CN104192914B - A kind of preparation method of manganese tungstate monocrystal nanowire - Google Patents
A kind of preparation method of manganese tungstate monocrystal nanowire Download PDFInfo
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- CN104192914B CN104192914B CN201410432109.2A CN201410432109A CN104192914B CN 104192914 B CN104192914 B CN 104192914B CN 201410432109 A CN201410432109 A CN 201410432109A CN 104192914 B CN104192914 B CN 104192914B
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Abstract
A kind of preparation method of manganese tungstate monocrystal nanowire, elder generation for raw material with Manganous chloride tetrahydrate, salt of wormwood and Seignette salt, prepares manganous carbonate precursor, is then mixed with the manganous carbonate precursor prepared by sodium wolframate, at 120 ~ 200 DEG C, hydro-thermal reaction obtains manganese tungstate monocrystal nanowire; The present invention has morphology controllable, technique is simple, with low cost, is easy to the advantage realizing suitability for industrialized production.The manganese tungstate nano wire that the present invention obtains has single crystal structure and very high length-to-diameter ratio, and thus have a very wide range of applications prospect in multi-iron material, photocatalyst, photoluminescence, optical fiber, scintillator, humidity sensor and magneticsubstance etc.
Description
Technical field
The present invention relates to field of inorganic nonmetallic material, relate to a kind of preparation method of manganese tungstate monocrystal nanowire specifically.
Background technology
Manganese tungstate is a kind of important functional materials with wolframite structure, has a wide range of applications in multi-iron material, photocatalyst, photoluminescence, optical fiber, scintillator, humidity sensor and magneticsubstance etc.
Manganese tungstate nano wire, because having larger length-to-diameter ratio, less crystal boundary and defect sites and more surface atom, thus can significantly improve its catalytic activity and often show physical and chemical performance excellent especially.The common method preparing nano wire is at present template and surfactant method.Introducing tensio-active agent can to environment, and complicated operation.Only American adopts template successfully to prepare manganese tungstate nano wire at present, but template just plays confinement effect from outside to the growth of crystal, crystal grain becomes the shape of template through reunion, what therefore obtain is only manganese tungstate multicrystal nano-wire, and template complicated operation, after template is expensive, reaction terminates, in the process removing template, easily produce pollution.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of manganese tungstate monocrystal nanowire, it is under the condition not using template and tensio-active agent, the oriented growth of crystal is controlled by controlling reaction precursor, have simple to operate, morphology controllable, the advantage such as with low cost, the manganese tungstate monocrystal nanowire that the present invention prepares has very high length-to-diameter ratio, its physical and chemical performance of effective raising, has extraordinary industrial applications prospect.
The technical solution adopted in the present invention is: a kind of preparation method of manganese tungstate monocrystal nanowire, comprises the following steps:
Step one, prepare the deionized water solution of Manganous chloride tetrahydrate, Seignette salt and salt of wormwood respectively;
Step 2, get the obtained Manganous chloride tetrahydrate deionized water solution of step one and Seignette salt deionized water solution mixes according to equimolar amount, obtain manganous tartrate precipitation solution as reaction precursor, for subsequent use;
The salt of wormwood deionized water solution that mole step one is prepared such as to add in step 3, the manganous tartrate precipitation solution that obtains in step 2, join after mixing in hydrothermal reaction kettle and carry out hydro-thermal reaction, generate manganous carbonate precipitation solution, for subsequent use;
Step 4, the hydrothermal reaction kettle in step 3 is cooled to room temperature, the sodium wolframate powder with Manganous chloride tetrahydrate equimolar amount in step 2 is added in this hydrothermal reaction kettle, sealing, carry out hydro-thermal reaction, after having reacted, hydrothermal reaction kettle is cooled to room temperature, unloads still, use distilled water wash reaction product, after filtration, oven dry, obtain manganese tungstate monocrystal nanowire.
The purity of described sodium wolframate, Manganous chloride tetrahydrate, salt of wormwood, Seignette salt is all not less than chemical pure.
In described step one, the concentration of the Manganous chloride tetrahydrate of preparation, the deionized water solution of Seignette salt and salt of wormwood is 0.1 ~ 3.0mol/L, and in described step 3 and step 4, hydro-thermal reaction is all carried out under 120 ~ 200 DEG C of conditions, and the reaction times is 4 ~ 12 hours.
Beneficial effect of the present invention: the manganese tungstate monocrystal nanowire that the present invention obtains has high length-diameter ratio, its length-to-diameter ratio reaches more than 50, at photoluminescence, optical fiber, multi-iron material, photocatalyst, scintillator, the aspect such as humidity sensor and magneticsubstance has a wide range of applications, the present invention adopts twice hydro-thermal reaction, through the precursor manganous carbonate of hydro-thermal reaction generation first, can not only effectively obtain manganese tungstate monocrystal nanowire, and make the nano wire quality that obtains good, the hydro-thermal reaction time of the present invention is 4 ~ 12 hours, the time that effectively prevent is too short can not prepare required product, overlong time causes the problem of energy dissipation.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the manganese tungstate monocrystal nanowire that the present invention synthesizes;
Fig. 2 is the transmission electron microscope picture of the manganese tungstate monocrystal nanowire that the present invention synthesizes;
Fig. 3 is the electron-diffraction diagram of the manganese tungstate monocrystal nanowire that the present invention synthesizes.
Embodiment
As shown in the figure, a kind of preparation method of manganese tungstate monocrystal nanowire, comprises the following steps:
Step one, prepare the deionized water solution of Manganous chloride tetrahydrate, Seignette salt and salt of wormwood respectively;
Step 2, get the obtained Manganous chloride tetrahydrate deionized water solution of step one and Seignette salt deionized water solution mixes according to equimolar amount, obtain manganous tartrate precipitation solution as reaction precursor, for subsequent use;
The salt of wormwood deionized water solution that mole step one is prepared such as to add in step 3, the manganous tartrate precipitation solution that obtains in step 2, join after mixing in hydrothermal reaction kettle and carry out hydro-thermal reaction, generate manganous carbonate precipitation solution, for subsequent use;
Step 4, the hydrothermal reaction kettle in step 3 is cooled to room temperature, the sodium wolframate powder with Manganous chloride tetrahydrate equimolar amount in step 2 is added in this hydrothermal reaction kettle, sealing, carry out hydro-thermal reaction, after having reacted, hydrothermal reaction kettle is cooled to room temperature, unloads still, use distilled water wash reaction product, after filtration, oven dry, obtain manganese tungstate monocrystal nanowire.
The purity of described sodium wolframate, Manganous chloride tetrahydrate, salt of wormwood, Seignette salt is all not less than chemical pure.
In described step one, the concentration of the Manganous chloride tetrahydrate of preparation, the deionized water solution of Seignette salt and salt of wormwood is 0.1 ~ 3.0mol/L, and in described step 3 and step 4, hydro-thermal reaction is all carried out under 120 ~ 200 DEG C of conditions, and the reaction times is 4 ~ 12 hours.
In described step 3, the compactedness of hydrothermal reaction kettle is 70% ~ 90%.
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
Step one, Manganous chloride tetrahydrate is dissolved in deionized water, form the Manganous chloride tetrahydrate aqueous solution, the concentration of the Manganous chloride tetrahydrate in regulator solution is 0.1mol/L;
Step 2, Seignette salt is dissolved in deionized water, form aqueous sodium potassium tartrate, the concentration of the Seignette salt in regulator solution is 0.1mol/L;
Step 3, salt of wormwood is dissolved in deionized water, form wet chemical, the concentration of the salt of wormwood in regulator solution is 0.1mol/L;
Step 4, by manganese chloride solution obtained for step one and the obtained potassium sodium tartrate solution of step 2 according to etc. mole mixing, obtain manganous tartrate precipitation as reaction precursor;
The obtained manganous tartrate precipitation solution of step 5, solution of potassium carbonate that step 3 is obtained and step 4 according to etc. mole to mix, then join in reactor inner bag, regulate the reaction mass volume in reactor inner bag to reach 70% of reactor inner bag volume with distilled water;
Step 6, reactor inner bag step 5 being equipped with reaction mass are placed in reactor, sealing, and at 120 DEG C, insulation carries out hydrothermal treatment consists in 4 hours, then allows reactor naturally cool to room temperature;
Step 7, by after the reactor of cool to room temperature is opened in step 6, in reactor inner bag, put into the equimolar sodium wolframate powder with manganous carbonate;
Step 8, reactor inner bag step 7 being equipped with reaction mass are placed in reactor, sealing, at 120 DEG C, insulation carries out hydrothermal treatment consists in 4 hours, then reactor is allowed to naturally cool to room temperature, after unloading still, by distilled water repetitive scrubbing reaction product, after filtration, oven dry, obtain the manganese tungstate monocrystal nanowire of well-crystallized.The length of manganese tungstate nano wire is about 1-1.5um, and diameter is about 20-30nm, and length-to-diameter ratio is about 50.Its XRD figure spectrum is shown in Fig. 1; Transmission electron microscope picture is shown in Fig. 2, and Fig. 3 is shown in by electron-diffraction diagram; Electron diffraction picture proves that the manganese tungstate nano wire that the present invention prepares has single crystal structure.
Embodiment 2
Step one, Manganous chloride tetrahydrate is dissolved in deionized water, form the Manganous chloride tetrahydrate aqueous solution, the concentration of the Manganous chloride tetrahydrate in regulator solution is 2.1mol/L;
Step 2, Seignette salt is dissolved in deionized water, form aqueous sodium potassium tartrate, the concentration of the Seignette salt in regulator solution is 2.1mol/L;
Step 3, salt of wormwood is dissolved in deionized water, form wet chemical, the concentration of the salt of wormwood in regulator solution is 2.1mol/L;
Step 4, by manganese chloride solution obtained for step one and the obtained potassium sodium tartrate solution of step 2 according to etc. mole mixing, obtain manganous tartrate precipitation as reaction precursor;
The obtained manganous tartrate precipitation solution of step 5, solution of potassium carbonate that step 3 is obtained and step 4 according to etc. mole to mix, then join in reactor inner bag, regulate the reaction mass volume in reactor inner bag to reach 80% of reactor inner bag volume with distilled water;
Step 6, reactor inner bag step 5 being equipped with reaction mass are placed in reactor, sealing, and at 160 DEG C, insulation carries out hydrothermal treatment consists in 12 hours, then allows reactor naturally cool to room temperature;
Step 7, by after the reactor of cool to room temperature is opened in step 6, in reactor inner bag, put into the equimolar sodium wolframate powder with manganous carbonate;
Step 8, reactor inner bag step 7 being equipped with reaction mass are placed in reactor, sealing, at 200 DEG C, insulation carries out hydrothermal treatment consists in 6 hours, then reactor is allowed to naturally cool to room temperature, after unloading still, by distilled water repetitive scrubbing reaction product, after filtration, oven dry, obtain manganese tungstate monocrystal nanowire.
Embodiment 3
Step one, Manganous chloride tetrahydrate is dissolved in deionized water, form the Manganous chloride tetrahydrate aqueous solution, the concentration of the Manganous chloride tetrahydrate in regulator solution is 3.0mol/L;
Step 2, Seignette salt is dissolved in deionized water, form aqueous sodium potassium tartrate, the concentration of the Seignette salt in regulator solution is 3.0mol/L;
Step 3, salt of wormwood is dissolved in deionized water, form wet chemical, the concentration of the salt of wormwood in regulator solution is 3.0mol/L;
The potassium sodium tartrate solution that step 4, manganese chloride solution step one obtained and step 2 obtain mixes according to equimolar amount, obtains manganous tartrate precipitation as reaction precursor;
The manganous tartrate precipitation solution that step 5, the solution of potassium carbonate and the step 4 that step 3 are obtained obtain mixes according to equimolar amount, then join in reactor inner bag, regulate the reaction mass volume in reactor inner bag to reach 90% of reactor inner bag volume with distilled water;
Step 6, reactor inner bag step 5 being equipped with reaction mass are placed in reactor, sealing, and at 200 DEG C, insulation carries out hydrothermal treatment consists in 6 hours, then allows reactor naturally cool to room temperature;
Step 7, by after the reactor of cool to room temperature is opened in step 6, in reactor inner bag, put into the equimolar sodium wolframate powder with manganous carbonate;
Step 8, reactor inner bag step 7 being equipped with reaction mass are placed in reactor, sealing, at 160 DEG C, insulation carries out hydrothermal treatment consists in 12 hours, then reactor is allowed to naturally cool to room temperature, after unloading still, by distilled water repetitive scrubbing reaction product, after filtration, oven dry, obtain manganese tungstate monocrystal nanowire.
Claims (2)
1. a preparation method for manganese tungstate monocrystal nanowire, is characterized in that: comprise the following steps:
Step one, prepare the deionized water solution of Manganous chloride tetrahydrate, Seignette salt and salt of wormwood respectively, the concentration of the deionized water solution of the Manganous chloride tetrahydrate of described preparation, Seignette salt and salt of wormwood is 0.1 ~ 3.0mol/L;
Step 2, getting the obtained Manganous chloride tetrahydrate deionized water solution of step one and Seignette salt deionized water solution mixes according to equimolar amount, obtaining solution containing manganous tartrate precipitation as reacting precursor, for subsequent use;
Step 3, the salt of wormwood deionized water solution containing in the solution of manganous tartrate precipitation mole step one preparations such as adding obtained in step 2, join after mixing in hydrothermal reaction kettle, hydro-thermal reaction is carried out 4 ~ 12 hours under temperature is 120 ~ 200 DEG C of conditions, generate the solution containing manganous carbonate precipitation, for subsequent use;
Step 4, the hydrothermal reaction kettle in step 3 is cooled to room temperature, the sodium wolframate powder with Manganous chloride tetrahydrate equimolar amount in step 2 is added in this hydrothermal reaction kettle, sealing, hydro-thermal reaction is carried out 4 ~ 12 hours under temperature is 120 ~ 200 DEG C of conditions, after having reacted, hydrothermal reaction kettle is cooled to room temperature, unloads still, use distilled water wash reaction product, after filtration, oven dry, obtain manganese tungstate monocrystal nanowire.
2. the preparation method of a kind of manganese tungstate monocrystal nanowire as claimed in claim 1, is characterized in that: the purity of described sodium wolframate, Manganous chloride tetrahydrate, salt of wormwood, Seignette salt is all not less than chemical pure.
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| CN106673439B (en) * | 2016-12-28 | 2019-01-29 | 蒙娜丽莎集团股份有限公司 | A kind of glaze compositions and preparation method thereof using manganese tungstate as active material with photo-catalysis function |
| CN107486200A (en) * | 2017-09-21 | 2017-12-19 | 柳州若思纳米材料科技有限公司 | A kind of preparation method of the compound wolframic acid Mn catalyst of carbon |
| CN107497454A (en) * | 2017-09-21 | 2017-12-22 | 柳州若思纳米材料科技有限公司 | A kind of preparation method of thio wolframic acid Mn catalyst |
| CN111704169B (en) * | 2020-07-01 | 2022-09-30 | 洛阳理工学院 | Preparation method of manganese molybdate nanosheet crystal |
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| CN102664105A (en) * | 2012-04-28 | 2012-09-12 | 中国科学院福建物质结构研究所 | Manganese tungstate electrode material and preparation method thereof |
| CN102951686A (en) * | 2012-11-14 | 2013-03-06 | 陕西科技大学 | Preparation method for granular manganese tungstate nanocrystals |
| CN102951685A (en) * | 2012-11-14 | 2013-03-06 | 陕西科技大学 | Preparation method of rod-like manganese tungstate microcrystal |
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| CN102664105A (en) * | 2012-04-28 | 2012-09-12 | 中国科学院福建物质结构研究所 | Manganese tungstate electrode material and preparation method thereof |
| CN102951686A (en) * | 2012-11-14 | 2013-03-06 | 陕西科技大学 | Preparation method for granular manganese tungstate nanocrystals |
| CN102951685A (en) * | 2012-11-14 | 2013-03-06 | 陕西科技大学 | Preparation method of rod-like manganese tungstate microcrystal |
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