CN102815749B - Preparation method of molybdenum dioxide nanorod - Google Patents
Preparation method of molybdenum dioxide nanorod Download PDFInfo
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Abstract
The invention discloses a preparation method of a molybdenum dioxide nanorod. The preparation method comprises the following steps of: by taking sodium molybdate as a molybdenum source, acetic oxide as an additive, dimethylformamide as a solvent, concentrated hydrochloric acid as an acidifier, and tetrabutylammonium bromide as a settling agent, through a simple experiment device and reaction steps, controlling concentration of molybdate suspension, an additive amount of the additive, a pH value of the solution and the amount of the settling agent, recrystalizing and purifying to obtain precursor tetrabutyl ammonium hexamolybdate; and thermally treating the precursor tetrabutyl ammonium hexamolybdate in a quartz tube under an inert atmosphere to have decomposition to obtain a monoclinic phase molybdenum dioxide nanorod. The method, prepared by the invention, has the advantages of low cost and high reaction yield, and capability of overcoming the vices of expensive instrument device, rigorous reaction conditions and reduction at high temperature with H2 with safety hidden trouble of the conventional preparation method.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of preparation method of molybdenum dioxide nanometer rod.
Background technology
Transition metal oxide molybdenum dioxide belongs to oblique system, has the rutile crystal structure of distortion.Due to its special structure, molybdenum dioxide has high conductivity, high-melting-point, high chemical stability, and its efficient charge transmission makes it extensive in aspect application prospects such as catalyzer, sensor, electrochromic display device, recording materials, electric chemical super capacitor, ionization cell and field emmision materials.
The preparation method of molybdenum dioxide nano material has been reported at present.The people such as Wang Zhonglin (Advanced Materials, 2003,15:1835) are heated to metal molybdenum 1100 ℃ in vacuum oven, then pass into shielding gas Ar, obtain molybdenum dioxide nano-wire array in monocrystal silicon substrate; The people such as Liu Huarong (Solid State Sciences; 2006; 8:526) take molybdic oxide as raw material; method by gammairradiation and the combination of hydrogen shield pyroprocessing has been prepared molybdenum dioxide; these two kinds of preparation methods need expensive plant and instrument and harsh preparation condition, have limited the application of molybdenum dioxide.The people such as Shi Yifeng (Nano Letters, 2009,9:4215) are take phospho-molybdic acid as presoma, and mesoporous silicon oxide KIT-6 is hard template, at 10% H
2under atmosphere, prepared the mesoporous nano molybdenum dioxide of high-sequential by gaseous techniques, this molybdenum dioxide has the reversible charging and discharging capacity up to 750mAh/g, it is the potential lithium-ion secondary cell anode material of tool, this preparation method may cause material damage while existing molybdenum dioxide material to separate with template, and is difficult to realize the shortcomings such as batch production.The people such as Hu Bin (ACS Nano, 2009,3:478) are with MoO
3nano belt is raw material, under high temperature, uses H
2reduce and successfully prepared molybdenum dioxide nanometer rod, product pattern heterogeneity, particularly H that the method obtains
2security at high temperature makes this method have various hidden danger.
There is apparatus expensive in above synthetic method, synthesis temperature high mostly, and energy consumption is large, and synthesis condition harshness need to be employed the H that has potential safety hazard
2problem.
Summary of the invention
The object of this invention is to provide a kind of preparation method of molybdenum dioxide nanometer rod, solved existing method and prepared molybdenum dioxide nanometer rod, apparatus expensive, synthesis temperature is high, and energy consumption is large, synthesis condition harshness,, there is the problem of potential safety hazard in product pattern heterogeneity.
The technical solution adopted in the present invention is, a kind of preparation method of molybdenum dioxide nanometer rod specifically implements according to following steps:
Step 1: by Sodium orthomolybdate grind into powder at ambient temperature, be dissolved in dimethyl formamide, it is 0.1-0.4molL that magnetic agitation obtains concentration
-1suspension liquid, continue stir in the situation that, in suspension liquid, add acetic anhydride, stir 10min;
Step 2: in the situation that continuing to stir, in the suspension liquid obtaining to step 1, slowly add concentrated hydrochloric acid, after concentrated hydrochloric acid adds, suspension liquid becomes yellow solution, and the generation of adularescent precipitation, continues to stir 15min, after stirring finishes, the yellow solution that contains white precipitate obtaining is filtered, and filtering white precipitate, obtains yellow transparent filtrate;
Step 3: the in the situation that of magnetic agitation, be 0.3-0.5molL by concentration
-1the dimethyl formamide solution of Tetrabutyl amonium bromide join in the yellow transparent filtrate that step 2 obtains, until there is yellow mercury oxide to produce, continue vigorous stirring 30min, it is fully precipitated;
Step 4: after stirring finishes, the solution filter that contains yellow mercury oxide that step 3 is obtained, obtain yellow mercury oxide product, by the yellow solid product of acquisition first with ethanol lotion 3-5 time, use ether lotion 3-5 time again, finally yellow solid product is carried out to recrystallization purification take acetone as solvent, after completing, recrystallization by yellow crystals product collection, dry in a vacuum, obtains presoma six molybdic acid TBuAs;
Step 5: the presoma six molybdic acid TBuAs that step 4 recrystallization is obtained are placed in the silica tube in tube furnace heat-treats, and obtains monoclinic phase molybdenum dioxide nanometer rod.
Feature of the present invention is also,
In step 1 wherein, the volume ratio of acetic anhydride and suspension liquid is 1:10-1:30.
The add-on of concentrated hydrochloric acid in step 2 wherein, makes the pH value of solution be adjusted to 0.5-1.5.
The volume ratio of the dimethyl formamide solution of the Tetrabutyl amonium bromide adding in step 3 wherein and yellow transparent filtrate is 1:1-1:2.
Thermal treatment in step 5 wherein, at N
2in atmosphere, carry out, temperature 600-700 ℃, insulation 2-3h,, then naturally cools to room temperature by temperature rise rate 25-35 ℃/min.
The invention has the beneficial effects as follows, first take Sodium orthomolybdate as molybdenum source, acetic anhydride is additive, dimethyl formamide is solvent, and concentrated hydrochloric acid is souring agent, and Tetrabutyl amonium bromide is precipitation agent, by simple experimental installation and reactions steps, by controlling molybdate suspension liquid concentration, additive add-on, the potential of hydrogen of solution and the consumption of precipitation agent, and carry out recrystallization purification, obtain presoma six molybdic acid TBuAs.Secondly the presoma of acquisition six molybdic acid TBuAs are heat-treated in silica tube under inert atmosphere, it is decomposed, obtain monoclinic phase molybdenum dioxide nanometer rod.The method raw materials cost is low, and reaction yield is high.Processing method of the present invention, has overcome the H that has potential safety hazard under existing preparation method's plant and instrument costliness, severe reaction conditions and employing high temperature
2the drawback of reducing, changes gas phase reduction process into precursor thermal decomposition method, utilizes solution deposit synthesis of nano particle size easily to control, and equipment is simple, the synthetic precursor six molybdic acid TBuAs of advantage that cost is low; Utilize thermal decomposition method charging capacity large, sufficient reacting, the synthetic molybdenum dioxide nanometer rod of advantage that productive rate is high.By presoma thermal decomposition method, can realize maroscopic quantity completely and prepare molybdenum dioxide nanometer rod, reduce preparation cost, significant for the industrialization preparation and application of molybdenum dioxide nanometer rod.
Accompanying drawing explanation
Fig. 1 is molybdenum dioxide nanometer rod TEM figure prepared by the embodiment of the present invention 1;
Fig. 2 is molybdenum dioxide nanometer rod XRD figure prepared by the embodiment of the present invention 1;
Fig. 3 is the ED figure of the molybdenum dioxide nanometer rod prepared of the embodiment of the present invention 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The present invention prepares the method for molybdenum dioxide nanometer rod, and preparation process is divided into two steps.First utilize the precipitator method to prepare precursor six molybdic acid TBuAs, take Sodium orthomolybdate as molybdenum source, acetic anhydride is additive, and dimethyl formamide is solvent, and concentrated hydrochloric acid is souring agent, Tetrabutyl amonium bromide is precipitation agent, acetone is the solvent of recrystallization, utilizes simple experimental installation and reactions steps, by controlling the consumption of molybdate suspension liquid concentration, additive add-on, concentrated hydrochloric acid and precipitation agent, and carry out recrystallization purification, obtain presoma six molybdic acid TBuAs.Secondly by the presoma six molybdic acid TBuAs that obtain in silica tube at rare gas element N
2under protection, heat-treat, it is decomposed, obtain molybdenum dioxide nanometer rod.
Concrete operations technique is, Sodium orthomolybdate grinds to form the thinner powder of granularity at ambient temperature, pours into and fills in dimethyl formamide beaker, and it is 0.1-0.4molL that magnetic agitation obtains concentration
-1suspension liquid, then in suspension liquid, add 1-3ml acetic anhydride, continue stir 10min; In the situation that continuing to stir, in above-mentioned suspension liquid, add concentrated hydrochloric acid to carry out acidifying to it, after concentrated hydrochloric acid adds, suspension liquid becomes the yellow transparent solution that contains white precipitate, the add-on of concentrated hydrochloric acid, the pH value that finally makes solution after acidifying is 0.5-1.5, continues to stir 15min; After stirring finishes, the yellow souring soln that contains white precipitate obtaining is filtered, elimination white depositions, obtains yellow transparent filtrate; The in the situation that of magnetic agitation, be 0.3-0.5molL by concentration
-1the dimethyl formamide solution of Tetrabutyl amonium bromide joins in the yellow filtrate of acquisition, has yellow mercury oxide to generate in filtrate, continues vigorous stirring 30min, and it is fully precipitated; By the solution filter after fully precipitating, obtain yellow mercury oxide product, by the yellow solid product of acquisition first with ethanol lotion 3-5 time, use ether lotion 3-5 time again, finally this yellow solid product is carried out to recrystallization take acetone as solvent, after recrystallization completes by yellow crystals product collection, dry under vacuum condition, obtain the presoma six molybdic acid TBuAs of preparing molybdenum dioxide nanometer rod; The six molybdic acid TBuAs that recrystallization is obtained are placed in the silica tube in tube furnace, give the speed logical rare gas element N of silica tube with 400ml/min
2, after 30min, with the temperature rise rate heated quarty tube of 25-35 ℃/min, to 600-700 ℃, insulation 2-3h, then at N
2in atmosphere, naturally cool to room temperature, can obtain monoclinic phase molybdenum dioxide nanometer rod powder.The key that obtains pure molybdenum dioxide nanometer rod is to obtain pure precursor six molybdic acid TBuAs.If during with the dimethyl formamide suspension liquid of concentrated hydrochloric acid acidifying sodium wolframate, finally contain the pH value of yellow solution of white precipitate not at 0.5-1.5, after adding the dimethyl formamide solution of precipitation agent Tetrabutyl amonium bromide in the yellow filtrate obtaining after filtering, will can not obtain six pure molybdic acid TBuAs precipitations.In addition, purity and the recrystallizing technology of the precursor six molybdic acid TBuAs of acquisition are closely related, and bad if recrystallization process is processed, the precursor of acquisition is not effectively purified, and finally can not obtain pure molybdenum dioxide nanometer rod.
Sodium wolframate is dissolved in dimethyl formamide after grinding, and it is 0.1molL that magnetic agitation obtains concentration
-1sodium orthomolybdate suspension liquid; In the situation that continuing to stir, in Sodium orthomolybdate suspension liquid, add 1ml acetic anhydride, continue to stir after 10min; In above-mentioned suspension liquid, slowly add concentrated hydrochloric acid to carry out acidifying to it, after concentrated hydrochloric acid adds, suspension liquid becomes the yellow solution that contains white precipitate, the add-on of concentrated hydrochloric acid, and finally making the pH value of solution after acidifying is 1.5, continues to stir 15min; After stirring finishes, the yellow solution that contains white precipitate after acidifying is filtered, elimination white precipitate, obtains yellow transparent filtrate; The in the situation that of magnetic agitation, be 0.3molL by concentration
-1the dimethyl formamide solution of Tetrabutyl amonium bromide join in the yellow transparent filtrate of acquisition, have yellow mercury oxide to produce, continue vigorous stirring 30min, it is fully precipitated; By the solution filter after fully precipitating, obtain yellow mercury oxide product, the yellow solid product of acquisition is first used to ethanol lotion 3 times, use again ether lotion 5 times, finally this yellow solid product is carried out to recrystallization take acetone as solvent, after recrystallization completes, the yellow crystals obtaining is collected, dry under vacuum condition, obtain precursor six molybdic acid TBuAs; The presoma six molybdic acid TBuAs that recrystallization is obtained are placed in the silica tube in tube furnace, give the speed logical rare gas element N of silica tube with 400ml/min
2, after 30min, with the temperature rise rate heated quarty tube to 600 ℃ of 25 ℃/min, insulation 3h, then at N
2in atmosphere, naturally cool to room temperature, can obtain monoclinic phase molybdenum dioxide nanometer rod powder.
Fig. 2 is the molybdenum dioxide nanometer rod XRD figure of preparation, the position of each diffraction peak of XRD figure of synthetic product and relative intensity all with JCPDS card NO.78-1070(a=0.5620nm, b=0.4860nm, c=0.5630nm) in full accord, show that product is the molybdenum dioxide of monoclinic phase.Fig. 1 is the molybdenum dioxide nanometer rod TEM figure of preparation, and the molybdenum dioxide as can be seen from the figure obtaining is club shaped structure, nanometer rod shape rule, smooth surface, length 0.6-1.2um, diameter 40-80nm.Fig. 3 is the ED figure of the molybdenum dioxide nanometer rod of preparation, and ED figure is diffraction spot clearly, shows that synthetic product is single crystal structure.Compared with other preparation methods, the inventive method equipment is simple, and productive rate is high, and cost is low, without potential safety hazard.
Embodiment 2
Sodium wolframate is dissolved in dimethyl formamide after grinding, and it is 0.4molL that magnetic agitation obtains concentration
-1sodium orthomolybdate suspension liquid; In the situation that continuing to stir, in Sodium orthomolybdate suspension liquid, add 3ml acetic anhydride, continue to stir after 10min; In above-mentioned suspension liquid, slowly add concentrated hydrochloric acid to carry out acidifying to it, after concentrated hydrochloric acid adds, suspension liquid becomes the yellow solution that contains white precipitate, the add-on of concentrated hydrochloric acid, and finally making the pH value of solution after acidifying is 0.5, continues to stir 15min; After stirring finishes, the yellow solution that contains white precipitate after acidifying is filtered, elimination white precipitate, obtains yellow transparent filtrate; The in the situation that of magnetic agitation, be 0.5molL by concentration
-1the dimethyl formamide solution of Tetrabutyl amonium bromide join in the yellow transparent filtrate of acquisition, have yellow mercury oxide to produce, continue vigorous stirring 30min, it is fully precipitated; By the solution filter after fully precipitating, obtain yellow mercury oxide product, the yellow solid product of acquisition is first used to ethanol lotion 5 times, use again ether lotion 3 times, finally this yellow solid product is carried out to recrystallization take acetone as solvent, collect the yellow crystals that recrystallization obtains, dry under vacuum condition, obtain precursor six molybdic acid TBuAs; The presoma six molybdic acid TBuAs that recrystallization is obtained are placed in the silica tube in tube furnace, give the speed logical rare gas element N of silica tube with 400ml/min
2, after 30min, with the temperature rise rate heated quarty tube to 700 ℃ of 35 ℃/min, insulation 2h, then at N
2in atmosphere, naturally cool to room temperature, can obtain monoclinic phase molybdenum dioxide nanometer rod powder.
Embodiment 3
Sodium wolframate is dissolved in dimethyl formamide after grinding, and it is 0.3molL that magnetic agitation obtains concentration
-1sodium orthomolybdate suspension liquid; In the situation that continuing to stir, in Sodium orthomolybdate suspension liquid, add 2ml acetic anhydride, continue to stir after 10min; In above-mentioned suspension liquid, slowly add concentrated hydrochloric acid to carry out acidifying to it, after concentrated hydrochloric acid adds, suspension liquid becomes the yellow solution that contains white precipitate, the add-on of concentrated hydrochloric acid, and finally making the pH value of solution after acidifying is 1.0, continues to stir 15min; After stirring finishes, the yellow solution that contains white precipitate after acidifying is filtered, elimination white depositions, obtains yellow transparent filtrate; The in the situation that of magnetic agitation, be 0.4molL by concentration
-1the dimethyl formamide solution of Tetrabutyl amonium bromide join in the yellow transparent filtrate of acquisition, have yellow mercury oxide to produce, continue vigorous stirring 30min, it is fully precipitated; By the solution filter after fully precipitating, obtain yellow mercury oxide product, the yellow solid product of acquisition is first used to ethanol lotion 4 times, use again ether lotion 4 times, finally this yellow solid product is carried out to recrystallization take acetone as solvent, collect the yellow crystals product obtaining after recrystallization, dry under vacuum condition, obtain and prepare precursor six molybdic acid TBuAs; The presoma six molybdic acid TBuAs that recrystallization is obtained are placed in the silica tube in tube furnace, give the speed logical rare gas element N of silica tube with 400ml/min
2, after 30min, with the temperature rise rate heated quarty tube to 650 ℃ of 30 ℃/min, insulation 2.5h, then at N
2in atmosphere, naturally cool to room temperature, can obtain monoclinic phase molybdenum dioxide nanometer rod powder.
Embodiment 4
Sodium wolframate is dissolved in dimethyl formamide after grinding, and it is 0.2molL that magnetic agitation obtains concentration
-1sodium orthomolybdate suspension liquid; In the situation that continuing to stir, in Sodium orthomolybdate suspension liquid, add 2.5ml acetic anhydride, continue to stir after 10min; In above-mentioned suspension liquid, slowly add concentrated hydrochloric acid to carry out acidifying to it, after concentrated hydrochloric acid adds, suspension liquid becomes the yellow solution that contains white precipitate, the add-on of concentrated hydrochloric acid, and finally making the pH value of solution after acidifying is 1.2, continues to stir 15min; After stirring finishes, the yellow solution that contains white precipitate after acidifying is filtered, elimination white precipitate, obtains yellow transparent filtrate; The in the situation that of magnetic agitation, be 0.35molL by concentration
-1the dimethyl formamide solution of Tetrabutyl amonium bromide join in the yellow transparent filtrate of acquisition, have yellow mercury oxide to produce, continue vigorous stirring 30min, it is fully precipitated; By the solution filter after fully precipitating, obtain yellow mercury oxide product, the yellow solid product of acquisition is first used to ethanol lotion 5 times, use again ether lotion 4 times, finally this yellow solid product is carried out to recrystallization take acetone as solvent, after recrystallization completes, the yellow crystals obtaining is collected, dry under vacuum condition, obtain precursor six molybdic acid TBuAs; The presoma six molybdic acid TBuAs that recrystallization is obtained are placed in the silica tube in tube furnace, give the speed logical rare gas element N of silica tube with 400ml/min
2, after 30min, with the temperature rise rate heated quarty tube to 680 ℃ of 28 ° of C/min, insulation 2.2h, then at N
2in atmosphere, naturally cool to room temperature, can obtain monoclinic phase molybdenum dioxide nanometer rod powder.
Claims (4)
1. a preparation method for molybdenum dioxide nanometer rod, is characterized in that, specifically implements according to following steps:
Step 1: by Sodium orthomolybdate grind into powder at ambient temperature, be dissolved in dimethyl formamide, it is 0.1-0.4molL that magnetic agitation obtains concentration
-1suspension liquid, continue stir in the situation that, in suspension liquid, add acetic anhydride, stir 10min;
Step 2: in the situation that continuing to stir, in the suspension liquid obtaining to step 1, slowly add concentrated hydrochloric acid, after concentrated hydrochloric acid adds, suspension liquid becomes yellow solution, and the generation of adularescent precipitation, continues to stir 15min, after stirring finishes, the yellow solution that contains white precipitate obtaining is filtered, and filtering white precipitate, obtains yellow transparent filtrate;
Step 3: the in the situation that of magnetic agitation, be 0.3-0.5molL by concentration
-1the dimethyl formamide solution of Tetrabutyl amonium bromide join in the yellow transparent filtrate that step 2 obtains, until there is yellow mercury oxide to produce, continue vigorous stirring 30min, it is fully precipitated;
Step 4: after stirring finishes, the solution filter that contains yellow mercury oxide that step 3 is obtained, obtain yellow mercury oxide product, by the yellow solid product of acquisition first with ethanol lotion 3-5 time, use ether lotion 3-5 time again, finally yellow solid product is carried out to recrystallization purification take acetone as solvent, after completing, recrystallization by yellow crystals product collection, dry in a vacuum, obtains presoma six molybdic acid TBuAs;
Step 5: the presoma six molybdic acid TBuAs that step 4 recrystallization is obtained are placed in the silica tube in tube furnace heat-treats, and obtains monoclinic phase molybdenum dioxide nanometer rod; Described thermal treatment, at N
2in atmosphere, carry out, temperature 600-700 ℃, insulation 2-3h,, then naturally cools to room temperature by temperature rise rate 25-35 ℃/min.
2. the preparation method of molybdenum dioxide nanometer rod according to claim 1, is characterized in that, in described step 1, the volume ratio of acetic anhydride and suspension liquid is 1:10-1:30.
3. the preparation method of molybdenum dioxide nanometer rod according to claim 1, is characterized in that, the add-on of concentrated hydrochloric acid in described step 2 makes the pH value of solution be adjusted to 0.5-1.5.
4. the preparation method of molybdenum dioxide nanometer rod according to claim 1, is characterized in that, the volume ratio of the dimethyl formamide solution of the Tetrabutyl amonium bromide adding in described step 3 and yellow transparent filtrate is 1:1-1:2.
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| CN111621645A (en) * | 2020-06-09 | 2020-09-04 | 西安迈斯拓扑科技有限公司 | Irradiation from accelerator100Mo production99mRecovery from Tc process effluent100Method for Mo |
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