is conducted and Nd₄[Ti₂O₄(OH)₁₂] is obtained. From 208 to 390 °C, the terminal OH^?-groups are separated and Nd₄[Ti₂O₇(OH)₆] is formed. In the range of 390–824 °C, the bridging OH^?-groups are completely decomposed to Nd₂TiO₅. The optimal conditions for obtaining nanocrystalline Nd₂TiO₅ are 900 °C for 6 h and 20–80 nm.     

Synthesis and characterization of La<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>Co<Subscript>0.5</Subscript>Fe<Subscript>0.5</Subscript>O<Subscript>3±δ</Subscript> nanopowders by microwave assisted sol–gel route

Nano-crystalline La_0.8Sr_0.2Co_0.5Fe_0.5O_3±δ powder has been successfully synthesized by microwave assisted sol–gel (MWSG) method. The decomposition and crystallization behavior of the gel-precursor was studied by Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) analysis. From the result of FT-IR and X-ray diffraction patterns, it is found that a perovskite La_0.8Sr_0.2Co_0.5Fe_0.5O_3±δ was formed by irradiating the precursor at 700 W for 3 min, but the well-crystalline perovskite La_0.8Sr_0.2Co_0.5Fe_0.5O_3±δ was obtained at 700 W for 35 min. Morphological and specific area analysis of the powder were done by transmission electron microscopy (TEM), scanning electron microscope (SEM) and Brunauer–Emmett–Teller (BET). The surface areas measured was 38.9 m²/g and the grain size was ∼23 nm. Electrochemical properties of pure LSCF cathode on YSZ electrolyte at intermediate temperatures were investigated by using AC impedance analyzer, which shows a low area specific resistance (0.077 Ω cm² at 1073 K and 0.672 Ω cm² at 953 K). Moreover, the synthesis period of 20 h usually observed for conventional heating mode is reduced to a few minutes. Thus, the MWSG method is proved to be a novel, extremely facile, time-saving and energy-efficient route to synthesize LSCF powders.     

The properties of nickel aluminate nanoparticles prepared by sol–gel and impregnation methods

Nickel aluminates were prepared by sol–gel and impregnation methods and calcined at 1100 °C. The sol–gel made samples were prepared with different amounts of nickel (Ni/Al molar ratio equal to 0, 0.25, 0.5, and 0.75) and aging times (24 and 48 h). The samples were characterized by X-ray diffraction, induced couple plasma, nitrogen physisorption, transmission and scanning electron microscopy, and ammonia temperature programmed desorption (NH₃-TPD). In the sol–gel made samples, only the NiAl₂O₄ structure of nickel aluminate was defined, while for impregnation, NiAl₁₀O₁₆ was formed as well. The sol–gel made samples had low specific surface areas (7.7–12.4 m²/g), but a sample prepared by impregnation method had higher specific surface area (67.2 m²/g). The surface acidity density decreased by increasing the amount of nickel and was the lowest for impregnation method.