Element superconductors with the single atoms provide clean and fundamental platforms for studying superconductivity.Although elements with d electrons are usually not favored by conventional BCS,the record supercondu...Element superconductors with the single atoms provide clean and fundamental platforms for studying superconductivity.Although elements with d electrons are usually not favored by conventional BCS,the record superconducting critical temperature(T_(c))in element scandium(S_(c))has further ignited the intensive attention on transition metals.The element molybdenum(M_o)with a half-full d-orbital is studied in our work,which fills the gap in the study of Mo under high pressure and investigates the pressure dependence of superconductivity.In this work,we exhibit a robust superconductivity of Mo in the pressure range of 5 GPa to 160 GPa via high-pressure electrical transport measurements,the T_(c) varies at a rate of0.013 K/GPa to 8.56 K at 160 GPa.Moreover,the superconductivity is evidenced by the T_(c) shifting to lower temperature under applied magnetic fields,and the upper critical magnetic fields are extrapolated by the WHH equation and GL equation;the results indicate that the maximum upper critical magnetic field is estimated to be 8.24 T at 137 GPa.We further investigate the superconducting mechanism of Mo,the theoretical calculations indicate that the superconductivity can be attributed to the strong coupling between the electrons from the partially filled d band and the phonons from the frequency zone of 200-400 cm^(-1).展开更多
We present measurements of the 2p-3d transition opacity of a hot molybdenum-scandium sample with nearly half-vacant molybdenum M-shell configurations.A plastic-tamped molybdenum-scandium foil sample is radiatively hea...We present measurements of the 2p-3d transition opacity of a hot molybdenum-scandium sample with nearly half-vacant molybdenum M-shell configurations.A plastic-tamped molybdenum-scandium foil sample is radiatively heated to high temperature in a compact D-shaped gold Hohlraum driven by∼30 kJ laser energy at the SG-100 kJ laser facility.X rays transmitted through the molybdenum and scandium plasmas are diffracted by crystals and finally recorded by image plates.The electron temperatures in the sample in particular spatial and temporal zones are determined by the K-shell absorption of the scandium plasma.A combination of the IRAD3D view factor code and the MULTI hydrodynamic code is used to simulate the spatial distribution and temporal behavior of the sample temperature and density.The inferred temperature in the molybdenum plasma reaches a average of 138±11 eV.A detailed configuration-accounting calculation of the n=2–3 transition absorption of the molybdenum plasma is compared with experimental measurements and quite good agreement is found.The present measurements provide an opportunity to test opacity models for complicated M-shell configurations.展开更多
The molybdenum carbide(Mo_(2)C)has been regarded as one of the most cost-efficient and stable electrocatalyst for the hydrogen evolution reaction(HER)by the virtue of its Pt-like electronic structures.However,the inhe...The molybdenum carbide(Mo_(2)C)has been regarded as one of the most cost-efficient and stable electrocatalyst for the hydrogen evolution reaction(HER)by the virtue of its Pt-like electronic structures.However,the inherent limitation of high density of empty valence band significantly reduces its catalytic reactivity by reason of strong hydrogen desorption resistance.Herein,we propose a multiscale confinement synthesis method to design the nitrogen-rich Mo_(2)C for modulating the band structure via decomposing the pre-coordination bonded polymer in a pressure-tight tube sealing system.Pre-bonded c/N-Mo in the coordination precursor constructs a micro-confinement space,enabling the homogeneous nitrogenization in-situ happened during the formation of Mo_(2)C.Simultaneously,the evolved gases from the precursor decomposition in tube sealing system establish a macro-confinement environment,preventing the lattice N escape and further endowing a continuous nitridation.Combining the multiscale confinement effects,the nitrogen-rich Mo2C displays as high as 25%N-Mo concentration in carbide lattice,leading to a satisfactory band structure.Accordingly,the constructed nitrogen-rich Mo_(2)C reveals an adorable catalytic activity for HER in both alkaline and acid solution.It is anticipated that the multiscale confinement synthesis strategy presents guideline for the rational design of electrocatalysts and beyond.展开更多
The preparation process of sodium molybdate has the disadvantages of high energy consumption,low thermal efficiency,and high raw material requirement of molybdenum trioxide,in order to realize the green and efficient ...The preparation process of sodium molybdate has the disadvantages of high energy consumption,low thermal efficiency,and high raw material requirement of molybdenum trioxide,in order to realize the green and efficient development of molybdenum concentrate resources,this paper proposes a new process for efficient recovery of molybdenum from molybdenum concentrate and preparation of sodium molybdate by microwave-enhanced roasting and alkali leaching.Thermodynamic analysis indicated the feasibility of oxidation roasting of molybdenum concentrate.The effects of roasting temperature,holding time,and power-to-mass ratio on the oxidation product and leaching product sodium molybdate (Na_(2)MoO_(4)·2H_(2)O) were investigated.Under the optimal process conditions:roasting temperature of 700℃,holding time of 110 min,and power-to-mass ratio of 110 W/g,the molybdenum state of existence was converted from MoS_(2) to Mo O3.The process of preparing sodium molybdate by alkali leaching of molybdenum calcine was investigated,the optimal leaching conditions include a solution concentration of 2.5 mol/L,a liquid-to-solid ratio of 2 mL/g,a leaching temperature of 60℃,and leaching solution termination at pH 8.The optimum conditions result in a leaching rate of sodium molybdate of 96.24%.Meanwhile,the content of sodium molybdate reaches 94.08wt%after leaching and removing impurities.Iron and aluminum impurities can be effectively separated by adjusting the pH of the leaching solution with sodium carbonate solution.This research avoids the shortcomings of the traditional process and utilizes the advantages of microwave metallurgy to prepare high-quality sodium molybdate,which provides a new idea for the highvalue utilization of molybdenum concentrate.展开更多
The molybdenum(Mo)isotope system is pivotal in reconstructing marine redox changes throughout Earth’s history and has emerged as a promising tracer for igneous and metamorphic processes.Understanding its composition ...The molybdenum(Mo)isotope system is pivotal in reconstructing marine redox changes throughout Earth’s history and has emerged as a promising tracer for igneous and metamorphic processes.Understanding its composition and variation across major geochemical reservoirs is essential for its application in investigating high-temperature processes.However,there is debate regarding theδ^(98/95)Mo value of the Earth’s mantle,with estimates ranging from sub-chondritic to super-chondritic values.Recent analyses of global mid-ocean ridge basalt(MORB)glasses revealed significantδ^(98/95)Mo variations attributed to mantle heterogeneity,proposing a two-component mixing model to explain the observed variation.Complementary studies confirmed the sub-chondriticδ^(98/95)Mo of the depleted upper mantle,suggesting remixing of subduction-modified oceanic crust as a plausible mechanism.These findings underscore the role of Mo isotopes as effective tracers for understanding dynamic processes associated with mantle-crustal recycling.展开更多
Hydrogen production via water electrolysis defines the novel energy vector for achieving a sustainable society.However,the true progress of the given technology is hindered by the sluggish and complex hydrogen evoluti...Hydrogen production via water electrolysis defines the novel energy vector for achieving a sustainable society.However,the true progress of the given technology is hindered by the sluggish and complex hydrogen evolution reaction(HER)occurring at the cathodic side of the system where overpriced and scarce Pt-based electrocatalysts are usually employed.Therefore,efficient platinum group metals(PGMs)-free electrocatalysts to carry out HER with accelerated kinetics are urgently demanded.In this scenario,molybdenum disulfide(MoS_(2))owing to efficacious structural attributes and optimum hydrogen-binding free energy(ΔG_(H*))is emerging as a reliable alternative to PGMs.However,the performance of MoS_(2)-based electrocatalysts is still far away from the benchmark performance.The HER activity of MoS_(2)can be improved by engineering the structural parameters i.e.,doping,defects inducement,modulating the electronic structure,stabilizing the 1 T phase,creating nanocomposites,and altering the morphologies using appropriate fabrication pathways.Here,we have comprehensively reviewed the majority of the scientific endeavors published in recent years to uplift the HER activity of MoS_(2)-based electrocatalysts using different methods.Advancements in the major fabrication strategies including hydrothermal synthesis methods,chemical vapor deposition,exfoliation techniques,plasma treatments,chemical methodologies,etc.to tune the structural parameters and hence their ultimate influence on the electrocatalytic activity in acidic and/or alkaline media have been thoroughly discussed.This study can provide encyclopedic insights about the fabrication routes that have been pursued to improve the HER performance of MoS_(2)-based electrocatalysts.展开更多
Currently the catalysis of hydrogen evolution reaction(HER)is mainly focused on the inherent electrocatalytic activity at relatively lower current densities while scarce at high current densities.Nevertheless,the latt...Currently the catalysis of hydrogen evolution reaction(HER)is mainly focused on the inherent electrocatalytic activity at relatively lower current densities while scarce at high current densities.Nevertheless,the latter is highly demanding in efficient mass-production of hydrogen.A SiO_(2) nanospheres template-synthesis is used to prepare mesoporous molybdenum carbide nanocrystals-embedded nitrogen-doped carbon foams(mp-Mo_(2)C/NC).The material shows much more excellent catalytic activity than the non-etched Mo_(2)C/NC toward hydrogen evolution reaction(HER)in acidic medium.More interestingly mp-Mo_(2)C/NC still has larger overpotential than Pt/C at lower current densities,but possess remarkably smaller overpotential than the latter at higher current densities for much better electrocatalytic performance.An approach is developed to investigate the electrode kinetics by Tafel plots,especially with eliminating the diffusion effect,indicating that Pt/C and mp-Mo_(2)C/NC display different reaction mechanisms.At low current densities the former presents reversible reaction,while the latter shows mixed electrochemical polarization/reversible electrode process.In the region of higher current densities,the former becomes totally gas-diffusion controlled with large overpotential,while the latter can still retain an electrode polarization process for much lower overpotential at the same current density.Result endorses that the meso-porously structured mp-Mo_(2)C/NC plays a critical role in avoiding gas diffusion control-resulting large overpotential at high current densities.This work holds great potential for an inexpensive catalyst better than Pt/C in practical applications of mass-production hydrogen at high current densities,while clearly shedding fundamental lights on designs of rational HER catalysts for the uses at high current densities.展开更多
In a single sample plot,the total amount of heavy metals in the soil could not necessarily reflect the contents of their effective states.This must be considered when attempting to determine the degree of soil heavy-m...In a single sample plot,the total amount of heavy metals in the soil could not necessarily reflect the contents of their effective states.This must be considered when attempting to determine the degree of soil heavy-metal pollution in an area.In the present study,the soil around the molybdenum mining area in Huludao,China,was surveyed and sampled to evaluate soil heavy-metal pollution using the Nemerow multifactor pollution index method.The Tessier continuous extraction method was used to analyze the distribution of heavy-metal forms'and their content changes in the soil of this area.Thus,the bioactivity of heavy metals in the soil,the absorption of heavy metals by plants,and the distribution of heavy metals in plants were explored to provide data supporting the use of phytoremediation technology to treat the heavy-metal pollution in the molybdenum mining area and develop ecological restoration strategies for the area's wastelands.The pollution index results indicate that heavy-metal pollution in the soil around the tailings pond is severe,mainly due to Pb and Zn heavy metals.Heavy-metal pollution in the surrounding land is mainly due to Cd and Zn.Content analysis of the heavy-metal forms/states in soils shows that exchangeable forms,which are most effective and toxic to plants,of the following metals are highest in the following areas:Cd,Cu,and Zn in the mountains around the stope;Zn,Mo,and Cu in the cultivated land around the dump;and Cd,Zn,and Mo in the cultivated land around the tailings pond.The pollution index analysis provides a basic overview of soil heavy-metal pollution across the entire mining area.However,content analysis of heavy-metal forms/states better reflects the relationship between the availability of heavy metals in the soil and the effectiveness of plants.Thus,the latter analysis can help ensure that phytoremediation strategies are adequately targeted,science-based,and effective.展开更多
Selective synthesis of ethanol from syngas under the Co-based catalysts is still challenging due to the hard of regulating the active site Co^(0) and Co^(2+)ratio.In this work,a series of CaTi_(0.9-x)Co_(x)Mo_(0.1)O_(...Selective synthesis of ethanol from syngas under the Co-based catalysts is still challenging due to the hard of regulating the active site Co^(0) and Co^(2+)ratio.In this work,a series of CaTi_(0.9-x)Co_(x)Mo_(0.1)O_(3)(x=0,0.1-0.4)and CaTi_(0.7)Co_(0.3)O_(3) catalysts were prepared by using citric acid complexation method to promote the synthesis of ethanol.It was found that Mo species in the perovskite lattice can regulate the Co^(0) and Co^(2+)ratio through the domain-limiting effect of perovskite and the degree of Co reduction could be adjusted by changing the Co/Mo molar ratio.Among these investigated catalysts,the total selectivity of alcohols over the catalyst with the optimal Co/Mo ratio CaTi_(0.6)Co_(0.3)Mo_(0.1)O_(3) reached 39.1%,with ethanol accounting for 74.7%,which was ascribed to the moderate and tightly bound ratio of dissociative to non-dissociative adsorption sites on the surface and the balance of CH_(x)-CH_(y) coupling and C^(O) insertion.展开更多
Zero-dimensional environmentally friendly carbon quantum dots(CQDs)combined with two-di-mensional materials have a wide range of applications in optoelec-tronic devices.We combined steady-state and transient absorp-ti...Zero-dimensional environmentally friendly carbon quantum dots(CQDs)combined with two-di-mensional materials have a wide range of applications in optoelec-tronic devices.We combined steady-state and transient absorp-tion spectroscopies to study the energy transfer dynamics between CQDs and molybdenum disulfide(MoS_(2)).Transient absorption plots showed photoinduced absorption and stimulated emission features,which involved the intrinsic and defect states of CQDs.Adding MoS_(2)to CQDs solution,the lowest unoccupied molecular orbital of CQDs transferred energy to MoS_(2),which quenched the intrinsic emission at 390 nm.With addition of MoS_(2),CQD-MoS_(2)composites quenched defect emission at 490 nm and upward absorption,which originated from another energy transfer from the defect state.Two energy transfer paths between CQDs and MoS_(2)were efficiently manipulated by changing the concentration of MoS_(2),which laid a foundation for improving device performance.展开更多
Metal-ion capacitors could merit advantages from both batteries and capacitors,but they need to overcome the severe restrictions from their sluggish reaction kinetics of the battery type electrode and low specific cap...Metal-ion capacitors could merit advantages from both batteries and capacitors,but they need to overcome the severe restrictions from their sluggish reaction kinetics of the battery type electrode and low specific capacitance of capacitor type electrode for both high energy and power density.Herein,we use the Kirkendall effect for the first time to synthesize unique tubular hierarchical molybdenum dioxide with encapsulated nitrogen-doped carbon sheets while in situ realizing phosphorus-doping to create rich oxygen vacancies(P-MoO_(2-x)@NP-C)as a sodium-ion electrode.Experimental and theoretical analysis confirm that the P-doping introduced oxygen defects can partially convert the high-bond-energy Mo–O to low-bond-energy Mo–P,resulting in a low oxidation state of molybdenum for enhanced surface reactivity and rapid reaction kinetics.The as-prepared P-MoO_(2-x)@NP-C as an ion-battery electrode is further used to pair active N-doped carbon nanosheet(N-C-A)electrode for Na-ion hybrid capacitor,delivering excellent performance with an energy density of 140.3 Wh kg^(−1),a power density of 188.5 W kg^(−1)and long stable life in non-aqueous solution,which ranks the best among all reported MoO x-based hybrid capacitors.P-MoO_(2-x)@NP-C is also used to fabricate a zinc-ion hybrid capacitor,also accomplishing a remarkable energy density of 43.8 Wh kg^(−1),a power density of 93.9 W kg^(−1),and a long stable life@2A g^(−1)of 32000 cycles in aqueous solutions,solidly verifying its universal significance.This work not only demonstrates an innovative approach to synthesize high-performance metal ion hybrid capacitor materials but also reveals certain scientific insights into electron transfer enhancement mechanisms.展开更多
The Daheishan supergiant porphyry molybdenum deposit(also referred to as the Daheishan deposit)is the second largest molybdenum deposit in Asia and ranks fifth among the top seven molybdenum deposits globally with tot...The Daheishan supergiant porphyry molybdenum deposit(also referred to as the Daheishan deposit)is the second largest molybdenum deposit in Asia and ranks fifth among the top seven molybdenum deposits globally with total molybdenum reserves of 1.65 billion tons,an average molybdenum ore grade of 0.081%,and molybdenum resources of 1.09 million tons.The main ore body is housed in the granodiorite porphyry plutons and their surrounding inequigranular granodiorite plutons,with high-grade ores largely located in the ore-bearing granodiorite porphyries in the middle-upper part of the porphyry plutons.Specifically,it appears as an ore pipe with a large upper part and a small lower part,measuring about 1700 m in length and width,extending for about 500 m vertically,and covering an area of 2.3 km^(2).Mineralogically,the main ore body consists of molybdenite,chalcopyrite,and sphalerite horizontally from its center outward and exhibits molybdenite,azurite,and pyrite vertically from top to bottom.The primary ore minerals include pyrite and molybdenite,and the secondary ore minerals include sphalerite,chalcopyrite,tetrahedrite,and scheelite,with average grades of molybdenum,copper,sulfur,gallium,and rhenium being 0.081%,0.033%,1.67%,0.001%,and 0.0012%,respectively.The ore-forming fluids of the Daheishan deposit originated as the CO_(2)-H_(2)O-NaCl multiphase magmatic fluid system,rich in CO_(2)and bearing minor amounts of CH4,N2,and H2S,and later mixed with meteoric precipitation.In various mineralization stages,the ore-forming fluids had homogenization temperatures of>420℃‒400℃,360℃‒350℃,340℃‒230℃,220℃‒210℃,and 180℃‒160℃and salinities of>41.05%‒9.8%NaCleqv,38.16%‒4.48%NaCleqv,35.78%‒4.49%NaCleqv,7.43%NaCleqv,and 7.8%‒9.5%NaCleqv,respectively.The mineralization of the Daheishan deposit occurred at 186‒167 Ma.The granites closely related to the mineralization include granodiorites(granodiorite porphyries)and monzogranites(monzogranite porphyries),which were mineralized after magmatic evolution(189‒167 Ma).Moreover,these mineralization-related granites exhibit low initial strontium content and high initial neodymium content,indicating that these granites underwent crust-mantle mixing.The Daheishan deposit formed during the Early-Middle Jurassic,during which basaltic magma underplating induced the lower-crust melting,leading to the formation of magma chambers.After the fractional crystallization of magmas,ore-bearing fluids formed.As the temperature and pressure decreased,the ore-bearing fluids boiled drops while ascending,leading to massive unloading of metal elements.Consequently,brecciated and veinlet-disseminated ore bodies formed.展开更多
A direct hydrometallurgical route for nickel and molybdenum extraction from a nickel-molybdenum （Ni-Mo） ore using pressure acid leaching was studied. The nickel and molybdenum were extracted by acid leaching under o...A direct hydrometallurgical route for nickel and molybdenum extraction from a nickel-molybdenum （Ni-Mo） ore using pressure acid leaching was studied. The nickel and molybdenum were extracted by acid leaching under oxygen pressure. Compared with traditional roasting methods, this hydrometallurgical method eliminates SO2 and As203 emission （the Ni-Mo ore containing 15%-25% S）. Compared with existing alkali leaching recovery of molybdenum process, almost all the nickel and considerable molybdenum were extracted in the acid leaching process. Under oxygen pressure conditions, almost all the nickel and a substantial part of the molybdenum were dissolved into the acid leaching liquor and the other part of the molybdenum was left in the acid leach residue. The acid leach residue was further leached under alkaline （NaOH） conditions. Under optimal experimental conditions, the extraction rates nickel and molybdenum reached 97% and 96%, respectively.展开更多
The properties of a metal-oxide-semiconductor device on a single layer MoS_(2)(molybdenum disulfide)semiconductor are determined theoretically utilizing the concept of physics that the carrier effective masses in mate...The properties of a metal-oxide-semiconductor device on a single layer MoS_(2)(molybdenum disulfide)semiconductor are determined theoretically utilizing the concept of physics that the carrier effective masses in materials are related to the intrinsic Fermi energy levels in materials by the universal mass-energy equivalence equation given as dE/E=dm/m,where E is the energy and m is the mass of the free electron.The known parameters of electron effective mass of 0.48 m and the direct bandgap of 1.8 eV for monolayer MoS_(2) semiconductor are utilized to determine the properties of the MOS(metal-oxide-semiconductor)device,with the given previous research consequence that the threshold for electron heating in SiO_(2) is 2 MV/cm-eV.展开更多
The bioleaching of molybdenum from its sulfide ore using a Mo-resistant thermophilic bacterium sulfolobus metallics combined with a membrane biological reactor（MBR） was studied.The experimental results showed that t...The bioleaching of molybdenum from its sulfide ore using a Mo-resistant thermophilic bacterium sulfolobus metallics combined with a membrane biological reactor（MBR） was studied.The experimental results showed that the concentration of Mo can be controlled by filter of the membrane in MBR and the toxicity of Mo to microorganism is decreased in the process of bioleaching.It was also evidenced that there were different leaching rates of Ni and Mo when the concentration of Mo was different.After leaching for 20 d in the MBR at Mo concentration of 395 mg/L,the leaching rates of Ni and Mo reached the maximum of 79.57% and 56.23% respectively under the conditions of 100 g/L of mineral density,65 ℃,pH=2 and 1.0 L/min of the aeration rate.While 75.59% Ni and 54.33% Mo were leached out in column without membrane under the same conditions.展开更多
The adsorption behavior of D301 for molybdenum blue was investigated.The thermodynamics parameters in adsorption process were calculated and the adsorption kinetics was studied.The experimental results show that the a...The adsorption behavior of D301 for molybdenum blue was investigated.The thermodynamics parameters in adsorption process were calculated and the adsorption kinetics was studied.The experimental results show that the adsorption characteristic of D301 for molybdenum blue fits well with the Freundlich adsorption isotherm equation.In the adsorption process of D301 for molybdenum blue,both the enthalpy change ΔH and entropy change ΔS are positive,while the free energy change ΔG is negative when temperatures are in the range of 303-333 K.It is indicated that the adsorption is a spontaneous and endothermic process,and the elevated temperatures benefit to the adsorption.Kinetic studies show that the kinetic data are well described by double driving-force model,and the adsorption rate of molybdenum blue on D301 is controlled by the intraparticle diffusion during the adsorption process.The total kinetic equation is determined.展开更多
The effects of Ca-based additives on roasting properties of low-grade molybdenum concentrate were studied. The resultsshow that calcium-based additives can react with molybdenum concentrate to form CaSO4 and CaMoO4. T...The effects of Ca-based additives on roasting properties of low-grade molybdenum concentrate were studied. The resultsshow that calcium-based additives can react with molybdenum concentrate to form CaSO4 and CaMoO4. The initial oxidationtemperature of MoS2 is 450℃, while the formation of CaMoO4 and CaSO4 occurs above 500℃. The whole calcification reactionsare nearly completed between 600 and 650℃. However, raising the temperature further helps for the formation of CaMoO4 but isdisadvantageous to sulfur fixing rate and molybdenum retention rate. Calcification efficiency of Ca-based additives follows theorder： Ca（OH）2〉CaO〉CaCO3. With increasing the dosage of Ca（OH）2, the molybdenum retention rate and sulfur-fixing rate rise, butexcessive dosages would consume more acid during leaching process. The appropriate mass ratio of Ca（OH）2 to molybdenumconcentrate is 1：1. When roasted at 650 ℃ for 90 min, the molybdenum retention rate and the sulfur-fixing rate of low-grademolybdenum concentrate reach 100% and 92.92%, respectively, and the dissolution rate of molybdenum achieves 99.12% withcalcines being leached by sulphuric acid.展开更多
Based on the difference in tendency to polymerize between tungsten and molybdenum, a new method using D309 resin was propounded. The batch tests indicate that the optimum pH value and contact time for the separation a...Based on the difference in tendency to polymerize between tungsten and molybdenum, a new method using D309 resin was propounded. The batch tests indicate that the optimum pH value and contact time for the separation are 7.0 and 4 h respectively, the maxium separation factor of W and Mo is 9.29. And the experimental resules show that isothermal absorbing tungsten and molybdenum belongs to Langmuir model and Freundlich model respectively, and the absorbing kinetics for tungsten is controlled by intra-particle diffusion. With a solution containing 70 g/L WO3 and 28.97 g/L Mo, the effluent with a mass ratio of Mo to WO3 of 76 and the eluate with a mass ratio of WO3 to Mo of 53.33 are obtained after column test.展开更多
In order to develop a low-cost approach for separating macro amounts of Mo and W, the effects of parameters on the separation using FeSO4 as precipitation reagent were studied. The results show that the optimum reacti...In order to develop a low-cost approach for separating macro amounts of Mo and W, the effects of parameters on the separation using FeSO4 as precipitation reagent were studied. The results show that the optimum reaction temperature is 10 °C, and the separation factor does not further improve after a reaction time of 7 h. Moreover, slow dropping speed of the precipitation reagent is beneficial for improving the separation efficiency. When the H＋/W molar ratio is below 1/1, the addition of acid to a neutral solution is favorable to the separation. For the solution with an ammonium concentration below 3 mol/L, the separation factor is high due to the high W-precipitation rate. Furthermore, the method is also effective when it is applied to industrial solution containing some other impurities. All these indicate the ferrous salts have great potential for removing W from Mo on a commercial scale.展开更多
The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0....The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.展开更多
基金Project supported by the National Key R&D Program of China (Grant No.2022YFA1405500)the National Natural Science Foundation of China (Grant Nos.52372257 and 52072188)+1 种基金the Program for Changjiang Scholars and Innovative Research Team in University (Grant No.IRT-15R23)the Zhejiang Provincial Science and Technology Innovation Team (Grant No.2021R01004)。
文摘Element superconductors with the single atoms provide clean and fundamental platforms for studying superconductivity.Although elements with d electrons are usually not favored by conventional BCS,the record superconducting critical temperature(T_(c))in element scandium(S_(c))has further ignited the intensive attention on transition metals.The element molybdenum(M_o)with a half-full d-orbital is studied in our work,which fills the gap in the study of Mo under high pressure and investigates the pressure dependence of superconductivity.In this work,we exhibit a robust superconductivity of Mo in the pressure range of 5 GPa to 160 GPa via high-pressure electrical transport measurements,the T_(c) varies at a rate of0.013 K/GPa to 8.56 K at 160 GPa.Moreover,the superconductivity is evidenced by the T_(c) shifting to lower temperature under applied magnetic fields,and the upper critical magnetic fields are extrapolated by the WHH equation and GL equation;the results indicate that the maximum upper critical magnetic field is estimated to be 8.24 T at 137 GPa.We further investigate the superconducting mechanism of Mo,the theoretical calculations indicate that the superconductivity can be attributed to the strong coupling between the electrons from the partially filled d band and the phonons from the frequency zone of 200-400 cm^(-1).
基金supported by the National Nature Science Foundation of China(Grant Nos.12335015,12375238,12374261,11734013,and 11704350)the Presidential Foundation of the China Academy of Engineering Physics(Grant No.YZJJLX2017010)+2 种基金the CAEP Foundation(Grant No.CX2019023)the Science Challenge Project(Grant Nos.TZ2018001 and TZ2018005)the National Key R&D Program of China(Grant No.2017YFA0403200).
文摘We present measurements of the 2p-3d transition opacity of a hot molybdenum-scandium sample with nearly half-vacant molybdenum M-shell configurations.A plastic-tamped molybdenum-scandium foil sample is radiatively heated to high temperature in a compact D-shaped gold Hohlraum driven by∼30 kJ laser energy at the SG-100 kJ laser facility.X rays transmitted through the molybdenum and scandium plasmas are diffracted by crystals and finally recorded by image plates.The electron temperatures in the sample in particular spatial and temporal zones are determined by the K-shell absorption of the scandium plasma.A combination of the IRAD3D view factor code and the MULTI hydrodynamic code is used to simulate the spatial distribution and temporal behavior of the sample temperature and density.The inferred temperature in the molybdenum plasma reaches a average of 138±11 eV.A detailed configuration-accounting calculation of the n=2–3 transition absorption of the molybdenum plasma is compared with experimental measurements and quite good agreement is found.The present measurements provide an opportunity to test opacity models for complicated M-shell configurations.
基金supported by the National Natural Science Foundation of China(52372201,52125202,52202247)the Natural Science Foundation of Jiangsu Province(1192261031693)the Fundamental Research Funds for the Central Universities(30919011110,1191030558)。
文摘The molybdenum carbide(Mo_(2)C)has been regarded as one of the most cost-efficient and stable electrocatalyst for the hydrogen evolution reaction(HER)by the virtue of its Pt-like electronic structures.However,the inherent limitation of high density of empty valence band significantly reduces its catalytic reactivity by reason of strong hydrogen desorption resistance.Herein,we propose a multiscale confinement synthesis method to design the nitrogen-rich Mo_(2)C for modulating the band structure via decomposing the pre-coordination bonded polymer in a pressure-tight tube sealing system.Pre-bonded c/N-Mo in the coordination precursor constructs a micro-confinement space,enabling the homogeneous nitrogenization in-situ happened during the formation of Mo_(2)C.Simultaneously,the evolved gases from the precursor decomposition in tube sealing system establish a macro-confinement environment,preventing the lattice N escape and further endowing a continuous nitridation.Combining the multiscale confinement effects,the nitrogen-rich Mo2C displays as high as 25%N-Mo concentration in carbide lattice,leading to a satisfactory band structure.Accordingly,the constructed nitrogen-rich Mo_(2)C reveals an adorable catalytic activity for HER in both alkaline and acid solution.It is anticipated that the multiscale confinement synthesis strategy presents guideline for the rational design of electrocatalysts and beyond.
基金financially supported by the National Natural Science Foundation of China (No.51964046)。
文摘The preparation process of sodium molybdate has the disadvantages of high energy consumption,low thermal efficiency,and high raw material requirement of molybdenum trioxide,in order to realize the green and efficient development of molybdenum concentrate resources,this paper proposes a new process for efficient recovery of molybdenum from molybdenum concentrate and preparation of sodium molybdate by microwave-enhanced roasting and alkali leaching.Thermodynamic analysis indicated the feasibility of oxidation roasting of molybdenum concentrate.The effects of roasting temperature,holding time,and power-to-mass ratio on the oxidation product and leaching product sodium molybdate (Na_(2)MoO_(4)·2H_(2)O) were investigated.Under the optimal process conditions:roasting temperature of 700℃,holding time of 110 min,and power-to-mass ratio of 110 W/g,the molybdenum state of existence was converted from MoS_(2) to Mo O3.The process of preparing sodium molybdate by alkali leaching of molybdenum calcine was investigated,the optimal leaching conditions include a solution concentration of 2.5 mol/L,a liquid-to-solid ratio of 2 mL/g,a leaching temperature of 60℃,and leaching solution termination at pH 8.The optimum conditions result in a leaching rate of sodium molybdate of 96.24%.Meanwhile,the content of sodium molybdate reaches 94.08wt%after leaching and removing impurities.Iron and aluminum impurities can be effectively separated by adjusting the pH of the leaching solution with sodium carbonate solution.This research avoids the shortcomings of the traditional process and utilizes the advantages of microwave metallurgy to prepare high-quality sodium molybdate,which provides a new idea for the highvalue utilization of molybdenum concentrate.
基金the National Natural Science Foundation of China(Nos.42176087,42322605)the Laoshan Laboratory(No.LSKJ202204100)the Youth Innovation Promotion Association,Chinese Academy of Sciences(No.2021206)。
文摘The molybdenum(Mo)isotope system is pivotal in reconstructing marine redox changes throughout Earth’s history and has emerged as a promising tracer for igneous and metamorphic processes.Understanding its composition and variation across major geochemical reservoirs is essential for its application in investigating high-temperature processes.However,there is debate regarding theδ^(98/95)Mo value of the Earth’s mantle,with estimates ranging from sub-chondritic to super-chondritic values.Recent analyses of global mid-ocean ridge basalt(MORB)glasses revealed significantδ^(98/95)Mo variations attributed to mantle heterogeneity,proposing a two-component mixing model to explain the observed variation.Complementary studies confirmed the sub-chondriticδ^(98/95)Mo of the depleted upper mantle,suggesting remixing of subduction-modified oceanic crust as a plausible mechanism.These findings underscore the role of Mo isotopes as effective tracers for understanding dynamic processes associated with mantle-crustal recycling.
基金the Italian Ministry of University and Research(MUR)through the“Rita Levi Montalcini 2018”Fellowship(Grant number PGR18MAZLI)ENEA–UNIMIB PNRR agreement(Attività1.1.3 del PNRR POR H2)+1 种基金the Ministry of Science and Technology(State of Israel)and the Ministry of Foreign Affairs and International Cooperation–Directorate General for Cultural and Economic Promotion and Innovation(Italian Republic),respectively,within the bilateral project Italy-Israel(WE-CAT)the Italian ministry MUR for funding through the FISR 2019 project AMPERE(FISR2019_01294)。
文摘Hydrogen production via water electrolysis defines the novel energy vector for achieving a sustainable society.However,the true progress of the given technology is hindered by the sluggish and complex hydrogen evolution reaction(HER)occurring at the cathodic side of the system where overpriced and scarce Pt-based electrocatalysts are usually employed.Therefore,efficient platinum group metals(PGMs)-free electrocatalysts to carry out HER with accelerated kinetics are urgently demanded.In this scenario,molybdenum disulfide(MoS_(2))owing to efficacious structural attributes and optimum hydrogen-binding free energy(ΔG_(H*))is emerging as a reliable alternative to PGMs.However,the performance of MoS_(2)-based electrocatalysts is still far away from the benchmark performance.The HER activity of MoS_(2)can be improved by engineering the structural parameters i.e.,doping,defects inducement,modulating the electronic structure,stabilizing the 1 T phase,creating nanocomposites,and altering the morphologies using appropriate fabrication pathways.Here,we have comprehensively reviewed the majority of the scientific endeavors published in recent years to uplift the HER activity of MoS_(2)-based electrocatalysts using different methods.Advancements in the major fabrication strategies including hydrothermal synthesis methods,chemical vapor deposition,exfoliation techniques,plasma treatments,chemical methodologies,etc.to tune the structural parameters and hence their ultimate influence on the electrocatalytic activity in acidic and/or alkaline media have been thoroughly discussed.This study can provide encyclopedic insights about the fabrication routes that have been pursued to improve the HER performance of MoS_(2)-based electrocatalysts.
基金supported by the Start-up grant from Suzhou University of Science and Technology.
文摘Currently the catalysis of hydrogen evolution reaction(HER)is mainly focused on the inherent electrocatalytic activity at relatively lower current densities while scarce at high current densities.Nevertheless,the latter is highly demanding in efficient mass-production of hydrogen.A SiO_(2) nanospheres template-synthesis is used to prepare mesoporous molybdenum carbide nanocrystals-embedded nitrogen-doped carbon foams(mp-Mo_(2)C/NC).The material shows much more excellent catalytic activity than the non-etched Mo_(2)C/NC toward hydrogen evolution reaction(HER)in acidic medium.More interestingly mp-Mo_(2)C/NC still has larger overpotential than Pt/C at lower current densities,but possess remarkably smaller overpotential than the latter at higher current densities for much better electrocatalytic performance.An approach is developed to investigate the electrode kinetics by Tafel plots,especially with eliminating the diffusion effect,indicating that Pt/C and mp-Mo_(2)C/NC display different reaction mechanisms.At low current densities the former presents reversible reaction,while the latter shows mixed electrochemical polarization/reversible electrode process.In the region of higher current densities,the former becomes totally gas-diffusion controlled with large overpotential,while the latter can still retain an electrode polarization process for much lower overpotential at the same current density.Result endorses that the meso-porously structured mp-Mo_(2)C/NC plays a critical role in avoiding gas diffusion control-resulting large overpotential at high current densities.This work holds great potential for an inexpensive catalyst better than Pt/C in practical applications of mass-production hydrogen at high current densities,while clearly shedding fundamental lights on designs of rational HER catalysts for the uses at high current densities.
基金financially supported by the National Natural Science Foundation of China (51504066).
文摘In a single sample plot,the total amount of heavy metals in the soil could not necessarily reflect the contents of their effective states.This must be considered when attempting to determine the degree of soil heavy-metal pollution in an area.In the present study,the soil around the molybdenum mining area in Huludao,China,was surveyed and sampled to evaluate soil heavy-metal pollution using the Nemerow multifactor pollution index method.The Tessier continuous extraction method was used to analyze the distribution of heavy-metal forms'and their content changes in the soil of this area.Thus,the bioactivity of heavy metals in the soil,the absorption of heavy metals by plants,and the distribution of heavy metals in plants were explored to provide data supporting the use of phytoremediation technology to treat the heavy-metal pollution in the molybdenum mining area and develop ecological restoration strategies for the area's wastelands.The pollution index results indicate that heavy-metal pollution in the soil around the tailings pond is severe,mainly due to Pb and Zn heavy metals.Heavy-metal pollution in the surrounding land is mainly due to Cd and Zn.Content analysis of the heavy-metal forms/states in soils shows that exchangeable forms,which are most effective and toxic to plants,of the following metals are highest in the following areas:Cd,Cu,and Zn in the mountains around the stope;Zn,Mo,and Cu in the cultivated land around the dump;and Cd,Zn,and Mo in the cultivated land around the tailings pond.The pollution index analysis provides a basic overview of soil heavy-metal pollution across the entire mining area.However,content analysis of heavy-metal forms/states better reflects the relationship between the availability of heavy metals in the soil and the effectiveness of plants.Thus,the latter analysis can help ensure that phytoremediation strategies are adequately targeted,science-based,and effective.
基金National Natural Science Foundation of China(21872101,21962014)Science and Technology Program of Zungeer County,Inner Mongolia(2020YY-12)。
文摘Selective synthesis of ethanol from syngas under the Co-based catalysts is still challenging due to the hard of regulating the active site Co^(0) and Co^(2+)ratio.In this work,a series of CaTi_(0.9-x)Co_(x)Mo_(0.1)O_(3)(x=0,0.1-0.4)and CaTi_(0.7)Co_(0.3)O_(3) catalysts were prepared by using citric acid complexation method to promote the synthesis of ethanol.It was found that Mo species in the perovskite lattice can regulate the Co^(0) and Co^(2+)ratio through the domain-limiting effect of perovskite and the degree of Co reduction could be adjusted by changing the Co/Mo molar ratio.Among these investigated catalysts,the total selectivity of alcohols over the catalyst with the optimal Co/Mo ratio CaTi_(0.6)Co_(0.3)Mo_(0.1)O_(3) reached 39.1%,with ethanol accounting for 74.7%,which was ascribed to the moderate and tightly bound ratio of dissociative to non-dissociative adsorption sites on the surface and the balance of CH_(x)-CH_(y) coupling and C^(O) insertion.
基金supported by the National Natural Science Foundation of China(No.61805134 and No.11974229)Applied Basic Research Program in Shanxi Province,China(No.201801D221016 and No.202103021223254)+2 种基金Scientific and Technological Innovation Pro-grams of Higher Education Institutions in Shanxi(No.2020L0235 and No.2021L257)Linfen Key Re-search and Development Program(No.2028)Graduate Innovation Project in Shanxi Province(No.2022Y498).
文摘Zero-dimensional environmentally friendly carbon quantum dots(CQDs)combined with two-di-mensional materials have a wide range of applications in optoelec-tronic devices.We combined steady-state and transient absorp-tion spectroscopies to study the energy transfer dynamics between CQDs and molybdenum disulfide(MoS_(2)).Transient absorption plots showed photoinduced absorption and stimulated emission features,which involved the intrinsic and defect states of CQDs.Adding MoS_(2)to CQDs solution,the lowest unoccupied molecular orbital of CQDs transferred energy to MoS_(2),which quenched the intrinsic emission at 390 nm.With addition of MoS_(2),CQD-MoS_(2)composites quenched defect emission at 490 nm and upward absorption,which originated from another energy transfer from the defect state.Two energy transfer paths between CQDs and MoS_(2)were efficiently manipulated by changing the concentration of MoS_(2),which laid a foundation for improving device performance.
基金the financial support from the National Natural Science Foundation of China(51802269).
文摘Metal-ion capacitors could merit advantages from both batteries and capacitors,but they need to overcome the severe restrictions from their sluggish reaction kinetics of the battery type electrode and low specific capacitance of capacitor type electrode for both high energy and power density.Herein,we use the Kirkendall effect for the first time to synthesize unique tubular hierarchical molybdenum dioxide with encapsulated nitrogen-doped carbon sheets while in situ realizing phosphorus-doping to create rich oxygen vacancies(P-MoO_(2-x)@NP-C)as a sodium-ion electrode.Experimental and theoretical analysis confirm that the P-doping introduced oxygen defects can partially convert the high-bond-energy Mo–O to low-bond-energy Mo–P,resulting in a low oxidation state of molybdenum for enhanced surface reactivity and rapid reaction kinetics.The as-prepared P-MoO_(2-x)@NP-C as an ion-battery electrode is further used to pair active N-doped carbon nanosheet(N-C-A)electrode for Na-ion hybrid capacitor,delivering excellent performance with an energy density of 140.3 Wh kg^(−1),a power density of 188.5 W kg^(−1)and long stable life in non-aqueous solution,which ranks the best among all reported MoO x-based hybrid capacitors.P-MoO_(2-x)@NP-C is also used to fabricate a zinc-ion hybrid capacitor,also accomplishing a remarkable energy density of 43.8 Wh kg^(−1),a power density of 93.9 W kg^(−1),and a long stable life@2A g^(−1)of 32000 cycles in aqueous solutions,solidly verifying its universal significance.This work not only demonstrates an innovative approach to synthesize high-performance metal ion hybrid capacitor materials but also reveals certain scientific insights into electron transfer enhancement mechanisms.
基金This study was jointly funded by a project of the National Natural Science Foundation of China(42102087)a project of the China Postdoctoral Science Foundation(2022M712966)a key special project of the Ministry of Science and Technology of China(2021QZKK0304).
文摘The Daheishan supergiant porphyry molybdenum deposit(also referred to as the Daheishan deposit)is the second largest molybdenum deposit in Asia and ranks fifth among the top seven molybdenum deposits globally with total molybdenum reserves of 1.65 billion tons,an average molybdenum ore grade of 0.081%,and molybdenum resources of 1.09 million tons.The main ore body is housed in the granodiorite porphyry plutons and their surrounding inequigranular granodiorite plutons,with high-grade ores largely located in the ore-bearing granodiorite porphyries in the middle-upper part of the porphyry plutons.Specifically,it appears as an ore pipe with a large upper part and a small lower part,measuring about 1700 m in length and width,extending for about 500 m vertically,and covering an area of 2.3 km^(2).Mineralogically,the main ore body consists of molybdenite,chalcopyrite,and sphalerite horizontally from its center outward and exhibits molybdenite,azurite,and pyrite vertically from top to bottom.The primary ore minerals include pyrite and molybdenite,and the secondary ore minerals include sphalerite,chalcopyrite,tetrahedrite,and scheelite,with average grades of molybdenum,copper,sulfur,gallium,and rhenium being 0.081%,0.033%,1.67%,0.001%,and 0.0012%,respectively.The ore-forming fluids of the Daheishan deposit originated as the CO_(2)-H_(2)O-NaCl multiphase magmatic fluid system,rich in CO_(2)and bearing minor amounts of CH4,N2,and H2S,and later mixed with meteoric precipitation.In various mineralization stages,the ore-forming fluids had homogenization temperatures of>420℃‒400℃,360℃‒350℃,340℃‒230℃,220℃‒210℃,and 180℃‒160℃and salinities of>41.05%‒9.8%NaCleqv,38.16%‒4.48%NaCleqv,35.78%‒4.49%NaCleqv,7.43%NaCleqv,and 7.8%‒9.5%NaCleqv,respectively.The mineralization of the Daheishan deposit occurred at 186‒167 Ma.The granites closely related to the mineralization include granodiorites(granodiorite porphyries)and monzogranites(monzogranite porphyries),which were mineralized after magmatic evolution(189‒167 Ma).Moreover,these mineralization-related granites exhibit low initial strontium content and high initial neodymium content,indicating that these granites underwent crust-mantle mixing.The Daheishan deposit formed during the Early-Middle Jurassic,during which basaltic magma underplating induced the lower-crust melting,leading to the formation of magma chambers.After the fractional crystallization of magmas,ore-bearing fluids formed.As the temperature and pressure decreased,the ore-bearing fluids boiled drops while ascending,leading to massive unloading of metal elements.Consequently,brecciated and veinlet-disseminated ore bodies formed.
基金Projects(51174104,50874053)supported by the National Natural Science Foundation of ChinaProject(2009AA06Z106)supported by Hi-Tech Research and Development Program of ChinaProject(20115314110001)supported by Doctoral Fund of Ministry of Education of China
文摘A direct hydrometallurgical route for nickel and molybdenum extraction from a nickel-molybdenum （Ni-Mo） ore using pressure acid leaching was studied. The nickel and molybdenum were extracted by acid leaching under oxygen pressure. Compared with traditional roasting methods, this hydrometallurgical method eliminates SO2 and As203 emission （the Ni-Mo ore containing 15%-25% S）. Compared with existing alkali leaching recovery of molybdenum process, almost all the nickel and considerable molybdenum were extracted in the acid leaching process. Under oxygen pressure conditions, almost all the nickel and a substantial part of the molybdenum were dissolved into the acid leaching liquor and the other part of the molybdenum was left in the acid leach residue. The acid leach residue was further leached under alkaline （NaOH） conditions. Under optimal experimental conditions, the extraction rates nickel and molybdenum reached 97% and 96%, respectively.
文摘The properties of a metal-oxide-semiconductor device on a single layer MoS_(2)(molybdenum disulfide)semiconductor are determined theoretically utilizing the concept of physics that the carrier effective masses in materials are related to the intrinsic Fermi energy levels in materials by the universal mass-energy equivalence equation given as dE/E=dm/m,where E is the energy and m is the mass of the free electron.The known parameters of electron effective mass of 0.48 m and the direct bandgap of 1.8 eV for monolayer MoS_(2) semiconductor are utilized to determine the properties of the MOS(metal-oxide-semiconductor)device,with the given previous research consequence that the threshold for electron heating in SiO_(2) is 2 MV/cm-eV.
文摘The bioleaching of molybdenum from its sulfide ore using a Mo-resistant thermophilic bacterium sulfolobus metallics combined with a membrane biological reactor（MBR） was studied.The experimental results showed that the concentration of Mo can be controlled by filter of the membrane in MBR and the toxicity of Mo to microorganism is decreased in the process of bioleaching.It was also evidenced that there were different leaching rates of Ni and Mo when the concentration of Mo was different.After leaching for 20 d in the MBR at Mo concentration of 395 mg/L,the leaching rates of Ni and Mo reached the maximum of 79.57% and 56.23% respectively under the conditions of 100 g/L of mineral density,65 ℃,pH=2 and 1.0 L/min of the aeration rate.While 75.59% Ni and 54.33% Mo were leached out in column without membrane under the same conditions.
基金Project(2007AA06Z129) supported by the High-tech Research and Development Program of China
文摘The adsorption behavior of D301 for molybdenum blue was investigated.The thermodynamics parameters in adsorption process were calculated and the adsorption kinetics was studied.The experimental results show that the adsorption characteristic of D301 for molybdenum blue fits well with the Freundlich adsorption isotherm equation.In the adsorption process of D301 for molybdenum blue,both the enthalpy change ΔH and entropy change ΔS are positive,while the free energy change ΔG is negative when temperatures are in the range of 303-333 K.It is indicated that the adsorption is a spontaneous and endothermic process,and the elevated temperatures benefit to the adsorption.Kinetic studies show that the kinetic data are well described by double driving-force model,and the adsorption rate of molybdenum blue on D301 is controlled by the intraparticle diffusion during the adsorption process.The total kinetic equation is determined.
基金Project(51304245)supported by the National Natural Science Foundation of ChinaProject(2014T70691)supported by the Postdoctoral Science Foundation of China+1 种基金Project(2015CX005)supported by the Innovation Driven Plan of Central South University,ChinaProject supported by the Hunan Provincial Co-innovation Center for Clean and Efficient Utilization of Strategic Metal Mineral Resources,China
文摘The effects of Ca-based additives on roasting properties of low-grade molybdenum concentrate were studied. The resultsshow that calcium-based additives can react with molybdenum concentrate to form CaSO4 and CaMoO4. The initial oxidationtemperature of MoS2 is 450℃, while the formation of CaMoO4 and CaSO4 occurs above 500℃. The whole calcification reactionsare nearly completed between 600 and 650℃. However, raising the temperature further helps for the formation of CaMoO4 but isdisadvantageous to sulfur fixing rate and molybdenum retention rate. Calcification efficiency of Ca-based additives follows theorder： Ca（OH）2〉CaO〉CaCO3. With increasing the dosage of Ca（OH）2, the molybdenum retention rate and sulfur-fixing rate rise, butexcessive dosages would consume more acid during leaching process. The appropriate mass ratio of Ca（OH）2 to molybdenumconcentrate is 1：1. When roasted at 650 ℃ for 90 min, the molybdenum retention rate and the sulfur-fixing rate of low-grademolybdenum concentrate reach 100% and 92.92%, respectively, and the dissolution rate of molybdenum achieves 99.12% withcalcines being leached by sulphuric acid.
基金Project(51174232)supported by the National Natural Science Foundation of China
文摘Based on the difference in tendency to polymerize between tungsten and molybdenum, a new method using D309 resin was propounded. The batch tests indicate that the optimum pH value and contact time for the separation are 7.0 and 4 h respectively, the maxium separation factor of W and Mo is 9.29. And the experimental resules show that isothermal absorbing tungsten and molybdenum belongs to Langmuir model and Freundlich model respectively, and the absorbing kinetics for tungsten is controlled by intra-particle diffusion. With a solution containing 70 g/L WO3 and 28.97 g/L Mo, the effluent with a mass ratio of Mo to WO3 of 76 and the eluate with a mass ratio of WO3 to Mo of 53.33 are obtained after column test.
基金Project (2007AA06Z129) supported by the National High-tech Research and Development Program of China
文摘In order to develop a low-cost approach for separating macro amounts of Mo and W, the effects of parameters on the separation using FeSO4 as precipitation reagent were studied. The results show that the optimum reaction temperature is 10 °C, and the separation factor does not further improve after a reaction time of 7 h. Moreover, slow dropping speed of the precipitation reagent is beneficial for improving the separation efficiency. When the H＋/W molar ratio is below 1/1, the addition of acid to a neutral solution is favorable to the separation. For the solution with an ammonium concentration below 3 mol/L, the separation factor is high due to the high W-precipitation rate. Furthermore, the method is also effective when it is applied to industrial solution containing some other impurities. All these indicate the ferrous salts have great potential for removing W from Mo on a commercial scale.
基金supported by the National Natural Science Foundation of China(21173100 and 21320102001)~~
文摘The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.
