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
To enhance the mechanical properties of molybdenum alloys at both room and high temperatures,Mo-14Re-1CeO_(2)alloy was synthesized using the powder metallurgy method,and the corresponding microstructure and mechanical...To enhance the mechanical properties of molybdenum alloys at both room and high temperatures,Mo-14Re-1CeO_(2)alloy was synthesized using the powder metallurgy method,and the corresponding microstructure and mechanical properties were characterized.The results indicate that the ultimate tensile strength of Mo-14Re-1CeO_(2)reaches 657 MPa,with a total elongation of 35.2%,significantly higher than those of pure molybdenum(453 MPa,and 7.01%).Furthermore,the compression strength of Mo-14Re-1CeO_(2)at high temperature(1200℃)achieves 355 MPa,which is still larger than that of pure molybdenum(221 MPa).It is revealed that there is a coherent interface between CeO_(2)and the Mo-14Re matrix with CeO_(2)particles uniformly distributed in both intergranular and intragranular regions.The improvements in mechanical properties are primarily attributed to the formation of Mo-Re solid solution,grain refinement,and dispersion strengthening effect of CeO_(2).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
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 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
Molybdenum is one of the dominant minerals in China because of its rich reserves.In recent years,outstanding breakthroughs have been made in molybdenum prospecting in China,and the distribution of molybdenum deposits ...Molybdenum is one of the dominant minerals in China because of its rich reserves.In recent years,outstanding breakthroughs have been made in molybdenum prospecting in China,and the distribution of molybdenum deposits in China is found to have a "planar pattern".In general,the molybdenum deposits are concentrated in eastern China,including the largest molybdenum reserves of Henan Province.In terms of the scale of molybdenum deposits,the identified resources of the superlarge deposits are the most important,which account for about 53% of the whole country,and those of the large deposits account for about 30%,those of the medium-sized deposits account for about 14%,those of the small-sized deposits,mine spots and mineralization account for about 3%.The molybdenum deposits are mainly classified as porphyry type,skarn type,hydrothermal(vein) type and sedimentary(metamorphic) type in genesis,and the identified resources of these types account for 85.75%,8.83%,2.79%and 2.63% of the total resources respectively.Based on the statistics of precise chronology data of molybdenites Re-Os,Mo-mineralization can be divided into 6 periods in Chinese geological history,which are Precambrian(〉800 Ma),Cambrian-Silurian(540-415 Ma,Caledonian),Devonian-Permian(400-290 Ma,Hecynian),Triassic(260-200 Ma,Indosinian),Jurassic-Cretaceous(195-70 Ma,Yanshanian) and Paleogene-Neogene(65-10 Ma,Himalayan).Mo mineralization during the Yanshanian period is the strongest one,in which about 76.69% of the Chinese total identified resources was formed.The second is the Himalayan period.According to spatial-temporal distribution characteristics of molybdenum deposits,the metallogenic regularity of molybdenum deposits was preliminarily summarized,and 41 level-Ⅲ molybdenum-forming belts,13 level-Ⅱ molybdenum-forming provinces and 4 level-Ⅰ molybdenum-forming domains were ascertained in the mainland of China.There are 39 metallogenic series of and 60 sub-series of molybdenum deposits with molybdenum as the dominant metal and corresponding representative molybdenum deposits proposed.Metallogenic lineages of molybdenum deposits were also established.Spatial-temporal evolution of different types of molybdenum deposits,and the relationship between Mo-mineralization and tectonic evolution have been discussed in this paper.On this basis,the authors think that element Mo is an effective tracer for recording the crustal evolution history of China.At present,there are some problems in the exploration of Mo deposits in China,such as uneven exploration degrees in eastern and western China,shallow exploration depth,low and uneven grade,complex associated components,difficulty of mineral development and utilization,increasing costs of prospecting,and so on.According to successful experience of superficial and deep prospecting and considering also the discussion above,some suggestions are proposed for the prospecting of molybdenum deposits in the future.展开更多
The phase composition, microstructure, thermal expansion coefficients, oxygen permeation properties and chemical stability of SrCo0.8Fe0.2O3-δ (SCFM) were investigated and compared with those of SrCo0.8Fe0.2O3-δ(...The phase composition, microstructure, thermal expansion coefficients, oxygen permeation properties and chemical stability of SrCo0.8Fe0.2O3-δ (SCFM) were investigated and compared with those of SrCo0.8Fe0.2O3-δ(SCF). Single phase SCFM was successfully prepared by a combined EDTA-citric method. SCFM shows a lower thermal expansion coefficient (24× 10^-6-29× 10^-6/K) than SCF between 500 and 1050 ℃, indicating a more stable structure. SCFM shows a high oxygen permeation flux, although the oxygen flux of SCFM decreases slightly because of Mo dopant. Furthermore, it was demonstrated that the doping of Mo in SCF can prevent the order-disorder transition and improves the chemical stability to CO2.展开更多
The performance of supported and unsupported molybdenum carbide for thepartial oxidation of methane (POM) to syngas was investigated. An evaluation of the catalystsindicates that bulk molybdenum carbide has a higher m...The performance of supported and unsupported molybdenum carbide for thepartial oxidation of methane (POM) to syngas was investigated. An evaluation of the catalystsindicates that bulk molybdenum carbide has a higher methane conversion during the initial stage buta lower selectivity to CO and H_2/CO ratio in the products. The rapid deactivation of the catalystis also a significant problem. However, the supported molybdenum carbide catalyst shows a muchhigher methane conversion, increased selectivity and significantly improved catalytic stability. Thecharacterization by XRD and BET specific area measurements depict an improved dispersion ofmolybdenum carbide when using alumina as a carrier. The bulk or the supported molybdenum carbideexists in the β-MO_2C phase, while it is transformed into molybdenum dioxide postcatalysis which isan important cause of molybdenum carbide deactivation.展开更多
A new method for the preparation of dinuclear molybdenum dithiocarbamates(MoDDCs) is reported.This new method allows for the control of the amount of sulfurization of the Mo2SxO4-x core(x = 1 to 4) in the dinuclear Mo...A new method for the preparation of dinuclear molybdenum dithiocarbamates(MoDDCs) is reported.This new method allows for the control of the amount of sulfurization of the Mo2SxO4-x core(x = 1 to 4) in the dinuclear MoDDCs.This control assists in the tailoring of specific tribological properties of the MoDDCs in both greases and lubricating oils.展开更多
To extract molybdenum and nickel from the roasted Ni-Mo ore, a process of hydrochloric acid leaching, sulphation roasting and water leaching was investigated. The results showed that this process could get a high leac...To extract molybdenum and nickel from the roasted Ni-Mo ore, a process of hydrochloric acid leaching, sulphation roasting and water leaching was investigated. The results showed that this process could get a high leaching rate of Mo and Ni. Under the optimum conditions of hydrochloric acid leaching (roasted Ni-Mo ore leached with 0.219 mL/g hydrochloric acid addition at 65 ℃ for 30 min with a L/S ratio of 3 mL/g), sulphation roasting (51.9% sulfiaric acid addition, roasting temperature 240 ℃ for 1 h), followed by leaching with the first stage hydrochloric acid leaching solution at 95 ℃ for 2 h, the leaching rates of Mo and Ni reached 95.8% and 91.3%, respectively.展开更多
The study of the leaching of vanadium(V) and molybdenum(Mo) from spent petrochemical catalysts in sodium hydroxide(NaO H) medium was performed using two approaches, namely, conventional leaching and microwave-assisted...The study of the leaching of vanadium(V) and molybdenum(Mo) from spent petrochemical catalysts in sodium hydroxide(NaO H) medium was performed using two approaches, namely, conventional leaching and microwave-assisted leaching methods. The influence of microwave power, leaching time, leaching temperature, and NaOH concentration on the leaching efficiency of spent petrochemical catalyst was investigated. Under microwave-assisted conditions(600 W, 10 min, 90°C, 2.0 mol·L^(-1) NaOH, and 0.20 g·mL^(-1) solid–liquid ratio), the leaching efficiencies of V and Mo reached 94.35% and 96.23%, respectively. It has been confirmed that microwave energy has considerable potential to enhance the efficiency of the leaching process and reduce the leaching time. It is suggested that the enhancement of the leaching efficiencies of V and Mo can be attributed to the existence of a thermal gradient between solid and liquid and the generation of cracks on the mineral surface.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supported by the National Key R&D Program of China(No.2022YFB3705402)。
文摘To enhance the mechanical properties of molybdenum alloys at both room and high temperatures,Mo-14Re-1CeO_(2)alloy was synthesized using the powder metallurgy method,and the corresponding microstructure and mechanical properties were characterized.The results indicate that the ultimate tensile strength of Mo-14Re-1CeO_(2)reaches 657 MPa,with a total elongation of 35.2%,significantly higher than those of pure molybdenum(453 MPa,and 7.01%).Furthermore,the compression strength of Mo-14Re-1CeO_(2)at high temperature(1200℃)achieves 355 MPa,which is still larger than that of pure molybdenum(221 MPa).It is revealed that there is a coherent interface between CeO_(2)and the Mo-14Re matrix with CeO_(2)particles uniformly distributed in both intergranular and intragranular regions.The improvements in mechanical properties are primarily attributed to the formation of Mo-Re solid solution,grain refinement,and dispersion strengthening effect of CeO_(2).
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 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.
基金funded by the National Natural Science Fund for Youth(Grant No.41402069)Scientific Research Fund of the China Central Non-Commercial Institute(Grant No.1305,K1022 and K1001)+1 种基金Geological Survey Program of comprehensive study of Chinese mineral geology and regional metallogenic regularity (Grant No.12120114039701,12120114039601)mineral resources potential evaluation(Grant No. 1212010633901)
文摘Molybdenum is one of the dominant minerals in China because of its rich reserves.In recent years,outstanding breakthroughs have been made in molybdenum prospecting in China,and the distribution of molybdenum deposits in China is found to have a "planar pattern".In general,the molybdenum deposits are concentrated in eastern China,including the largest molybdenum reserves of Henan Province.In terms of the scale of molybdenum deposits,the identified resources of the superlarge deposits are the most important,which account for about 53% of the whole country,and those of the large deposits account for about 30%,those of the medium-sized deposits account for about 14%,those of the small-sized deposits,mine spots and mineralization account for about 3%.The molybdenum deposits are mainly classified as porphyry type,skarn type,hydrothermal(vein) type and sedimentary(metamorphic) type in genesis,and the identified resources of these types account for 85.75%,8.83%,2.79%and 2.63% of the total resources respectively.Based on the statistics of precise chronology data of molybdenites Re-Os,Mo-mineralization can be divided into 6 periods in Chinese geological history,which are Precambrian(〉800 Ma),Cambrian-Silurian(540-415 Ma,Caledonian),Devonian-Permian(400-290 Ma,Hecynian),Triassic(260-200 Ma,Indosinian),Jurassic-Cretaceous(195-70 Ma,Yanshanian) and Paleogene-Neogene(65-10 Ma,Himalayan).Mo mineralization during the Yanshanian period is the strongest one,in which about 76.69% of the Chinese total identified resources was formed.The second is the Himalayan period.According to spatial-temporal distribution characteristics of molybdenum deposits,the metallogenic regularity of molybdenum deposits was preliminarily summarized,and 41 level-Ⅲ molybdenum-forming belts,13 level-Ⅱ molybdenum-forming provinces and 4 level-Ⅰ molybdenum-forming domains were ascertained in the mainland of China.There are 39 metallogenic series of and 60 sub-series of molybdenum deposits with molybdenum as the dominant metal and corresponding representative molybdenum deposits proposed.Metallogenic lineages of molybdenum deposits were also established.Spatial-temporal evolution of different types of molybdenum deposits,and the relationship between Mo-mineralization and tectonic evolution have been discussed in this paper.On this basis,the authors think that element Mo is an effective tracer for recording the crustal evolution history of China.At present,there are some problems in the exploration of Mo deposits in China,such as uneven exploration degrees in eastern and western China,shallow exploration depth,low and uneven grade,complex associated components,difficulty of mineral development and utilization,increasing costs of prospecting,and so on.According to successful experience of superficial and deep prospecting and considering also the discussion above,some suggestions are proposed for the prospecting of molybdenum deposits in the future.
文摘The phase composition, microstructure, thermal expansion coefficients, oxygen permeation properties and chemical stability of SrCo0.8Fe0.2O3-δ (SCFM) were investigated and compared with those of SrCo0.8Fe0.2O3-δ(SCF). Single phase SCFM was successfully prepared by a combined EDTA-citric method. SCFM shows a lower thermal expansion coefficient (24× 10^-6-29× 10^-6/K) than SCF between 500 and 1050 ℃, indicating a more stable structure. SCFM shows a high oxygen permeation flux, although the oxygen flux of SCFM decreases slightly because of Mo dopant. Furthermore, it was demonstrated that the doping of Mo in SCF can prevent the order-disorder transition and improves the chemical stability to CO2.
基金This work has been financially supported by Foundation of National Fundamental Research and Development.
文摘The performance of supported and unsupported molybdenum carbide for thepartial oxidation of methane (POM) to syngas was investigated. An evaluation of the catalystsindicates that bulk molybdenum carbide has a higher methane conversion during the initial stage buta lower selectivity to CO and H_2/CO ratio in the products. The rapid deactivation of the catalystis also a significant problem. However, the supported molybdenum carbide catalyst shows a muchhigher methane conversion, increased selectivity and significantly improved catalytic stability. Thecharacterization by XRD and BET specific area measurements depict an improved dispersion ofmolybdenum carbide when using alumina as a carrier. The bulk or the supported molybdenum carbideexists in the β-MO_2C phase, while it is transformed into molybdenum dioxide postcatalysis which isan important cause of molybdenum carbide deactivation.
文摘A new method for the preparation of dinuclear molybdenum dithiocarbamates(MoDDCs) is reported.This new method allows for the control of the amount of sulfurization of the Mo2SxO4-x core(x = 1 to 4) in the dinuclear MoDDCs.This control assists in the tailoring of specific tribological properties of the MoDDCs in both greases and lubricating oils.
基金Project(51104186)supported by the National Natural Science Foundation of ChinaProjects(2016zzts282,2016zzts283)supported by the Fundamental Research Funds for the Central Universities of Central South University,China
文摘To extract molybdenum and nickel from the roasted Ni-Mo ore, a process of hydrochloric acid leaching, sulphation roasting and water leaching was investigated. The results showed that this process could get a high leaching rate of Mo and Ni. Under the optimum conditions of hydrochloric acid leaching (roasted Ni-Mo ore leached with 0.219 mL/g hydrochloric acid addition at 65 ℃ for 30 min with a L/S ratio of 3 mL/g), sulphation roasting (51.9% sulfiaric acid addition, roasting temperature 240 ℃ for 1 h), followed by leaching with the first stage hydrochloric acid leaching solution at 95 ℃ for 2 h, the leaching rates of Mo and Ni reached 95.8% and 91.3%, respectively.
基金financially supported by the High-degree Talent Introduction Program of Guangdong Academy of Sciences(No.2017GDASCX-0841)the Science and Technology Program of Guangzhou(No.201607020021)+2 种基金the National Natural Science Foundation of China(No.51304055)the Innovative Platform Construction Program of Guangdong Academy of Sciences(No.2017GDASCX-0109)the Pearl River Nova Program of Guangzhou(No.201806010016)
文摘The study of the leaching of vanadium(V) and molybdenum(Mo) from spent petrochemical catalysts in sodium hydroxide(NaO H) medium was performed using two approaches, namely, conventional leaching and microwave-assisted leaching methods. The influence of microwave power, leaching time, leaching temperature, and NaOH concentration on the leaching efficiency of spent petrochemical catalyst was investigated. Under microwave-assisted conditions(600 W, 10 min, 90°C, 2.0 mol·L^(-1) NaOH, and 0.20 g·mL^(-1) solid–liquid ratio), the leaching efficiencies of V and Mo reached 94.35% and 96.23%, respectively. It has been confirmed that microwave energy has considerable potential to enhance the efficiency of the leaching process and reduce the leaching time. It is suggested that the enhancement of the leaching efficiencies of V and Mo can be attributed to the existence of a thermal gradient between solid and liquid and the generation of cracks on the mineral surface.