Study on the reduction of commercial MoO3 with carbon black to prepare MoO2 and Mo2C nanoparticles

A simple method was developed to synthesize MoO₂ and Mo₂C nanoparticles via controlling nucleation and growth in carbothermic reduction of commercial MoO₃ with carbon black. It was found that the appropriate C/MoO₃ molar ratio for preparation of Mo₂C was 2.8, and the carbothermic reduction process followed the sequence: MoO₃ → transport phase (TP) → MoO₂ → Mo₂C. It was revealed that the most crucial issues for controlling number of produced particles of product were migration of Mo source and aid of nucleating agent, which can be achieved by using MoO₃ and carbon black as starting materials. MoO₂ nanosheets with the thickness of 12 nm and lateral size of 60 nm, as well as Mo₂C nanoparticles with particle size of 30 nm were prepared via reduction of MoO₃ with carbon black. However, MoO₂ and Mo₂C produced via reducing MoO₃ by other kinds of carbon sources (activated carbon, graphite) or gas reductants (10% CH₄/H₂, CO) had much larger particle sizes of a few micrometers, which were tens of times than those using MoO₃ and carbon black, due to the too small amount of formed nuclei. The effects of C/MoO₃ molar ratio (0.5-2.8), molybdenum sources and carbon sources on the reaction mechanisms were investigated in detail.     

Study on Reduction of MoO2 Powders with CO to Produce Mo2C

Molybdenum hemicarbide (Mo₂C), which is widely applied in steel and metal ceramics as well as catalysts, was successfully synthesized by using a simple method of reducing MoO₂ powders by CO. It was found that the final reduction product was all Mo₂C under both isothermal and nonisothermal conditions. However, the reduction mechanisms were significantly different at lower and higher temperatures: at lower temperatures (1070 to 1342 K), reduction of MoO₂ to Mo₂C followed a one‐step reaction (simultaneous reduction and carburization), while at higher temperatures (1423 to 1485 K), MoO₂ was first reduced to metallic Mo, and then Mo was carburized to Mo₂C. Mo₂C particles obtained at higher temperatures contained micrometer‐sized surface features which formed during the MoO₂ to Mo reduction step.     

Synthesis,microstructure evolution,and phase transformation of novel MoCoB–Co cermets

To develop tungsten-free cermets, a novel MoCoB–Co cermet composed of MoCoB as a hard phase and Co as a binder phase was synthesized by the reaction sintering of Mo, Co, and B powders. The microstructure evolution, phase transformation, and mechanical properties of the cermet were investigated. We demonstrated that the mixed powders experienced three solid-phase reactions, Co + B → Co₂B, 11Mo + 15Co₂B → Mo₂Co₂₁B₆ + 9MoCoB, and 4Mo + Mo₂Co₂₁B₆ → 6MoCoB +15Co, and underwent two liquid-phase reactions. Nanosized, tremella-like Co structures were formed on the surface of the particles between 1100 and 1200 °C. The formation of these structures may be due to the Kirkendall effect. Further, the first liquid, L₁, was formed at 1242 °C by a eutectic reaction between the tremella-like Co structures and MoCoB. This led to an increase in the relative density of the sample from 43% to 71.7%. At 1268 °C, the second liquid, L₂, was formed as a result of a eutectic reaction between Co and MoCoB that further increased the relative density of the sample to 95%. At 1300 °C, the cermet exhibited the highest hardness and transverse rupture strength of 83.9 HRA and 1700 MPa, respectively.     

Remarkable support effect of ZrO2 upon the CO2 reforming of CH4 over supported molybdenum carbide catalysts

In reforming of CH₄ with CO₂ over molybdenum carbide catalysts, the catalytic performance of unsupported hexagonal Mo₂C prepared by direct carburization of MoO₃ was considerably different from a similar composition, cubic MoC_1−x (x≈0.5), prepared through nitriding before carburization. The conversion levels over MoC_1−x were substantially higher than those over Mo₂C, although the turnover frequencies were lower. X‐ray diffraction analysis indicated that Mo₂C deactivated by conversion to MoO₂ during the reaction, but the MoC_1−x was transformed to the hexagonal Mo₂C and remained stable. The activity of Mo₂C dispersed on various supports for the CH₄–CO₂ reaction was also investigated. The performance depended strongly on the property of supports, with the ZrO₂‐supported Mo₂C catalyst exhibiting the highest activity and durability for this reaction. Moreover, deactivation of Mo₂C/ZrO₂ at ambient pressure was suppressed by decreasing the loading amount of Mo₂C. This revised version was published online in August 2006 with corrections to the Cover Date.     

Selective Isopropylation of Biphenyl to 4,4′-DIPB over Mordenite (MOR) Type Zeolite Obtained from a Layered Sodium Silicate Magadiite

Molybdenum carbide catalysts for water–gas shift (WGS) reaction were investigated to develop an alternate commercial LTS (Cu-Zn/Al₂O₃) catalyst for an onboard gasoline fuel processor. The catalysts were prepared by a temperature-programmed method and were characterized by N₂ physisorption, CO chemisorption, XRD and XPS. It was found that the Mo₂C catalyst showed higher activity and stability than the commercial LTS catalyst, even though both catalysts were deactivated during the thermal cycling runs. The optimum carburization temperature for preparing Mo₂C was in the range of 640–650 °C. It was found that the deactivation of the Mo₂C catalyst was caused by the transition of Mo^δ+ (IV < δ⁺ < VI, MoO_xC_y), Mo^IV and Mo₂C on the surface of the Mo₂C catalyst to Mo^VI (MoO₃) with the reaction of H₂O in the reactant. It was identified that molybdenum carbide catalyst is an attractive candidate for the alternate Cu-Zn/Al₂O₃ catalyst for automotive applications.     

Preparation, characterization, and catalytic properties of the Mo2C/SBA-15 catalysts

A series of Mo₂C/SBA-15 catalysts with different Mo contents were prepared by temperature-programmed carburization (TPC). The materials obtained and their oxide precursors (MoO₃/SBA-15) were characterized by Nitrogen adsorption-desorption isotherms, X-ray diffraction (XRD), and Fourier transform-infrared (FT-IR) spectroscopy. The activities of the catalysts for deep hydrodesulfurization (HDS) of thiophene were evaluated. The results of N₂ adsorption-desorption isotherms indicated that the surface area and pore diameter of the oxide precursors increase after carburization. The XRD patterns show that Mo₂C particles are highly dispersed in the SBA-15 ordered mesoporous. The test results show that Mo₂C/SBA-15 catalysts have an excellent performance for the deep HDS under the lower temperature region.     

Crystal structure,infrared-reflectivity spectra,and microwave dielectric properties of novel Ce2(MoO4)2(Mo2O7) ceramics

Novel Ce₂(MoO₄)₂(Mo₂O₇) (CMO) ceramics were prepared by a conventional solid-state method, and the microwave dielectric properties were investigated. X-ray diffraction results illustrated that pure Ce₂(MoO₄)₂(Mo₂O₇) structure formed upon sintering at 600 °C-725 °C. [CeO₇], [CeO₈], [MoO₄], and [MoO₆] polyhedra were connected to form a three-dimensional structure of CMO ceramics. Analysis based on chemical bond theory indicated that the Mo–O bond critically affected the ceramics’ performance. Furthermore, infrared-reflectivity spectra analysis revealed that the primary polarisation contribution was from ionic polarisation. Notably, the optimum microwave dielectric properties of ε_r = 10.69, Q·f = 49,440 GHz (@ 9.29 GHz), and τ_f = −30.4 ppm/°C were obtained in CMO ceramics sintered at 700 °C.     

Flame-made MoO3/SiO2–Al2O3 metathesis catalysts with highly dispersed and highly active molybdate species

MoO₃/SiO₂–Al₂O₃ catalysts are prepared via flame spray pyrolysis and evaluated in the self-metathesis of propene to ethene and butene. Their specific surface area ranges between 100 and 170 m² g^?1 depending on the MoO₃ loading (1–15 wt.%, corresponding to Mo surface density between 0.3 and 6.1 Mo atoms per nm²). The catalysts were characterized by N₂-physisorption, X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectroscopy (ToF-SIMS). The silica–alumina matrix condenses first in the flame and forms non-porous spherical particles of 5–20 nm, followed by the dispersion of Mo oxide at their surface. Depending on the MoO₃ loading, different MoO_x species are stabilized: dispersed and amorphous molybdates (mono- and oligomeric) at low loadings (<5 wt.%, <1.5 Mo nm^?2) and crystalline MoO₃ species at higher loadings. Raman spectroscopy suggests the presence of monomeric species for surface densities of 0.3, 0.5 and 0.8 Mo nm^?2. The formation of MoOMo bonds is, however, clearly established by ToF-SIMS from surface densities as low as 0.5 Mo nm^?2. At 1.5 Mo nm^?2, crystallites of β-MoO₃ (2–3 nm) are detected and further increasing the loading induces the formation of bigger α- and β-MoO₃ crystals (around 20 nm). The speciation of Mo proves to have a marked impact on the metathesis activity of the catalysts. Catalysts with high Mo loading and exhibiting MoO₃ crystals are poorly active, whereas catalysts with low Mo loading (<5 wt.%) perform well in the reaction. The catalyst loaded with only 1 wt.% of MoO₃ (0.3 Mo nm^?2) is the most active, reaching turn over frequencies seven times higher than reference catalysts reported in the literature. Moreover, the specific metathesis activity is clearly inversely correlated to the degree of condensation of the molybdenum oxide phase (as evaluated by ToF-SIMS). The latter finding indicates that monomeric MoO_x species are the main active centres in the olefin metathesis.     

Phase equilibrium diagram and phase transformation for preparation of Mo2C: Thermodynamic study and experimental verification

Because of the extended application in catalytic reactions, numerous kinds of methods are developed for synthesis of Mo₂C catalysts. The repeated efforts on exploring the reaction conditions caused a huge waste of materials and a large consumption of the energy from researchers. In this work, a widely applicable guidance of phase equilibrium diagrams for Mo₂C production was provided by thermodynamic calculation. The phase equilibrium diagrams of both MoO₃–C and MoO₃–Na₂CO₃–C (Na₂MoO₄–C) systems were plotted, which reveals the reaction mechanisms and suggests the reaction conditions for preparation of Mo₂C. According to the phase equilibrium diagrams of Na₂MoO₄–C system, the reaction routes of molybdenum determined by the reduction temperature will experience Na₂MoO₄, Mo₂C, Mo in carbothermic reduction procedure, which is instructive for synthesis of Mo₂C catalysts. Results of this work will provide a theoretic guidance for the generation of Mo₂C, which will make the synthesis of molybdenum carbides much easier.     

MoOx-based catalysts for the oxidative dehydrogenation (ODH) of ethane to ethylene: Influence of vanadium and phosphorus on physicochemical and catalytic properties

The influence of vanadium and phosphorus on the physicochemical properties of the MoO_x oxide and on its catalytic properties in the oxidation of ethane to ethylene is examined. A series of MoO_x, MoVO_x (Mo/V = 11) and MoVPO_x (Mo/V = 11, V/P = 1) catalysts were prepared, characterized by several techniques (BET, XRD, XPS, LRS and ATG) and studied in the oxidative dehydrogenation of ethane to ethene at atmospheric pressure and at the temperature of reaction of 550 °C. Their structural properties, during reduction and re-oxidation, were examined by in situ X-ray diffraction and by X-ray photoelectron spectroscopy after pre-treatment. The sample containing phosphorus is the most active (conversion 14%) and selective to ethylene (SC₂H₄ = 67%). The formation of [PMo₁₁VO₄₀]⁴⁻ is assumed during preparation, and its decomposition during calcination leads to well dispersed phosphate groups and improved interactions between Mo and V species. During the catalytic reaction Mo^VI is stabilised by means of solid solutions of V in Mo₅O₁₄ and in MoO₃ (V_xMo_1−xO_3−x/2). A synergetic effect between these two phases could be responsible for the best performance of Mo₁₁VPO_x as compared to those of MoO_x and Mo₁₁VO_x.     

On the Rapid Synthesis of the Ternary Mo2GaC

The reaction path to form the Mo₂GaC MAX phase starting with Mo, Ga, and C (molar ratio, 2:1.2:1) powders was investigated in the 850°C and 1000°C temperature range. It was found that Mo₂GaC could be synthesized from reactions between Mo₃Ga and C or Mo₂C and Ga. Powders that contained >90 wt% Mo₂GaC were successfully fabricated by heating a 1:1.4 molar ratio of Mo₂C:Ga to 900°C for 24 h under flowing argon, followed by the dissolution of excess Ga by HCl. The a‐ and c‐lattice parameters were measured to be 3.022(1) and 13.179(5) Å.     

Ultra‐low Sintering Temperature Microwave Dielectric Ceramics Based on Na2O‐MoO3 Binary System

The compounds in Na₂O‐MoO₃ system were prepared by the solid‐state reaction route. The phase composition, crystal structures, microstructures, and microwave dielectric properties of the compounds have been investigated. This series of compounds can be sintered well at ultra‐low temperatures of 505°C–660°C. The sintered samples exhibit good microwave dielectric properties, with the relative permittivities (ε_r) of 4.1–12.9, the Q × f values of 19900–62400 GHz, and the τ_f values of ?115 ppm/°C to ?57 ppm/°C. Among the eight compounds in this binary system, three kinds of single‐phase ceramics, namely Na₂MoO₄, Na₂Mo₂O₇ and Na₆Mo₁₁O₃₆ were formed. Furthermore, the relationship between the structure and the microwave dielectric properties in this system has been discussed. The average Na^I‐O and Mo^VI‐O bond valences have an influence on the sintering temperatures in Na₂O‐MoO₃ system. The large valence deviations of Na and Mo lead to a large temperature coefficient of resonant frequency. The X‐ray diffraction and backscattered electron image results show that Na₂MoO₄ doesn't react with Ag and Al at 660°C. Also, Na₂Mo₂O₇ has a chemical compatibility with Al at 575°C.     

Mo+TiO2(110) Mixed Oxide Layer: Structure and Reactivity

We present a STM/XPS/TPD/LEED study of the structural and electronic properties of Mo+Ti mixed oxide layers on TiO₂(110), and of their interaction with water, methanol and ethanol. Several different preparation procedures were tested and layers with different degrees of Mo/Ti mixing were prepared. Ordered mixed oxide surface phases with distinct LEED patterns could not be found; for all investigated Mo concentrations a TiO₂(110) like pattern was observed. Mo tends to agglomerate on the surface where it is found predominantly as Mo⁶⁺ at low coverages and as Mo⁴⁺ at high coverages. Mo⁴⁺ was also identified in the bulk of the mixed oxide layer. The Mo3d binding energies categorize the Mo⁴⁺ species as being dimeric. A third Mo3d doublet is attributed to a Mo species (Mo ⁿ⁺) with an oxidation state between those reported for Mo in MoO₂ and metallic Mo. Two types of Mo-induced features could be identified in the STM images for low Mo concentrations (in the range of 1 %). At higher Mo concentrations (~50 %) the surface is characterized by stripes with limited lengths in [001] direction. The concentration of bridging oxygen vacancies, which are common defects on TiO₂(110), is reduced significantly even at low Mo concentrations. Methanol and ethanol TPD spectra reflect this effect by a decrease of the intensity of the features related to these surface defects. At elevated MoO _x coverages, the yield of reaction products in methanol and ethanol TPD spectra are somewhat smaller than those found for clean TiO₂(110) and the reactions occur at lower temperature.     

Non-oxidative methane conversion into aromatics on mechanically mixed Mo/HZSM-5 catalysts

The catalyst prepared by the physical mixing of powder MoO₃ and HZSM-5 exhibits a better performance for methane conversion at high Mo loading compared with those prepared by the impregnation method. The specific surface area is larger for physically mixed samples than that for impregnated samples with the same Mo loading. The preferential orientation of MoO₃ crystallite is along the (0 k 0) axis, while the (0 2 1) plane is exposed preferentially by MoO₃ to impregnated HZSM-5. Both hcp β-Mo₂C and fcc α-Mo₂C can be formed on physically mixed samples, while only hcp β-Mo₂C is found on the impregnated samples under the same reaction condition.     

In situ thermal,optical, and structural investigations on reversible thermochromism in bismuth molybdate

Reversible thermochromic inorganic materials show stable and perceptible color change with changing environmental temperatures. This property makes them excellent materials for fabricating temperature indicators, military camouflage materials, and thermal warning devices. However, the mechanism of thermochromism has not been fully understood. Here, we prepared novel bismuth molybdate materials by calcination of Bi₂O₃ and MoO₃ mixtures. The materials exhibit reversible thermochromism, gradually changing color from milky white at 25 °C to bright yellow at 500 °C. The phase composition of the product is tunable by adjusting the ratio of Bi₂O₃ and MoO₃ in the starting materials, producing either single phase of α-Bi₂Mo₃O₁₂ or mixed phases of α-Bi₂Mo₃O_12, β-Bi₂Mo₂O₉ and γ-Bi₂MoO₆. The mechanism of reversible thermochromism was studied by in situ UV/Vis diffuse reflectance spectroscopy (UV/Vis DRS), in situ synchrotron radiation powder X-ray diffraction (SRPXRD), and differential scanning calorimetry (DSC). In situ SRPXRD revealed no phase transition during heating and cooling, which agrees with DSC analysis with no thermal event detected until the melting temperature of α-Bi₂Mo₃O₁₂ at 661.6 °C. With increasing temperature, in situ SRPXRD also revealed anisotropic expansion of the α-Bi₂Mo₃O₁₂ lattice parameters, while in situ UV/Vis DRS showed a continuous red shift in the absorption edge and gradual decrease of band gap, suggesting that lattice expansion and shrinking upon heating and cooling is the main reason for the thermochromic behavior in bismuth molybdate materials.     

The morphological evolution of the Bi2Mo3O12(010) surface in air–H2O atmospheres

Atomic force microscopy (AFM) has been used to examine the morphological evolution of the Bi₂Mo₃O₁₂(010) surface at 400–600 °C in dry air and air–2.3% H₂O. The (010) cleavage surface is characterized by atomically flat terraces separated by straight steps that are integer multiples of b/2 (5.75 Å) in height. During treatments at or above 500 °C, the surface is etched due to the volatilization of Mo. In dry air, etching affects both steps and flat terraces and results in step recession, the development of half-unit-cell (b/2) step loops (pits and islands), and the accumulation of Bi-rich surface deposits. In air–2.3% H₂O, steps are etched with preference to terraces, and this leads to step recession as well as the formation of Bi-rich deposits. Mo volatilization proceeds at an enhanced rate in air–2.3% H₂O and culminates in the nucleation and growth of Bi₂MoO₆ and Bi₂Mo₂O₉ precipitates at 500 and 600 °C, respectively.     

Phase formation and dielectric properties of ultralow temperature sintered Li4Mo5O17 ceramics

The Li₂MoO₄-MoO₃ ceramic system can be densely sintered at ultralow temperatures (< 500 °C). However, the phase composition of the Li₂MoO₄-MoO₃ system at a molar ratio of 1:1 has always been controversial. In this study, the traditional solid-state method was used to synthesize Li₄Mo₅O₁₇ (400 °C, 10 h) and Li₂Mo₂O₇ (350–400 °C, 4 h). Li₂Mo₂O₇ is an intermediate phase that can be converted to Li₄Mo₅O₁₇ at higher temperatures. The Li₄Mo₅O₁₇ ceramic could be sintered and densified at only 490 °C in air, exhibiting a relative density of 95.6% and excellent dielectric properties, including ε′= 12.79 and tan δ = 0.0004 at 1 GHz. Such an ultralow sintering temperature and dielectric loss indicate that the Li₄Mo₅O₁₇ ceramic is a good candidate for high-frequency capacitance applications.     

Preparation and characterization of powellite ceramics Ca1-xLix/2Cex/2MoO4 (0 ≤ x ≤ 1) for Mo-rich HLW condition

Powellite ceramic represent one candidate to immobilize minor actinides and Mo from reprocessed UMo nuclear fuel. In this work, the Ca_1-xLi_x/2Ce_x/2MoO₄ (0 ≤ x ≤ 1) series is prepared via a solid-state reaction using Ce³⁺ as trivalent minor actinide (Am³⁺) surrogate, with structure/microstructure characterized by XRD, XPS, HRTEM, and SEM as well. The Ca_1-xLi_x/2Ce_x/2MoO₄ (0 ≤ x ≤ 1) compositions crystallize in tetragonal and are isostructural with scheelite. Rietveld refinements show that Ce³⁺ and Li⁺ simultaneously enter into the eight-fold coordinated Ca site of powellite crystal. The chemical durability of powellite phases is evaluated by the ASTM C1285-14 product consistency test method B. The leaching behaviours of Ce and Mo are accordance with the interfacial dissolution-reprecipitation mechanism. For all the Ca_1-xLi_x/2Ce_x/2MoO₄ (0 ≤ x ≤ 1) ceramics, 7-days NL_Ce and NL_Mo are found to be in the order of 10⁻³-10⁻⁵ g·m⁻² and 10⁻²-10⁻⁴ g·m⁻² respectively, which exhibit the great retention of Ce and Mo. Interestingly, the values of 7-days NL_Ce and NL_Mo are predominantly controlled by the distortion of MoO₄ tetrahedra and disordered arrangements of Ce³⁺ and Li⁺. Thus, our initial understanding on the structure and chemical durability relation will provide insight to design new waste forms for the Mo-rich HLW condition.     

Influence of Mo doping on the tribological behavior of Ti3AlC2 ceramic at different temperatures

(Ti_0·8Mo_0.2)₃AlC₂ solid solutions were successfully synthesized from Ti, Al, TiC, and Mo powders using the in situ hot-pressing sintering method. The tribological properties of (Ti_0·8Mo_0.2)₃AlC₂ and the reference Ti₃AlC₂ in the temperature range 25–800 °C were evaluated in ambient air with the counterpart of Al₂O₃ balls. The results show that (Ti_0·8Mo_0.2)₃AlC₂ has improved lubricating properties and wear resistance above 400 °C compared with Ti₃AlC₂. This can be contributed to the formation of tribo-oxidation films containing MoO₃ and MoO_3-x. Structural characterization of the tribo-oxidation films was conducted using SEM, EDS, Raman spectroscopy, and XPS to evaluate the effect of Mo doping on the wear mechanisms of Ti₃AlC₂ in detail.     

Synthesis of ZrB2–ZrC hybrid powders via boro-carbothermal reduction of ZrO2 by B4C and carbon black

ZrB₂–ZrC hybrid powders were synthesized by a novel two-step reduction on basis of ZrO₂ + B₄C + C→ ZrC + ZrB₂ + CO reaction in Ar atmosphere, using ZrO₂, B₄C, and carbon black powders as starting materials. Thermodynamics of relevant reactions were evaluated. Effects of excess additions of B₄C and C on phase constituents were investigated. Morphology and chemistry of the powder products were characterized by scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS) and transmission electron microscopy (TEM). The results showed that ZrB₂–ZrC hybrid powders with no obvious impurity content could be obtained after heating at 1350 °C for 1 h followed by further reaction at 1700 °C for 1 h with 16 wt% B₄C + 8 wt% C excess addition. Relative contents of the ZrB₂: ZrC phase in the product powders could be conveniently regulated by varying the B₄C and C content in the starting compositions. The resultant powders had good oxidation resistance with an oxidation activation energy value of 433 kJ/mol. Good sinterability of the powder products was demonstrated by hot pressing at 1950 °C for 60min under 30 MPa pressure, which resulted in fully dense ZrB₂–ZrC composite ceramics with Vickers hardness value larger than 18.3 ± 0.6 GPa.