Physicochemical characteristic of neodymium oxide-based catalyst for in-situ CO2/H2 methanation reaction

Carbon dioxide emission to the atmosphere is worsened as all the industries emit greenhouse gases (GHGs) to the atmosphere, particularly from refinery industries. The catalytic chemical conversion through methanation reaction is the most promising technology to convert this harmful CO₂ gas to wealth CH₄ gas for the combustion. Thus, supported neodymium oxide based catalyst doped with manganese and ruthenium was prepared via wet impregnation route. The screening was initiated with a series of Nd/Al₂O₃ catalysts calcined at 400?°C followed by optimization with respect to calcination temperatures, based ratios loading and various Ru loading. The Ru/Mn/Nd (5:20:75)/Al₂O₃ calcined at 1000?°C was the potential catalyst, attaining a complete CO₂ conversion and forming 40% of CH₄ at 400?°C reaction temperature. XRD results revealed an amorphous phase with the occurrence of active species of RuO₂, MnO_2, and Nd₂O₃, and the mass ratio of Mn was the highest among other active species as confirmed by EDX. The ESR resulted in the paramagnetic of Nd³⁺ at the g value of 2.348. Meanwhile nitrogen adsorption (NA) analysis showed the Type IV isotherm which exhibited the mesoporous structure with H3 hysteresis of slit shape pores.     

Luminescent Study on Nd3+ Complexes Containing Carboxylate‐Dithiolene and Alkoxide‐Dithiolene Ligands

Reaction of ligand L H₂ (4,5‐bis[carboxymethylthio]‐1,3‐dithiol‐2‐thione) with neodymium silyl‐amide (Nd[N(TMS)₂]₃; TMS= ‐SiMe₃), in a ratio 2:1, yields a neodymium‐dithiolene‐carboxylato complex ( 1 ) (Nd( L H) L ). Similarly, reaction of 2 equivalents of L′ H₂ (4,5‐bis[2′‐hydroxyethyl)thio]‐1,3‐dithiol‐2‐thione) and one equivalent of neodymium silyl‐amide (Nd[N(TMS)₂]₃) allowed the isolation of complex 2 , with a ligand:metal ratio of 3:2. ATR‐IR spectrum of 1 displays a broad band characteristic of an OH group showing that one carboxylate group remains protonated. Emission spectrum of complex 1 under excitation in the visible region (at 360 nm i.e. on the ligand) displayed typical emission bands of the Nd³⁺, showing that energy transfer from the ligand to the lanthanide was achieved (i.e. “antenna effect”). No significant quenching from the remaining –OH group was detected. In the case of complex 2 , the main emission bands characteristic of the Nd³⁺ ion have been observed, by excitation at 495 nm.     

Anhydrous Neodymium(III) Acetate

Anhydrous neodymium(III) acetate, Nd(OAc)₃ was obtained as light purple single crystals by direct oxidation of neodymium metal with malonic acid in a glass ampoule at 180 °C. It crystallizes with the monoclinic space group P2₁/a (no. 14) with a = 2201.7(2), b = 1850.0(1), c = 2419.0(3) pm, β = 96.127(8)°, V = 9796.8(1)·10⁶·pm³, Z = 40 [Nd(OAc)₃], R₁ = 0.0430 [I₀ > 2σ(I₀)]. Most of the Nd³⁺ cations are coordinated by nine (or eight) oxygen atoms of acetate ligands which bridge these polyhedra to slightly waved layers which are stacked in the [010] direction.     

Effects of temperature and Nd composition on non-linear transport properties in substituted Ce1−xNdxO2−δ cerium dioxides

Cerium dioxides doped or substituted by neodymium have been prepared using low- (320°C) and high-temperature (1600°C) processes. The Nd substituted ceria phase obtained at high temperature is a solid solution Ce_1−xNd_xO_2−δ 0?x?0.30. Electrical impedance spectroscopy analyses have been performed in the temperature range 40-700°C. At temperatures above 400°C, Nyquist representations allow to separate three signals corresponding to bulk, grain boundary and electrode responses. Non-linear variations of the resistance and the capacitance as functions of temperature and composition x are observed. In the case of grain boundary and electrode interface signals, constant phase elements with non-integer exponent n have been used to represent the equivalent circuits. For each contribution, the conductance strongly increases then reaches a limit value, above x=0.10. When composition x increases, the condensation of Nd-vacancy defect clusters might be at the origin of the non-linear evolution of the conductance. Bulk and grain boundary conductions present different activation energies (0.7 and 1.3 eV).     

Energetics of copper diphosphates – Cu2P2O7 and Cu3(P2O6OH)2

Differential scanning calorimetry and high temperature oxide melt solution calorimetry are used to study enthalpy of phase transition and enthalpies of formation of Cu₂P₂O₇ and Cu₃(P₂O₆OH)₂. α-Cu₂P₂O₇ is reversibly transformed to β-Cu₂P₂O₇ at 338–363 K with an enthalpy of phase transition of 0.15 ± 0.03 kJ mol⁻¹. Enthalpies of formation from oxides of α-Cu₂P₂O₇ and Cu₃(P₂O₆OH)₂ are −279.0 ± 1.4 kJ mol⁻¹ and −538.8 ± 2.7 kJ mol⁻¹, and their standard enthalpies of formation (enthalpy of formation from elements) are −2096.1 ± 4.3 kJ mol⁻¹ and −4302.7 ± 6.7 kJ mol⁻¹, respectively. The presence of hydrogen in diphosphate groups changes the geometry of Cu(II) and decreases acid–base interaction between oxide components in Cu₃(P₂O₆OH)₂, thus decreasing its thermodynamic stability.     

Synthesis and Structure of a Neodymium Complex with the Nitrilotriacetate Ligand: [NdIII(nta)]n

A neodymium complex, [Nd(nta)]_n ( 1 ) (H₃nta = nitrilotriacetic acid) was synthesized and characterized by X-ray diffraction analysis. Compound 1 exhibits a three-dimensional network, in which the Nd^III ion is coordinated by one nitrogen atom and seven carboxyl oxygen atoms with dodecahedral coordination. One striking feature is that in the Nd coordination center there is no water ligand found.     

Optimization and modeling of synthesis parameters of neodymium(III) bromide by dry method using full factorial design analysis

The synthesis of neodymium(III) bromide (NdBr₃) by sintering brominating of neodymium oxide (Nd₂O₃) with ammonium bromide (NH₄Br) was investigated. The influence of various synthesis parameters (temperature, contact time and stoichiometry) on the reaction yield was studied and optimized. The main interaction effects of the synthesis parameters on the reaction yield were also determined by a full 2³ factorial designs with six replicates at the center point.This study showed that the optimum conditions for the synthesis of NdBr₃ are following: contact time t = 60 min, stoichiometry in moles Nd₂O₃:NH₄Br = 1:24 and temperature T = 400 °C. The reaction yield for these parameters was equal to 97.80%. The first order model was obtained to predict the reaction yield as a function of these three parameters. It was shown that all parameters have a significant positive influence on reaction yield. In addition it was pointed out also that the interaction effects between them are significant.     

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.     

Isomorphic substitution of neodymium and gadolinium for calcium in synthetic hydroxovanadate

Isomorphic substitution of neodymium and gadolinium for calcium in synthetic hydroxovanadate Ca_{5 ? x} M _x (VO₄)₃(OH)_{1 ? x} O _x (M = Nd, Gd) is studied in the range 700–1000°C using X-ray powder diffraction, single-crystal X-ray diffraction (Rietveld technique), and IR spectroscopy. Single-phase solid solutions at 800°C are formed with x ≤ 0.35 for M(III) = Nd and x ≤ 0.3 for M(III) = Gd. With high x, the apatite solid solution coexists with Ca₃(VO₄)₂, Nd₂O₃, and X phases. With increasing x in the homogeneous region, the intensity of the bands of stretching vibrations and librations of OH groups decrease. Single-crystal X-ray diffraction shows that neodymium and gadolinium substitute for calcium in solid solutions mostly in Ca(2) positions.     

Preparation and characterization of the catalytically active forms of rare earth oxides

Catalytically active forms of the rare earth oxides Ln₂O₃(Ln = La, Sm, Eu, Dy, Ho, and Yb), Pr₆O₁₁, and CeO₂ have been prepared. The dehydration behavior of the precursors of these oxides has been studied by XRD, TG, DTA, TPD-MS, IR, and adsorption-desorption isotherms of N₂ at −196°C. Thermal analyses show that in most cases the dehydration takes place through an intermediate oxyhydroxide LnO (OH) that decomposes to the respective oxide at around 400°C. Strongly held difficult to remove carbonates were present on the surface, e.g., for Yb₂O₃ it was necessary raise the outgassing temperature to 700°C to achieve carbonate decomposition. At temperatures around 500°C these oxides are well crystallized and have moderate specific surface areas (10–40 m²g⁻¹). As a representative of the series, a detailed study of the dehydration and surface decarbonation of Yb₂O₃ was carried out by means of TPD-MS and infrared spectroscopy.     

Preparation and characterization of spherical V2O3 nanopowder

V₂O₃ nanopowder with spherical particles was prepared by reducing pyrolysis of the precursor, (NH₄)₅[(VO)₆(CO₃)₄(OH)₉]·10H₂O, in H₂ atmosphere. The thermolysis process of the precursor in a H₂ flow was investigated by thermogravimetric analysis and differential thermal analysis. The results indicate that pure V₂O₃ forms at 620°C and crystallizes at 730°C. The effects of various reductive pyrolysis conditions on compositions of V₂O₃ products were studied. Scanning electron micrographs show that the particles of the V₂O₃ powder obtained at 650°C for 1 h are spherical about 30 nm in size with more homogeneous distribution. Experiments show that nanopowder has larger adsorption capacity to gases and is more easily reoxidized by air at room temperature than micropowder. Differential scanning calorimetry experiment indicates that the temperature of phase transition of nano-V₂O₃ powder is −119.5°C on cooling or −99.2°C on heating. The transition heats are −12.55 J g⁻¹ on cooling and 11.42 J g⁻¹ on heating, respectively.     

立方Nd2O3上过氧物种光诱导生成的18O同位素示踪考察

采用原位显微Raman光谱和¹⁸O同位素示踪技术,以325 nm激光为激发光源,对立方Nd₂O₃上过氧物种的光诱导生成过程进行了详细表征,进一步证实过氧源于分子氧对晶格氧的氧化反应. 结果还表明,325 nm激光在室温下即可诱导过氧的生成,在实验条件下,生成的过氧物种可与Nd₂O₃的晶格氧发生快速的氧交换反应,位于Nd₂O₃体相的晶格氧也可迁移至样品表层进而参与过氧的生成. 325 nm激光照射有助于促进晶格氧的迁移以及晶格氧与分子氧之间的氧交换反应.     

(Ba<Subscript>0.93</Subscript>Nd<Subscript>0.07</Subscript>)TiO<Subscript>3</Subscript> thin films prepared by sol–gel method as a potential dielectric resonator antenna application

In this paper, we report the application of Neodymium (Nd) doped barium titanate thin films (Ba_1-xNd_x) TiO₃ with x = 0 and 0.07 as dielectric resonator antenna. The films were prepared using the sol–gel method and dip-coating technique. Barium acetate, titanium (IV) isopropoxide and neodymium (III) acetate hydrate were used as precursors while glacial acetic acid and acetylacetone were used as solvents. Si wafers were used as a substrate with dipping times varying from 10, 30, and 50 s. The 0.07 films were >800 nm thick and crystallized after being annealed at 800°C for 30 min. The films were tested as dielectric resonator antenna. It was found that, on the actual antenna circuit, the resonant frequency decreased as the (Ba_0.93Nd_0.07) TiO₃ films thickness increased (from 0.8379, to 5.4525 μm). All samples resonate in the range of 8.68–8.83 GHz with quasi omni-directional radiation patterns.     

NdHO, a novel oxyhydride

A new metal oxyhydride; neodymium oxyhydride, NdHO, has been synthesized from a reactant mixture of metal hydride (CaH₂ or NdH₃) and neodymium oxide (Nd₂O₃). The unit cell dimensions decrease smoothly in the series from LaHO, CeHO, PrHO to NdHO, in line with the lanthanide contraction. The crystal structure of NdHO is described on the basis of Rietveld refinement on neutron powder diffraction data:

Space group: P4/nmm (no. 129, D_4h⁷).

Axis lengths: a=7.8480(5) Å, c=5.5601(8) Å.

Volume: V=342.46(6) Å³.

The tetragonal structure is derived from the fluorite structure, showing complete ordering of hydride and oxide ions over the anion sublatttice. The formation of NdHO was further substantiated by Raman spectroscopy.     

Nitrato- and fluoroboracites M3B7O13NO3 and M3B7O13F

New boracites containing nitrato- or fluoroanions that appear to be true low-pressure phases have been synthesized at superatmospheric pressures. The M₃B₇O₁₃NO₃ compounds (M = Co, Ni, Cu, Zn, Cd) transform rapidly and reversibly in the temperature region 300–500°C between probable orthorhombic and face centered cubic symmetry, while the M₃B₇O₁₃F compounds (M = Mg, Mn, Fe, Co, Zn) appear to maintain rhombohedral symmetry up to their decomposition temperatures of 800–900°C. True high-pressure boracite-like phases containing F and Cr, Mn, Fe, or Co that decompose upon heating to M₃B₇O₁₃F have also been isolated.     

Low temperature sintering and color of a new compound Sn1.24Ti1.94O3.66(OH)1.50F1.42

Nanopowder of a new tin(II) titanium(IV) oxide hydroxide fluoride, Sn_1.24Ti_1.94O_3.66(OH)_1.50F_1.42 with the pyrochlore-type structure (cubic a = 10.3777(7) Å, space group Fd-3m) was prepared by using a microwave-assisted solvothermal reaction. The grain size of the nanopowder was 20–30 nm in diameter. Sn_1.24Ti_1.94O_3.66(OH)_1.50F_1.42 decomposed above 300 °C, but could be sintered to relative density greater than 99% by a hydrothermal hot-pressing (HHP) method at 270 °C and 80 MPa for 4 h. The synthesized powder and solidified body obtained using HHP showed significantly different color, probably due to the difference in water content.     

The energetics of lanthanum tantalate materials

Lanthanum tantalates are important refractory materials with application in photocatalysis, solid oxide fuel cells, and phosphors. Soft-chemical synthesis utilizing the Lindqvist ion, [Ta₆O₁₉]⁸⁻, has yielded a new phase, La₂Ta₂O₇(OH)₂. Using the hydrated phase as a starting material, a new lanthanum orthotantalate polymorph was formed by heating to 850 °C, which converts to a previously reported LaTaO₄ polymorph at 1200 °C. The stabilities of La₂Ta₂O₇(OH)₂ (LaTa−OH), the intermediate LaTaO₄ polymorph (LaTa-850), and the high temperature phase (LaTa-1200) were investigated using high-temperature oxide melt solution calorimetry. The enthalpy of formation from the oxides were calculated from the enthalpies of drop solution to be −87.1±9.6, −94.9±8.8, and −93.1±8.7 kJ/mol for LaTa−OH, LaTa-850, and LaTa-1200, respectively. These results indicate that the intermediate phase, LaTa-850, is the most stable. This pattern of energetics may be related to cation-cation repulsion of the tantalate cations. We also investigated possible LnTaO₄ and Ln₂Ta₂O₇(OH)₂ analogues of Ln=Pr, Nd to examine the relationship between cation size and the resulting phases.     

Nd3Si5AlON10 – Synthese,Kristallstruktur und Eigenschaften eines Sialons im La3Si6N11‐Strukturtyp

Nd₃Si₅AlON₁₀ – Synthesis, Crystal Structure, and Properties of a Sialon Isotypic with La₃Si₆N₁₁ Nd₃Si₅AlON₁₀ was synthesized by the reaction of silicon diimide, aluminium nitride, aluminium oxide, and neodymium in a pure nitrogen atmosphere at 1650 °C using a radiofrequency furnace. The compound was obtained as a coarsely crystalline solid. According to the single‐crystal structure determination the title compound is isotypic with Ln₃Si₆N₁₁ (Ln = La, Ce, Pr, Nd, Sm). Nd₃Si₅AlON₁₀ (P4bm, a = 1007.8(1), c = 486.3(1) pm, Z = 2, R₁ = 0.016, wR₂ = 0.031) is built up by a three‐dimensional network structure of corner sharing SiON₃ and (Si/Al)N₄ tetrahedra (molar ratio Si : Al = 3 : 1). According to lattice energetic calculations using the MAPLE concept a differentiation of O and N seems to be reasonable. One of the two different sites for the tetrahedral centres is probably occupied by Si (distances: Si–O: 168.4(1), Si–N: 173.6(3)–176.0(4) pm) the second site by Si and Al with the molar ratio 3 : 1 (distances: (Si/Al)–N: 172.0(3)–176.6(2) pm). The Nd³⁺ ions are located in the voids of the (Si₅AlON₁₀)^9– framework (distances: Nd–O: 261.07(8), Nd–N: 246.1(2)–286.6(2) pm).     

Zur Dimorphie von Nd3Cl[SiO4]2

On the Dimorphism of Nd₃Cl[SiO₄]₂ On reacting NdCl₃, Nd₂O₃, and SiO₂ (molar ratio: 1 : 4 : 6) at 850 °C in evacuated silica tubes, pale violet, hydrolysis resistant neodymium(III) chloride ortho‐silicate Nd₃Cl[SiO₄]₂ can be obtained within seven days. If equimolar amounts of NaCl are added as flux, rod‐ or platelet‐shaped, transparent single crystals of two modifications accumulate simultaneously. The one with the higher density (A‐Nd₃Cl[SiO₄]₂) crystallizes monoclinically (C2/c, no. 15; a = 1416.6(1), b = 638.79(6), c = 872.21(9) pm, β = 98.403(7)°; V_m = 117.55 cm³/mol, Z = 4), whereas the one with the lower density (B‐Nd₃Cl[SiO₄]₂) exhibits orthorhombic symmetry (Pnma, no. 62; a = 709.36(7), b = 1815.7(2), c = 631.48(6) pm; V_m = 122.45 cm³/mol, Z = 4). Two crystallographically independent Nd³⁺ cations exist in each of both crystal structures, which in the A type are surrounded by nine (1 Cl^– + 8 O^2–) and ten (2 Cl^– + 8 O^2–), whilst those in the B type by only two times eight (1 Cl^– + 7 O^2– and 2 Cl^– + 6 O^2–) anions, respectively. Thereby all oxygen atoms of both forms represent members of discrete ortho‐silicate tetrahedra ([SiO₄]^4–). Although both crystal structures are built of alternating anionic double layers {(Nd1)₂[SiO₄]₂}^2– and cationic single layers {(Nd2)Cl}²⁺, there is a higher cross‐linkage of the building units in the A‐type lattice, where the cations are coordinated by three and four tetrahedra edges of ortho‐silicate anions, compared to only two times two of them in the B type. From this an about 4% higher density of Nd₃Cl[SiO₄]₂ results for the A‐type structure (D_x = 5.55 g/cm³) in comparison with B‐type Nd₃Cl[SiO₄]₂ (D_x = 5.33 g/cm³).     

Polyol-mediated synthesis of Li4Ti5O12 nanoparticle and its electrochemical properties

Li₄Ti₅O₁₂ nanoparticles were precipitated from ethylene glycol solution of titanium tetra isopropoxide (Ti(O-iPr)₄) and Li₂O₂ by refluxing at 197 °C for 12 h. The obtained particles were filtered and dried at 100 °C for 12 h, and the dried powder samples were heated at 320, 500 and 800 °C for 3 h. The X-ray diffraction patterns of the obtained samples exhibited a good fit with the spinel phase. The field emission-SEM images of the dried powder sample and the samples heated at 320, 500 and 800 °C for 3 h showed a uniform spherical morphology with a particle size of 5, 8, 10 and 400 nm, respectively. According to the results of electrochemical testing, the dried powder sample and the samples heated at 320, 500, and 800 °C for 3 h showed initial capacities of 200, 310, 320, and 260 mA h/g, respectively, at a current density of 0.05 mA/cm². Nanosized (6–8 nm) particles with good crystallinity were obtained by controlling the synthesis conditions. The sample heated at 500 °C for 3 h exhibited a high capacity and an excellent rate capability over 60 cycles.