Intermediate molybdenum oxides involved in binary and ternary induced electrodeposition

The first stages of Co–Ni and Co–Ni–Mo deposition in sulphate–citrate medium at pH 4.0 were analysed. In both cases, the formation of non-hydrogenated nickel on the electrode before alloy deposition was detected by linear sweep voltammetry and inductively coupled plasma mass spectrometry. Co–Ni electrodeposition was anomalous since the Co/Ni ratio in the alloy was higher than the corresponding [Co(II)]/[Ni(II)] ratio in solution. The adsorption of Co(II) over the initial nickel could explain the anomalous codeposition, which persisted with the addition of molybdate to the Co–Ni bath. However, the formation of intermediate molybdenum oxides also took place. A mechanism has been proposed to describe the sequence of steps for Co–Ni–Mo electrodeposition. Under our conditions, the alloy is formed mainly from free Co²⁺ and Ni²⁺ cations, whereas molybdate is reduced firstly to molybdenum oxide from MoO₄(H₃Cit)²⁻ and, secondly, NiCit⁻ catalyses the subsequent reduction to molybdenum metal of the intermediate [MoO₂–NiCit⁻]_ads species.     

Ein Beitrag zur Kenntnis ternärer Phosphorlegierungen

Zusammenfassung Die Schnitte bei 25 und 33,3 At% P in den Dreistoffsystemen Cr–Mn–P, Cr–Fe–P, Cr–Ni–P, Cr–Cu–P, Mn–Fe–P, Mn–Ni–P, Mn–Cr–P, Fe–Ni–P, Fe–Cu–P und Ni–Cu–P werden röntgenographisch untersucht. Es wird das Ergebnis vonVogel und Mitarbeitern hinsichtlich der Mischbarkeit von Fe₃P–Ni₃P bzw. Cr₃P–Fe₃P bestätigt.Eine solche Mischreihe bilden auch Cr₃P und Mn₃P. Dagegen dürften Cr₃P und Ni₃P nur begrenzt mischbar sein; Fe₃P nimmt mindestens 25 Mol% Mn₃P auf. Ni₃P löst rund 50 Mol% des nicht isotypen Cu₃P, während zwischen den isotypen Phasen Mn₃P und Ni₃P sowie zwischen Cr₃P, Mn₃P, Fe₃P einerseits und Cu₃P keine merkliche Löslichkeit beobachtet wurde.Lückenlose Mischreihen bilden auch Mn₂P–Fe₂P, Fe₂P–Ni₂P sowie Ni₂P–Mn₂P. Obwohl keine isotype Cr₂P-Phase gefunden wird, besteht ein praktisch homogener Übergang zwischen Fe₂P–Cr₂P, Ni₂P–Cr₂P. Mn₂P löst rund 50 Mol% Cr₂P; Mn₂P sowie Fe₂P nehmen jeweils etwa 20 Mol% Cu₂P auf.Mit 4 Abbildungen     

Synthesis and structure of mixed-metal thiolate complex Cp′Cr(CO)2(μ-SBu)Pt(PPh3)2: Side-on-coordination of Cr–S double bond with platinum

The reaction of [Cp′Cr(CO)₂(μ-SBu)]₂ (1) (Cp′ = MeC₅H₄) with (PPh₃)₂Pt(PhCCPh) gives Cp′Cr(CO)₂(μ-SBu)Pt(PPh₃)₂ (2) which could be regarded as a product of the substitution of acetylene ligand at platinum by a monomeric chromium–thiolate fragment. According to the X-ray diffraction analysis 2 contains single Cr–Pt (2.7538(15)) and Pt–S (2.294(2) Å) bonds while Cr–S bond (2.274(3) Å) is shortened in comparison with ordinary Cr–S bonds (2.4107(4)–2.4311(4) Å) in 1. The bonding between Cr–S fragment and platinum atom is similar to the olefine coordination in their platinum complexes.     

Phase relations in the system K2MoO4–KPO3–MoO3–Bi2O3: A new phosphate K3Bi5(PO4)6

Phase equilibrium in the pseudo-quaternary system K₂O–MoO₃–P₂O₅–Bi₂O₃ was studied as three-component solvent K₂MoO₄–KPO₃–MoO₃ containing 15 mol% Bi₂O₃ during slow cooling and spontaneous crystallization. The results of the investigation were shown on a composition diagram, which indicates the crystallization fields of K₂Bi(PO₄)(MoO₄), K₅Bi(MoO₄)₄, BiPO₄ and K₃Bi₅(PO₄)₆. New phosphate K₃Bi₅(PO₄)₆ was characterized by single-crystal X-ray diffraction (space group C2/c, a=17.680(4), b=6.9370(14), c=18.700(4) Å, β=113.79(3)°) and FTIR spectroscopy. The possibility of lone electron pair stereoactivity of bismuth was suggested using the calculations of characteristics of the Voronoi–Dirichlet polyhedra for K₃Bi₅(PO₄)₆ and K₂Bi(PO₄)(MoO₄).     

Acetalization of glycerol using mesoporous MoO3/SiO2 solid acid catalyst

Acetalization of glycerol with various aldehydes has been carried out using mesoporous MoO₃/SiO₂ as a solid acid catalyst. A series of MoO₃/SiO₂ catalysts with varying MoO₃ loadings (1–20 mol%) were prepared by sol–gel technique using ethyl silicate-40 and ammonium heptamolybdate as silica and molybdenum source respectively. The sol–gel derived samples were calcined at 500 °C and characterized using various physicochemical characterization techniques. The XRD of the calcined samples showed the formation of amorphous phase up to 10 mol% MoO₃ loading and at higher loading of crystalline α-MoO₃ on amorphous silica support. TEM analyses of the materials showed the uniform distribution of MoO₃ nanoparticles on amorphous silica support. Raman spectroscopy showed the formation of silicomolybdic acid at low Mo loading and a mixture of α-MoO₃ and polymolybdate species at high Mo loadings. Moreover the Raman spectra of intermediate loading samples also suggest the presence of β-MoO₃. Acetalization of glycerol with benzaldehyde was carried out using series of MoO₃/SiO₂ catalysts with varying MoO₃ loadings (1–20 mol%). Among the series, MoO₃/SiO₂ with 20 mol% MoO₃ loadings was found to be the most active catalyst in acetalization under mild conditions. Maximum conversion of benzaldehyde (72%) was obtained in 8 h at 100 °C with 60% selectivity for the six-membered acetal using 20% MoO₃/SiO₂. Interestingly with substituted benzaldehydes under same reaction conditions the conversion of aldehydes decreased with increase in selectivity for six-membered acetals. These results indicate the potential of this catalyst for the acetalization of glycerol for an environmentally benign process.     

AES- und XPS-Untersuchungen zum Einflu? von Chrom, Nickel und Molybd?n auf das Korrosionsverhalten von rostfreien St?hlen in S?uren

Summary The alloys Fe17.8Cr, Fe16Cr2.4Mo and Fe18Cr14Ni2.5Mo (at%) were polarized in 0.5 mol/l H₂SO₄ or in 0.1 mol/l HC1 + 0.4 mol/l NaCl. The composition of the oxide layer and of the metallic layer beneath the oxide and the kinetics of the passive layer formation were determined by AES and XPS. In the active region, selective dissolution of Fe leads to an enrichment of Cr, Ni and Mo at the metal/electrolyte interface. In the passive region, the thickness of the rapidly formed passive layer is determined by the potential. The chromium content of the passive layer approaches a stationary, high value. The passive layer essentially consists of the anions O^2- and OH^– and of the cations of Cr, Fe, Mo, whereas Ni — and less pronounced Mo — are enriched below the layer.     

Hydrogen electrosorption in Ni–Pd alloys

Hydrogen absorption in Ni–Pd alloys has been investigated. The amount of absorbed hydrogen in alloys containing below 20 at.% of nickel is equal to the amount of hydrogen sorbed in pure palladium. Hydrogen absorption occurs in the range 0–40 at.% of nickel concentration. Cyclic voltammograms recorded at Ni–Pd alloys have characteristic peaks which overlap with the responses due to processes occurring on the surface at Ni and Pd atoms. Also some of the processes characteristic of the pure metals can be distinguished from the recorded voltammograms.     

Steric distortion of planar NiP<Subscript>2</Subscript>N<Subscript>2</Subscript> chromophores: a spectral,cyclic voltammetric and single crystal X-ray structural study

The complexes trans-[Ni(4-MP)₂(NCS)₂]·MeCN (1) and trans-[Ni(3-MP)₂(NCS)₂] (2) (4-MP = tri(4-methylphenyl)phosphine, 3-MP = tri(3-methylphenyl)phosphine) were prepared and characterized by IR, UV–visible, NMR spectra, CV, TGA and single crystal X-ray crystallography. Both the complexes have planar geometry and are diamagnetic. The Ni–P distances in both complexes are relatively short as a result of strong back donation from nickel to phosphorus. The phenyl rings in the 3-MP analogue (2) show increased pitching with reference to the plane formed by the ipso carbons due to increased steric effects. For complex (2), the N–Ni–N and P–Ni–P angles are significantly lower than the almost linear N–Ni–N and N–Ni–P angles observed for both complex (1) and trans-[Ni(PPh₃)₂(NCS)₂]. This observation indicates that the 3-methylphosphine ligand forces complex (2) to distort towards a tetrahedral geometry. IR spectra of both complexes show strong bands around 2,090 cm⁻¹ due to N-coordinated thiocyanate, while the electronic spectra contain d–d transitions around 452 nm. Cyclic voltammograms show that the irreversible one-electron reduction potentials increase in the following order: trans- [Ni(PPh₃)₂(NCS)₂] < trans- [Ni(3-MP)₂(NCS)₂] < trans-[Ni(4-MP)₂(NCS)₂], revealing the electron releasing effect of the methyl groups. The planar complexes exhibit interallogony in coordinating solvents.     

Self-powdering and nonlinear optical domain structures in ferroelastic β′-Gd2(MoO4)3 crystals formed in glass

Ferroelastic β′-Gd₂(MoO₄)₃, (GMO), crystals are formed through the crystallization of 21.25Gd₂O₃–63.75MoO₃–15B₂O₃ glass (mol%), and two scientific curious phenomena are observed. (1) GMO crystals formed in the crystallization break into small pieces with a triangular prism or pyramid shape having a length of 50–500 μm spontaneously during the crystallizations in the inside of an electric furnace, not during the cooling in air after the crystallization. This phenomenon is called “self-powdering phenomenon during crystallization” in this paper. (2) Each self-powdered GMO crystal grain shows a periodic domain structure with different refractive indices, and a spatially periodic second harmonic generation (SHG) depending on the domain structure is observed. It is proposed from polarized micro-Raman scattering spectra and the azimuthal dependence of second harmonic intensities that GMO crystals are oriented in each crystal grain and the orientation of (MoO₄)²⁻ tetrahedra in GMO crystals changes periodically due to spontaneous strains in ferroelastic GMO crystals.     

Synthesis of uniform-sized bimetallic iron–nickel phosphide nanorods

We synthesized uniform-sized nanorods of iron–nickel phosphides from the thermal decomposition of metal–phosphine complexes. Uniform-sized (Fe_xNi_1−x)₂P nanorods (0x1) of various compositions were synthesized by thermal decomposition of Ni–trioctylphosphine (TOP) complex and Fe–TOP complex. By measuring magnetic properties, we found that blocking temperature and coercive field depend on Ni content in the nanorods. Both parameters were more sensitive to doping compared with bulk samples.     

Electrochemically regenerative visible light-induced reactivity of α-Fe2O3 films with Ag(core)–AgCl(shell) microcrystal composites

Ag(core)–AgCl(shell) microcrystal composites (Ag@AgCl) have been formed on an α-Fe₂O₃ film-coated SnO₂ electrode by a 2 step method consisting of the electrochemical reduction of Ag⁺ ions and the subsequent electrochemical oxidation. The synergy of α-Fe₂O₃ and Ag@AgCl gave rise to a high visible light-induced reactivity (λ_ex > 420 nm) for the oxidation of 2-naphthol (2-NAP) used as a model water pollutant in the presence and absence of oxygen. These findings were attributable to the function of Ag@AgCl composites as an excellent charge-separation promoter and built-in acceptor.     

Study on the formation process of MoO3/Fe2(MoO4)3 by mechanochemical synthesis and their catalytic performance in methanol to formaldehyde

Mechanochemical method has applied to the green preparation of iron-molybdenum catalyst efficiently, and their catalytic performance was evaluated by the oxidation of methanol to formaldehyde. In order to investigate the formation process of iron-molybdenum catalyst based on mechanochemical method, various characterization techniques have been employed. Results indicate that iron-molybdenum catalyst could not be generated during ball milling process without calcining, and calcination is crucial step to regulate the ratio of MoO₃ and Fe₂(MoO₄)₃. For the formation of MoO₃ and Fe₂(MoO₄)₃ phase, 180 °C could be the key turning temperature point. Fe₂(MoO₄)₃ and MoO₃ phases are concurrently emerged when Mo/Fe atomic ratio exceeds 1.5. The aggregation of Fe₂(MoO₄)₃ is severe with the increasing calcination temperature. Fe₂(MoO₄)₃ is stable below 600 °C, while MoO₃ phase could be subliming with the increasing temperature. The catalytic performance of iron-molybdenum catalyst has closely correlation with the phase compositions, which can be controlled by synthesis temperature and Mo/Fe molar ratio. The iron-molybdenum catalyst with Mo/Fe atomic ratio of 2.6 calcined at 500 °C for 4 h showed the best methanol conversion (100%) and formaldehyde yield (92.27%).

     

Development of soft X-ray multilayer laminar-type plane gratings and varied-line-spacing spherical grating for flat-field spectrograph in the 1–8 keV region

W/C and Co/SiO₂ multilayer laminar-type holographic plane gratings (groove density 1/σ = 1200 lines/mm) in the 1–8 keV region are developed. For the Co/SiO₂ grating the diffraction efficiencies of 0.41 and 0.47 at 4 and 6 keV, respectively, and for the W/C grating 0.38 at 8 keV are observed. Taking advantage of the outstanding high diffraction efficiencies into practical soft X-ray spectrographs a Mo/SiO₂ multilayer varied-line-spacing (VLS) laminar-type spherical grating (1/σ = 2400 lines/mm) is also developed for use with a flat field spectrograph in the region of 1.7 keV. For the Mo/SiO₂ multilayer grating the diffraction efficiencies of 0.05–0.20 at 0.9–1.8 keV are observed. The FWHMs of the measured line profiles of Hf-Mα₁(1644.6 eV), Si-Kα₁(1740.0 eV), and W-Mα₁ (1775.4 eV) are 13.7 eV, 8.0 eV, and 8.7 eV, respectively.     

Enhanced sulfur‐resistant methanation performance over MoO3–ZrO2 catalyst prepared by solution combustion method

Sulfur‐resistant methanation of syngas was studied over MoO₃–ZrO₂ catalysts at 400°C. The MoO₃–ZrO₂ solid‐solution catalysts were prepared using the solution combustion method by varying MoO₃ content and temperature. The 15MoO₃–ZrO₂ catalyst achieved the highest methanation performance with CO conversion up to 80% at 400°C. The structure of ZrO₂ and dispersed MoO₃ species was characterized using X‐ray diffraction and transmission electron microscopy. The energy‐dispersive spectrum of the 15MoO₃–ZrO₂ catalyst showed that the solution combustion method gave well‐dispersed MoO₃ particles on the surface of ZrO₂. The structure of the catalysts depends on the Mo surface density. It was observed that in the 15MoO₃–ZrO₂ catalyst the Mo surface density of 4.2 Mo atoms nm^?2 approaches the theoretical monolayer capacity of 5 Mo atoms nm^?2. The addition of a small amount of MoO₃ to ZrO₂ led to higher tetragonal content of ZrO₂ along with a reduction of particle size. This leads to an efficient catalyst for the low‐temperature CO methanation process.     

Molybdenum(VI) network polymers based on anion–π interaction and hydrogen bonding: Synthesis, crystal structures and oxidation catalytic application

A crystallographic investigation of anion–π interactions and hydrogen bonds on the preferred structural motifs of molybdenum(VI) complexes has been carried out. Two molybdenum(VI) network polymers MoO₂F₄·(Hinca)₂ (1) and MoO₂F₃(H₂O)·(Hinpa) (2), where inca = isonicotinamide and inpa = isonipecotamide, have been synthesized, crystallographically characterized and successfully applied to alcohol oxidation reaction. Complex 1 crystallizes in the monoclinic space C2/c: a = 16.832(3) Å, b = 8.8189(15) Å, c = 12.568(2) Å, β = 118.929(3)°, V = 1560.1(5) Å³, Z = 4. Complex 2 crystallizes in the triclinic space P-1: a = 5.459(2) Å, b = 9.189(4) Å, c = 12.204(5) Å, α = 71.341(6)°, β = 81.712(7)°, γ = 77.705(7)°, V = 564.8(4) Å³, Z = 2. Complex 1 consists of hydrogen bonding and anion–π interactions, both of which are considered as important factors for controlling the geometric features and packing characteristics of the crystal structure. The geometry of the sandwich complex of [MoO₂F₄]²⁻ with two pyridine rings indicates that the anion–π interaction is an additive and provides a base for the design and synthesis of new complexes. For complex 2, the anions and the protonated inpa ligands form a 2D supramolecular network by four different types of hydrogen contacts (N–HF, N–HO, O–HF and O–HO). The catalytic ability of complexes 1 and 2 has also been evaluated by applying them to the oxidation of benzyl alcohol with TBHP as oxidant.     

Preparation and electrical properties of new oxide ion conductors Ce6−xDyxMoO15−δ (0.0 ≤ x ≤ 1.8)

Ce_6−xDy_xMoO_15−δ (0.0 ≤ x ≤ 1.8) were synthesized by modified sol–gel method. Structural and electrical properties were investigated by means of X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The XRD patterns showed that the materials were single phase with a cubic fluorite structure. Impedance spectroscopy measurement in the temperature range between 350 °C and 800 °C indicated a sharp increase in conductivity for the system containing small amount of Dy₂O₃. The Ce_5.6Dy_0.4MoO_15−δ detected to be the best conducting phase with the highest conductivity (σ_t = 8.93 × 10⁻³ S cm⁻¹) is higher than that of Ce_5.6Sm_0.4MoO_15−δ (σ_t = 2.93 × 10⁻³ S cm⁻¹) at 800 °C, and the corresponding activation energy of Ce_5.6Dy_0.4MoO_15−δ (0.994 eV) is lower than that of Ce_5.6Sm_0.4MoO_15−δ (1.002 eV).     

Spontaneous passivity of amorphous bulk Ni–Cr–Ta–Mo–Nb–P alloys in concentrated hydrochloric acids

Rod-shaped amorphous bulk Ni–Cr–Mo-22 at.%Ta-14 at.%Nb–P alloys resistant to concentrated hydrochloric acids were prepared by copper-mold casting. Alloys of amorphous single phase and mixture of nanocrystalline phases in the amorphous matrix were all spontaneously passive in 6 and 12 M HCl and were immune to corrosion in 6 M HCl, although the corrosion weight loss was detected for heterogeneous alloys in 12 M HCl. Spontaneous passivation is due to presence of stable air-formed films in which chromium was particularly concentrated in addition to enrichment of tantalum and niobium. The angle resolved X-ray photoelectron spectroscopy revealed that chromium and molybdenum are rich in the inner part of the film. The major molybdenum species is in the tetravalent state, although penta- and hexavalent state molybdenum is also included. The high corrosion resistance was interpreted in terms of the high stability of the outer triple oxyhydroxide, Cr_1−x−yTa_xNb_yO_z(OH)_3+2x+2y−2z, and the effective diffusion barrier of the inner Mo⁴⁺ and Cr³⁺ oxide layer. Contribution to the Fall Meeting of the European Materials Research Society, Symposium D: 9th International Symposium on Electrochemical/Chemical Reactivity of Metastable Materials, Warsaw, 17th-21st September, 2007.     

Synthesis,characterization, and dielectric properties of β-Gd<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript> thin films prepared by chemical solution deposition

A chemical solution was employed for deposition of gadolinium molybdate [β-Gd₂(MoO₄)₃] thin films. Gadolinium acetylacetonate hydrate {[CH₃COCH = C(O–)CH₃]₃Gd·xH₂O}, molybdenum isopropoxide {Mo[OCH(CH₃)₂]₅}, and acetylacetone were used in synthesis of this molybdate. Thermal gravimetry and differential scanning calorimetry suggested that crystallization of β-Gd₂(MoO₄)₃ occurs at around 480 °C. Phase-pure, orthorhombic β-Gd₂(MoO₄)₃ films were deposited on Pt/Ti/SiO₂/Si(100) substrates. β-Gd₂(MoO₄)₃ films crystallized at 750 °C showed a strong (00l) preferred orientation. The film dielectric constant measured was 10~14 and the dielectric loss was less than 3%. There was no marked signature in the permittivity at the bulk Curie temperature, approximately 159 °C.     

Removal, preconcentration and determination of Mo(VI) from water and wastewater samples using maghemite nanoparticles

Removal and recovery of Mo(VI) from aqueous solutions were investigated using maghemite (γ-Fe₂O₃) nanoparticles. Combination of nanoparticle adsorption and magnetic separation was used to the removal and recovery of Mo(VI) from water and wastewater solutions. The nanoscale maghemite with mean diameter of 50 nm was synthesized by reduction coprecipitation method followed by aeration oxidation. Various factors influencing the adsorption of Mo(VI), e.g. pH, temperature, initial concentration, and coexisting common ions were studied. Adsorption reached equilibrium within <10 min and was independent of initial concentration of Mo(VI). Studies were performed at different pH values to find out the pH at which maximum adsorption occurred. The maximum adsorption occurred at pHs between 4.0 and 6.0. The Langmuir adsorption capacity (q_max) was found to be 33.4 mg Mo(VI)/g of the adsorbent. The results showed that nanoparticle (γ-Fe₂O₃) is suitable for the removal of Mo(VI), as molybdate, from water and wastewater samples. The adsorbed Mo(VI) was then desorbed and determined spectrophotometrically using bromopyrogallol red as a complexation reagent. This allows the determination of Mo(VI) in the range 1.0–86.0 ng mL⁻¹.     

Hydrogen bond strength in chromates with kröhnkite-type chains, K2Me(CrO4)2·2H2O (Me = Mg, Co, Ni, Zn, Cd)

Infrared spectra of the title compounds with kröhnkite-type infinite octahedral–tetrahedral chains, K₂Me(CrO₄)₂·2H₂O (Me = Mg, Co, Ni, Zn, Cd), are presented in the regions of the uncoupled O–D stretching modes of matrix-isolated HDO molecules (isotopically dilute samples) and water librations. The strengths of the hydrogen bonds are discussed in terms of the respective O_wO bond distances, the Me–water interactions (synergetic effect), the proton acceptor capability of the chromate oxygen atoms as deduced from Brown's bond valence sum of the oxygen atoms. The spectroscopic experiments reveal that hydrogen bonds of medium strength are formed in the chromates. The hydrogen bond strengths decrease in the order Cd > Zn > Ni > Co in agreement with the decreasing covalency of the respective Me–OH₂ bonds in the same order, i.e. decreasing acidity of the water molecules. The infrared band positions corresponding to the water librations confirm the claim that the hydrogen bonds in K₂Cd(CrO₄)₂·2H₂O are stronger than those formed in K₂Mg(CrO₄)₂·2H₂O on one hand, and on the other—the hydrogen bonds in K₂Ni(CrO₄)₂·2H₂O are stronger than those in K₂Co(CrO₄)₂·2H₂O.