CN108910952A - A kind of foam-like molybdenum dioxide and preparation method thereof - Google Patents

A kind of foam-like molybdenum dioxide and preparation method thereof Download PDF

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CN108910952A
CN108910952A CN201811009299.1A CN201811009299A CN108910952A CN 108910952 A CN108910952 A CN 108910952A CN 201811009299 A CN201811009299 A CN 201811009299A CN 108910952 A CN108910952 A CN 108910952A
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molybdenum
molybdenum dioxide
foam
preparation
heating
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古思勇
张厚安
麻季冬
廉冀琼
陈莹
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Xiamen University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

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Abstract

The present invention relates to a kind of foam-like molybdenum dioxide and preparation method thereof, the method includes：Molybdenum source, ammonium nitrate, comburant and water are mixed, mixed solution is stirred to get, is heated to 80-180 DEG C, obtain colloidal sol, is heated to 200-300 DEG C later, reaction obtains molybdenum dioxide crude product, obtains foam-like molybdenum dioxide after purification.Foam-like molybdenum dioxide preparation method provided by the invention, process is short, and high-efficient, production cost is low, and foam-like molybdenum dioxide obtained is made of 20~30nm nanometer titanium dioxide molybdenum particle, show bubble porous structure, purity is high.

Description

A kind of foam-like molybdenum dioxide and preparation method thereof
Technical field
The present invention relates to nano transition metal oxides field, especially a kind of foam-like molybdenum dioxide and its preparation side Method.
Background technique
Molybdenum dioxide is the important existence form and application material of molybdenum oxide, because having good optics and electrochemistry Performance and high stability are in fields such as optical electrical mutagens color, lithium ion battery, supercapacitor, electrical/optical catalysis and therapeutic treatments Show huge application potential.Therefore, the synthesis with application of molybdenum dioxide and its composite material become grinding for Material Field Study carefully hot spot, wherein how to seek it is a kind of with cost effective again can flexible Effective Regulation molybdenum dioxide structure advanced synthesis Technology realizes the scale application of molybdenum dioxide, is always the research emphasis problem of scholars.
Compared to the molybdenum dioxide material of block, diffusion of the molybdenum dioxide of nanostructure due to shortening electronics and ion Path, bigger serface and high reaction power and have physically better chemical property.Therefore, it is synthesized using various synthetic technologys Nanoscale molybdenum oxide with special appearance with obtain improve its performance have become a hot topic of research.Currently, scholars use different conjunctions The molybdenum oxide that various forms nanostructure can be successfully prepared at technology, such as nanometer rods, nano particle, nanometer sheet, nanosphere and receives Popped rice etc., and show and the more excellent performance of non-nano structural material.
Currently, the method for synthesis nanometer titanium dioxide molybdenum mainly has hydro-thermal method, chemical vapour deposition, colloidal sol-gel method, surface Surfactant templating method, electrochemical deposition and chemical stripping method etc., the molybdenum dioxide using the synthesis of these methods have unique shape The problems such as state and performance, but to there is synthesis cycle in various degree long for the above method, low efficiency, higher cost.Simultaneously as receiving Rice molybdenum dioxide activity is high, formation MoO easy to oxidize3、Mo4O11Etc. high-valence states molybdenum-base oxide impurity, lead to nanometer titanium dioxide The performance of molybdenum cannot be not fully exerted, and how be purified to obtain the nanometer titanium dioxide molybdenum materials of high-purity to molybdenum dioxide material Material is also the important channel for improving molybdenum dioxide performance.Therefore, a kind of synthesis of the nanometer titanium dioxide molybdenum of cost effective is sought Technology and its purification technique are of great significance to the large-scale production for realizing nanometer titanium dioxide molybdenum with application.
Summary of the invention
The purpose of the invention is to overcome existing molybdenum dioxide synthesis cycle long, the problems such as low efficiency, higher cost, A kind of foam-like molybdenum dioxide and preparation method thereof is provided.
Concrete scheme is as follows：
A kind of preparation method of foam-like molybdenum dioxide, includes the following steps：
Step 1：Molybdenum source, ammonium nitrate, comburant and water are mixed, mixed solution is stirred to get；The molybdenum source is ammonium salt, The comburant has reproducibility；
Step 2：Mixed solution obtained in step 1 is heated to 80-180 DEG C, obtains colloidal sol；
Step 3：The colloidal sol that step 2 is obtained is heated to 200-300 DEG C, and reaction obtains molybdenum dioxide crude product；
Step 4：The molybdenum dioxide crude product that step 3 obtains is purified, foam-like molybdenum dioxide after purification is obtained.
Further, the molar ratio of molybdenum and ammonium nitrate is 7/20~7/15 in molybdenum source described in step 1；
Optional, the molar ratio of ammonium nitrate and comburant is 1/1~2/1 in step 1；
Optional, the ratio of the dosage of water and molybdenum in the molybdenum source is 800-1200 milliliters/0.7 mole in step 1.
Further, molybdenum source described in step 1 is positive in ammonium molybdate, ammonium paramolybdate, ammonium tetramolybdate or ammonium dimolybdate at least It is a kind of；
Optional, comburant described in step 1 is at least one of glycine, citric acid or urea.
Further, step 2 is that mixed solution obtained in step 1 is heated to 80-180 DEG C, makes the moisture in solution Volatilization is generated, when liquor capacity is reduced to original volume 40~60%, stops heating, obtains colloidal sol.
Further, heating described in step 3 is using any in microwave, ultrasonic Wave heating, electric furnace heating or infrared heating A kind of mode.
Further, step 3 includes：The colloidal sol that 3a obtains step 2 is laid into the sheet body with a thickness of 1-10 millimeters；3b is adopted With microwave heating, power is 800-2000 watts.
Further, the time of microwave heating is：When sol volume is less than or equal to 500 milliliters, heating time 3-6 point Clock；When sol volume is greater than 500 milliliters, heating time=[(numerical value -500 that sol volume presses milliliter metering)/100+5] point Clock.
Further, purifying described in step 4 is calcined at 500~550 DEG C, obtains foam-like titanium dioxide after purification Molybdenum.
The product that the present invention also protects the preparation method of the foam-like molybdenum dioxide to be prepared, including molybdenum dioxide Crude product or foam-like molybdenum dioxide.
Further, the molybdenum dioxide crude product show bubble porous structure, partial size are 20~30nm, the titanium dioxide Contain MoO in molybdenum crude product3、Mo4O11Or at least one of carbon impurity；
Optional, the foam-like molybdenum dioxide show bubble porous structure, partial size is 20~30nm, and purity is more than or equal to 99.9 weight %.
Beneficial effect：
It in the present invention, is mixed using the ammonium salt containing molybdenum with ammonium nitrate, is formed disperse uniform sol body in a heated condition System, and the high temperature of oxidation reaction formation and the reducibility gas of generation occur by ammonium nitrate, comburant, by molybdenum source high temperature point Molybdenum dioxide is solved and is reduced to, the synthetic method cost effective, and a large amount of extraneous supplemental heats are not needed, only it is heated to 200- 300 DEG C can complete reaction production molybdenum dioxide.
Moreover reaction can be rapidly completed by microwave heating colloidal sol, shorten the reaction time, production efficiency is improved 80%, it is convenient for industrial applicability.
Further, the residual carbon and MoO contained in reaction product is utilized by calcining at 500~550 DEG C3、Mo4O11 Carbothermic reduction reaction occurs for equal impurity, can effectively remove impurity, obtain the foam-like molybdenum dioxide nano-particle material of free from admixture.
In short, a kind of foam-like molybdenum dioxide preparation method provided by the invention, process is short, and high-efficient, production cost is low, Foam-like molybdenum dioxide obtained is made of 20~30nm nanometer titanium dioxide molybdenum particle, show bubble porous structure, and purity is big In equal to 99.9 weight %.
Detailed description of the invention
In order to illustrate more clearly of technical solution of the present invention, attached drawing will be briefly described below, it should be apparent that, The accompanying drawings in the following description merely relates to some embodiments of the present invention, rather than limitation of the present invention.
Fig. 1 is the preparation process flow for the foam-like molybdenum dioxide that the embodiment of the present invention 1 provides；
Fig. 2 is the XRD diffraction spectra for the molybdenum dioxide crude product that the embodiment of the present invention 1 provides；
Fig. 3 is the SEM photograph for the molybdenum dioxide crude product that the embodiment of the present invention 1 provides；
Fig. 4 is the TEM photo for the molybdenum dioxide crude product that the embodiment of the present invention 1 provides；
Fig. 5 is the XRD diffraction spectra for the foam-like molybdenum dioxide after purification that the embodiment of the present invention 2 provides；
Fig. 6 is the SEM photograph for the foam-like molybdenum dioxide after purification that the embodiment of the present invention 2 provides；
Fig. 7 is the TEM photo for the foam-like molybdenum dioxide after purification that the embodiment of the present invention 2 provides；
Fig. 8 is the XRD diffraction spectra for the molybdenum dioxide crude product that the embodiment of the present invention 3 provides；
Fig. 9 is the XRD diffraction spectra of comparative sample 1；
Figure 10 is the XRD diffraction spectra of comparative sample 2.
Specific embodiment
The definition of part term used in the present invention is given below, other terms that do not address have well known in the art Definition and meaning：
Positive ammonium molybdate：(NH4)2MoO4, the present invention in can use the positive ammonium molybdate aqueous solution containing excess ammonia；
Ammonium paramolybdate：(NH4)6Mo7O24, the present invention in ammonium paramolybdate can be water-free dry product, if be also possible to containing The product of the dry crystallization water；
Ammonium tetramolybdate：(NH4)2Mo4O13, the present invention in ammonium tetramolybdate can be water-free dry product, if be also possible to containing The product of the dry crystallization water
Ammonium dimolybdate：(NH4)2Mo2O7, the present invention in ammonium dimolybdate can be water-free dry product, if be also possible to containing The product of the dry crystallization water；
Comburant：In the method for the invention, ammonium nitrate is thermally decomposed, and generates a large amount of fuel gas, comburant Effect is that ammonium nitrate is made to be easier to decompose, and obtains fuel gas.
In method provided by the invention, the molybdenum source is ammonium salt, water-soluble, the ratio of molybdenum in the dosage of water and the molybdenum source Value is 800-1200 milliliter/0.7 mole, when the dosage of water is more than above-mentioned ratio, can make water heating volatilization time extension, i.e. step 2 can lengthen, and than relatively time-consuming, efficiency is reduced；When the dosage of water is lower than above-mentioned ratio, it is heavy that raw material can generate in heating volatilization process It forms sediment, especially molybdenum source.The molar ratio of molybdenum and ammonium nitrate is 7/20~7/15, preferably 7/19~7/16 in the molybdenum source, more excellent It is selected as 7/18.Ammonium nitrate is reducing agent, cooperatively forms with comburant glycine and reacts and generate high temperature, meanwhile, and generate Gas object, this is the key that so that molybdenum dioxide forms pumiceous texture and can not provide when ammonium nitrate dosage is lower than aforementioned proportion Enough energy, temperature of reaction system deficiency and gas generating amount are inadequate, cause that ideal foam-like and nanometer can not be formed Grain or even molybdenum source can not be successfully decomposition, and molybdenum dioxide can not synthesize；When ammonium nitrate dosage is higher than aforementioned proportion, excessive nitric acid Ammonium instead can heat in absorbing reaction system, cause reaction temperature to decline, be unfavorable for molybdenum dioxide pumiceous texture and nanometer The formation of particle.
In method provided by the invention, comburant effect is to promote ammonium nitrate fast reaction, routinely has in this field Help the decompose comburant of reaction of ammonium nitrate to be ok, preferably any one in glycine, citric acid or urea, on It is simple to state reagent molecule structure, pyrolytic is easy, and is suitable as comburant use.In addition, price is also relatively inexpensive.Ammonium nitrate Molar ratio with comburant is 1/1~2/1, which abides by stoichiometric ratio principle, is less than or greater than the ratio and can not Reach temperature needed for decomposing molybdenum source, meanwhile, the gas flow for reacting release also not enough forms ideal pumiceous texture and nanometer Particle.
In step 2 of the present invention heating obtain colloidal sol, the formation of colloidal sol be primarily due to molybdenum source in aqueous solution with ammonium nitrate Effect, the purpose of heating are to speed up moisture and generate volatilization, and colloidal sol is promoted to be formed.In addition it is also necessary to explanation, heating terminal is sentenced It is disconnected to be that colloidal sol is formed, such as when being heated to liquor capacity and reducing to original volume 40~60%, formed colloidal sol, should stop plus Heat can know that therefore not to repeat here to this those skilled in the art.
Step 3 of the present invention is heated to 200-300 DEG C of mode to the colloidal sol, and there is no particular limitation, as long as enabling to Colloidal sol reaction generates molybdenum dioxide.For example, the heating using microwave heating, ultrasonic Wave heating, electric furnace heating, it is infrared plus Hanker any one mode.Preferably microwave mode, the industrial microwave heating that microwave oven should select power to be greater than 2 kilowatts Furnace, efficiency highest, such as the microwave oven of model HAMiLab-V6.In one embodiment of the invention, by colloidal sol It is laid into the sheet body with a thickness of 1-10 millimeters, the power of microwave heating is 800-2000 watts, has most fast reaction speed, and obtain The molybdenum dioxide granularity obtained is uniform nanoscale, and crystallinity is high.In one embodiment of the invention, the time of microwave heating Preferably：When sol volume is less than or equal to 500 milliliters, heating time 3-6 minute；When sol volume is greater than 500 milliliters, Heating time=[(numerical value -500 that sol volume presses milliliter metering)/100+5] minute, microwave heating time is more than above-mentioned calculating The constant temperature of numerical value, product rises, and leads to molybdenum dioxide particle growth and sintered state occurs, meanwhile, also lead to more two Molybdenum oxide aoxidizes to form MoO3And Mo4O11, impurity content can sharply increase.
Step 4 of the present invention purifies molybdenum dioxide crude product, each component in the molybdenum dioxide crude product in the step Content：Molybdenum dioxide：90~95%, impurity MoO3And Mo4O11Account for about 5~10%, carbon：It is pure in order to improve less than or equal to 1% Degree, can further purify molybdenum dioxide crude product, and anaerobic is calcined preferably at 500~550 DEG C, not need at this time Other added regents, after molybdenum dioxide crude product is directly over calcining purification process, the granular size of foam-like molybdenum dioxide It is remained unchanged with pattern, MoO3、Mo4O11It is effectively removed with impurity such as carbon, obtains foam-like molybdenum dioxide after purification.Temperature Degree is lower than 500 DEG C, cannot completely remove impurity, although temperature, which is higher than 550 DEG C, can also remove partial impurities, will cause production The particle of object molybdenum dioxide significantly increases, and loses a nanometer advantage.The mode for keeping calcining system anaerobic can be to calcining system In by inert gas, for example, at least one of nitrogen and periodic table of elements group 0 element gas, to this art technology Personnel can know that therefore not to repeat here.It should be noted that the mode of molybdenum dioxide crude product purifying is not limited to foregoing description Mode, the removing to impurity in molybdenum dioxide crude product also may be implemented in other way of purification of this field, such as logical hydrogen calcining Deng.
The preferred embodiment of the present invention is described in more detail below.Although the following describe preferred implementations of the invention Mode, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by the embodiments set forth herein.It is real It applies and particular technique or condition person is not specified in example, according to the literature in the art described technology or conditions or according to product Specification carries out.Reagents or instruments used without specified manufacturer, being can be with conventional products that are commercially available.Under In the embodiment in face, such as it is not known and illustrates, " % " refers both to weight percent.
Test method used below includes：
XRD diffraction：The object phase of product, test condition are measured by X-ray diffractometer (Rigaku D/max-RB12, XRD) For Cu target, K α (λ=0.1541nm)
SEM test：Microstructure is carried out to product using field emission scanning electron microscope (FEI Quanta FEG450) Observation.
TEM test：Morphology analysis is carried out to sample using transmission electron microscope (FEI, Tecnai G2 F20, USA).
Purity calculation method：Contained using the carbon content and oxygen of elemental analyser (Thermo Fisher, 2000) test sample Amount；The constituent content Mo of ICP (Agilent, 720) test sample, according to Mo and oxygen content as a result, be calculated molybdenum dioxide and Miscellaneous phase content, wherein miscellaneous phase includes MoO3And Mo4O11, when calculating, by Mo4O11It treats as MoO3It is calculated with facilitating, purity is with weight Percentage meter.
The preparation process flow of foam-like molybdenum dioxide is as shown in Figure 1, include：Step 1：Molybdenum source, ammonium nitrate, burning are helped Agent and water mixing, stir to get mixed solution；The molybdenum source is ammonium salt, and the comburant has reproducibility；
Step 2：Mixed solution obtained in step 1 is heated to 80-180 DEG C, obtains colloidal sol；
Step 3：The colloidal sol that step 2 is obtained is heated to 200-300 DEG C, and reaction obtains molybdenum dioxide crude product；
Step 4：The molybdenum dioxide crude product that step 3 obtains is purified, foam-like molybdenum dioxide after purification is obtained. It is preferred that calcining way of purification.
Embodiment 1
Molybdenum dioxide crude product is prepared, steps are as follows：
(1) 0.15 mole of four water ammonium paramolybdate, 2.5 molar nitric acid ammoniums, 1.0 mole of glycine, 0.6 mole of lemon are weighed respectively Lemon acid, is added 1500 milliliters of deionized water, and dissolution is mixed and forms solution.
(2) prepared material solution is placed in heating furnace and is heated in 150 DEG C, generate the moisture in solution Volatilization forms thick colloidal sol when liquor capacity is reduced to original volume half, stops heating.
(3) colloidal sol is evenly laid out and kept for 2.5 millimeters of thickness, and it is put into microwave oven, in 1 kilowatt of microwave function It is heated 7.5 minutes under rate, molybdenum dioxide crude product is obtained after heating.
6 kilowatts of peak power output of the microwave oven that the present embodiment uses, model HAMiLab-V6.Implement below Example is all made of this model, no longer states.
XRD test and Electronic Speculum test are carried out to molybdenum dioxide crude product obtained respectively, as a result see Fig. 2-Fig. 4.
Fig. 2 is the XRD diffraction spectra of molybdenum dioxide crude product, from figure it is found that apparent molybdenum dioxide diffraction occurs in its product Peak, and diffraction maximum is sharp and intensity is high, shows that the crystallinity of molybdenum dioxide is high, meanwhile, three oxidations on a small quantity are contained in product Molybdenum and Mo4O11Impurity.Fig. 3 is the SEM photograph of molybdenum dioxide crude product, from figure it is found that product shows the foam-like of multi-hole state Structure.Fig. 4 is the TEM photo of molybdenum dioxide crude product, from figure it is found that molybdenum dioxide crude product is by two that partial size is 20-30nm Molybdenum oxide nanoparticles composition.
Embodiment 2
Molybdenum dioxide crude product prepared by embodiment 1 is put into tube furnace, it will be warm with 10 DEG C of heating rates per minute Degree rises to 525 DEG C, calcines 1.5 hours, after calcining, cools to room temperature with the furnace and takes out the foam-like titanium dioxide for obtaining purifying Molybdenum.The heating, heat preservation and cooling overall process for calcining purification process carry out under argon atmosphere.
XRD test and Electronic Speculum test are carried out to the foam-like molybdenum dioxide after calcining purification process respectively, as a result see Fig. 5- Fig. 6.
Fig. 5 is the XRD diffraction spectra for calcining the foam-like molybdenum dioxide after purification process, from figure it is found that product is all by two Molybdenum oxide composition, original molybdenum trioxide and Mo4O11Impurity has disappeared, and shows that impurity can significantly be removed by calcining purification process, be made Foam-like molybdenum dioxide is purified.Fig. 6 is the SEM photograph of foam-like molybdenum dioxide after calcining purification process, from figure it is found that producing Object still maintains original multi-hole state pumiceous texture, shows that pattern generation will not be significantly affected by calcining purification process.Fig. 7 is The TEM photo of foam-like molybdenum dioxide shows from figure it is found that nanometer titanium dioxide molybdenum particle is 20-30nm after calcining purification process Calcining purification process will not generate the partial size of molybdenum dioxide and significantly affect.
Embodiment 3
(1) 0.1 mole of four water ammonium paramolybdate, 1.8 molar nitric acid ammoniums, 1.0 mole of glycine are weighed respectively, and 1000 millis are added The deionized water risen is mixed dissolution and forms solution.
(2) prepared material solution is placed in heating furnace and is heated in 150 DEG C, generate the moisture in solution Volatilization forms thick colloidal sol when liquor capacity is reduced to original volume half, stops heating.
(3) colloidal sol is evenly laid out and kept for 2 millimeters of thickness, and it is put into microwave oven, in 1 kilowatt of microwave power Lower heating 5 minutes, obtains molybdenum dioxide crude product after heating.
XRD test is carried out to molybdenum dioxide crude product obtained, as a result sees Fig. 8.Fig. 8 is titanium dioxide manufactured in the present embodiment The XRD diffraction spectra of molybdenum crude product, from figure it is found that apparent molybdenum dioxide diffraction maximum occurs in its product, and diffraction maximum it is sharp and Intensity is high, shows that the crystallinity of molybdenum dioxide is high, meanwhile, a small amount of molybdenum trioxide and Mo are contained in product4O11Impurity, with implementation Example 1 is compared, the impurity content slightly difference due to the difference of material rate, in product.Through scanning electron microscope test, shape Looks are to form pumiceous texture by the molybdenum dioxide nano particle that partial size is 20-30nm.The molybdenum dioxide of embodiment preparation Scale particle size and porosity, compared with Example 1 difference.
Embodiment 4
Molybdenum dioxide crude product prepared by embodiment 3 is put into tube furnace, it will be warm with 10 DEG C of heating rates per minute Degree rises to 500 DEG C, calcines 2 hours, after calcining, cools to room temperature with the furnace and takes out the foam-like titanium dioxide for obtaining High Purity Molybdenum.The heating, heat preservation and cooling overall process for calcining purification process carry out under argon atmosphere.
XRD test and Electronic Speculum test are carried out respectively to the foam-like molybdenum dioxide after calcining purification process, the results showed that, it forges It burns purification process and is completely removed impurity, purify foam-like molybdenum dioxide.And it will not be to pattern and molybdenum dioxide Partial size generation significantly affects.
Embodiment 5
Foam-like molybdenum dioxide is prepared, steps are as follows：
(1) 0.175 mole of ammonium tetramolybdate, 2.0 molar nitric acid ammoniums, 2.0 mole of glycine are weighed respectively, are added 800 milliliters Deionized water, be mixed dissolution forms solution.
(2) prepared material solution is placed in heating furnace and is heated in 180 DEG C, generate the moisture in solution Volatilization forms thick colloidal sol when liquor capacity is reduced to original volume half, stops heating.
(3) colloidal sol is evenly laid out and kept for 2.5 millimeters of thickness, and it is put into microwave oven, in 2 kilowatts of microwave function It is heated 7 minutes under rate, molybdenum dioxide crude product is obtained after heating.
(4) the molybdenum dioxide crude product of preparation is put into tube furnace, with 10 DEG C of heating rates per minute by temperature liter It to 500 DEG C, calcines 1.5 hours, after calcining, cools to room temperature with the furnace and take out the foam-like molybdenum dioxide for obtaining purifying. Partial size is 20~30nm, and purity is 99.9 weight %.The heating, heat preservation and cooling overall process for calcining purification process are protected in argon gas It is carried out under atmosphere.
Embodiment 6
Foam-like molybdenum dioxide is prepared, steps are as follows：
(1) 0.35 mole of ammonium dimolybdate, 1.5 molar nitric acid ammoniums, 1 molar citric acid are weighed respectively, are added 1200 milliliters Deionized water is mixed dissolution and forms solution.
(2) prepared material solution is placed in heating furnace and is heated in 80 DEG C, generate the moisture in solution Volatilization forms thick colloidal sol when liquor capacity is reduced to original volume half, stops heating.
(3) colloidal sol is evenly laid out and kept for 2.5 millimeters of thickness, and it is put into microwave oven, in 800 watts of microwave function It is heated 8 minutes under rate, molybdenum dioxide crude product is obtained after heating.
(4) the molybdenum dioxide crude product of preparation is put into tube furnace, with 10 DEG C of heating rates per minute by temperature liter It to 550 DEG C, calcines 1.5 hours, after calcining, cools to room temperature with the furnace and take out the foam-like molybdenum dioxide for obtaining purifying. Partial size is 20~30nm, and purity is 99.9 weight %.The heating, heat preservation and cooling overall process for calcining purification process are protected in argon gas It is carried out under atmosphere.
Embodiment 7
Foam-like molybdenum dioxide is prepared, steps are as follows：
(1) 0.1 mole of four water ammonium paramolybdate, 1.8 molar nitric acid ammoniums, 1.6 mole of glycine are weighed respectively, and 1000 millis are added The deionized water risen is mixed dissolution and forms solution.
(2) prepared material solution is placed in heating furnace and is heated in 100 DEG C, generate the moisture in solution Volatilization forms thick colloidal sol when liquor capacity is reduced to original volume half, stops heating.
(3) colloidal sol is evenly laid out and kept for 2.5 millimeters of thickness, and it is put into microwave oven, in 1 kilowatt of microwave function It is heated 7.5 minutes under rate, molybdenum dioxide crude product is obtained after heating.
(4) the molybdenum dioxide crude product of preparation is put into tube furnace, with 10 DEG C of heating rates per minute by temperature liter It to 540 DEG C, calcines 1.5 hours, after calcining, cools to room temperature with the furnace and take out the foam-like molybdenum dioxide for obtaining purifying. Partial size is 20~30nm, and purity is 99.9 weight %.The heating, heat preservation and cooling overall process for calcining purification process are protected in argon gas It is carried out under atmosphere.
Comparative example 1
The case where when this comparative example describes glycine, citric acid and urea deficiency.
(1) 0.15 mole of four water ammonium paramolybdate, 2.5 molar nitric acid ammoniums, 0.5 mole of glycine, 0.3 mole of lemon are weighed respectively Lemon acid, is added 1500 milliliters of deionized water, and dissolution is mixed and forms solution.
(2) prepared material solution is placed in heating furnace and is heated in 150 DEG C, generate the moisture in solution Volatilization forms thick colloidal sol when liquor capacity is reduced to original volume half, stops heating.
(3) colloidal sol is evenly laid out and kept for 2.5 millimeters of thickness, and it is put into microwave oven, in 1 kilowatt of microwave function It is heated 7.5 minutes under rate, comparative sample 1 is obtained after heating.
6 kilowatts of microwave oven peak power output of this comparative example use, model HAMiLab-V6.
XRD test is carried out to comparative sample 1 obtained, as a result sees Fig. 9.
Fig. 9 is the XRD diffraction spectra of comparative sample 1, from figure it is found that its product is mainly (NH4)2MoO13Diffraction maximum, show Molybdenum dioxide can not successfully be synthesized.This is because fuel is to provide energy production high temperature primary raw material, and when fuel shortage, reaction Shi Wufa generates enough temperature and decomposes four water ammonium paramolybdates completely, leads to not synthesize molybdenum dioxide.
Comparative example 2
When this comparative example calcines purification process to description, the case where when temperature is too low.
Molybdenum dioxide crude product prepared by embodiment 1 is put into tube furnace, with 10 DEG C of heatings per minute of heating rate Temperature is risen to 400 DEG C by speed, is calcined 3 hours, after calcining, is cooled to room temperature with the furnace and is taken out acquisition comparative sample 2.Calcining Heating, heat preservation and the cooling overall process of purification process carry out under argon atmosphere.
XRD test, the result is shown in Figure 10 will be carried out using comparative sample 2.Figure 10 is the XRD diffraction spectra of comparative sample 2, can from figure Know, molybdenum trioxide and Mo are still contained in comparative sample4O11Impurity, the result do not have with the result (see Fig. 2) when not carrying out 400 DEG C of calcinings There is significant difference, shows to will be unable to successfully remove impurity when lower than calcining cleansing temp of the present invention.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (10)

1. a kind of preparation method of foam-like molybdenum dioxide, it is characterised in that：Include the following steps：
Step 1：Molybdenum source, ammonium nitrate, comburant and water are mixed, mixed solution is stirred to get；The molybdenum source is ammonium salt, described Comburant has reproducibility；
Step 2：Mixed solution obtained in step 1 is heated to 80-180 DEG C, obtains colloidal sol；
Step 3：The colloidal sol that step 2 is obtained is heated to 200-300 DEG C, and reaction obtains molybdenum dioxide crude product；
Step 4：The molybdenum dioxide crude product that step 3 obtains is purified, foam-like molybdenum dioxide after purification is obtained.
2. the preparation method of foam-like molybdenum dioxide according to claim 1, it is characterised in that：Molybdenum source described in step 1 The molar ratio of middle molybdenum and ammonium nitrate is 7/20~7/15；
Optional, the molar ratio of ammonium nitrate and comburant is 1/1~2/1 in step 1；
Optional, the ratio of the dosage of water and molybdenum in the molybdenum source is 800-1200 milliliters/0.7 mole in step 1.
3. the preparation method of foam-like molybdenum dioxide according to claim 1, it is characterised in that：Molybdenum source described in step 1 Be positive at least one of ammonium molybdate, ammonium paramolybdate, ammonium tetramolybdate or ammonium dimolybdate；
Optional, comburant described in step 1 is at least one of glycine, citric acid or urea.
4. the preparation method of foam-like molybdenum dioxide according to claim 1, it is characterised in that：Step 2 is will be in step 1 Obtained mixed solution is heated to 80-180 DEG C, so that the moisture in solution is generated volatilization, reduces to liquor capacity to original volume 40 When~60%, stops heating, obtain colloidal sol.
5. the preparation method of foam-like molybdenum dioxide according to claim 1, it is characterised in that：It is heated described in step 3 Using any one mode in microwave, ultrasonic Wave heating, electric furnace heating or infrared heating.
6. the preparation method of foam-like molybdenum dioxide according to claim 5, it is characterised in that：Step 3 includes：3a will be walked Rapid 2 obtained colloidal sols are laid into the sheet body with a thickness of 1-10 millimeters；3b uses microwave heating, and power is 800-2000 watts.
7. the preparation method of foam-like molybdenum dioxide according to claim 5 or 6, it is characterised in that：Microwave heating when Between be：When sol volume is less than or equal to 500 milliliters, heating time 3-6 minute；When sol volume is greater than 500 milliliters, add The hot time=[(numerical value -500 that sol volume presses milliliter metering)/100+5] minute.
8. the preparation method of foam-like molybdenum dioxide according to claim 1-6, it is characterised in that：In step 4 The purifying is calcined at 500~550 DEG C, and foam-like molybdenum dioxide after purification is obtained.
9. the product that the preparation method of foam-like molybdenum dioxide of any of claims 1-8 is prepared, including two Molybdenum oxide crude product or foam-like molybdenum dioxide.
10. the product that the preparation method of foam-like molybdenum dioxide according to claim 9 is prepared, it is characterised in that： The molybdenum dioxide crude product show bubble porous structure, partial size are 20~30nm, are contained in the molybdenum dioxide crude product MoO3、Mo4O11Or at least one of carbon impurity；
Optional, the foam-like molybdenum dioxide show bubble porous structure, partial size is 20~30nm, and purity is more than or equal to 99.9 Weight %.
CN201811009299.1A 2018-08-31 2018-08-31 A kind of foam-like molybdenum dioxide and preparation method thereof Withdrawn CN108910952A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110015693A (en) * 2019-04-01 2019-07-16 哈尔滨工业大学 A kind of efficient electro-catalysis nitrogen is the unformed MoO of two dimension of ammoniaxThe preparation method of material
CN111646504A (en) * 2020-05-29 2020-09-11 厦门理工学院 Nano lanthanum zirconate and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110015693A (en) * 2019-04-01 2019-07-16 哈尔滨工业大学 A kind of efficient electro-catalysis nitrogen is the unformed MoO of two dimension of ammoniaxThe preparation method of material
CN110015693B (en) * 2019-04-01 2021-07-16 哈尔滨工业大学 Two-dimensional amorphous MoO with ammonia as efficient electro-catalytic nitrogenxMethod for producing a material
CN111646504A (en) * 2020-05-29 2020-09-11 厦门理工学院 Nano lanthanum zirconate and preparation method thereof
CN111646504B (en) * 2020-05-29 2022-08-12 厦门理工学院 Nano lanthanum zirconate and preparation method thereof

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