CN104192914A - Preparation method of manganese tungsten single-crystalline nanowire - Google Patents
Preparation method of manganese tungsten single-crystalline nanowire Download PDFInfo
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- CN104192914A CN104192914A CN201410432109.2A CN201410432109A CN104192914A CN 104192914 A CN104192914 A CN 104192914A CN 201410432109 A CN201410432109 A CN 201410432109A CN 104192914 A CN104192914 A CN 104192914A
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Abstract
The invention discloses a preparation method of a manganese tungsten single-crystalline nanowire. The method comprises the following steps: firstly, preparing a manganese tungsten precursor by using manganese chloride, potassium carbonate and sodium potassium tartrate tetrahydrate; and then mixing sodium tungstate with the prepared manganese tungsten precursor; and carrying out hydrothermal reaction at 120-200 DEG C, so as to obtain the manganese tungsten single-crystalline nanowire. The manganese tungsten single-crystalline nanowire has the advantages of controllable morphology, simple process and low cost, can be put into industrial production, and has a single-crystalline structure and a very high draw ratio; therefore, the preparation method has a very wide application prospect on the aspects of multiferroic materials, photocatalysts, photoluminescence, optical fibers, scintillators, humidity sensors and magnetic materials.
Description
Technical field
The present invention relates to field of inorganic nonmetallic material, relate to specifically a kind of preparation method of wolframic acid manganese monocrystal nanowire.
Background technology
Wolframic acid manganese is a kind of important functional materials with wolframite structure, has a wide range of applications at aspects such as multi-iron material, photocatalyst, photoluminescence, optical fiber, scintillator, humidity sensor and magneticsubstances.
Wolframic acid manganese nano wire is because having larger length-to-diameter ratio, less crystal boundary and defect sites and more surface atom, thereby can significantly improve its catalytic activity and often show excellent especially physical and chemical performance.The common method of preparing at present nano wire is template and surfactant method.Introducing tensio-active agent can be to environment, and complicated operation.Only American adopts template successfully to prepare wolframic acid manganese 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 wolframic acid manganese multicrystal nano-wire, and template complicated operation, after template is expensive, reaction finishes, in the process of removing template, easily produces and pollute.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of wolframic acid manganese monocrystal nanowire, it is not using under the condition of template and tensio-active agent, react precursor and control the oriented growth of crystal by control, have simple to operate, the advantage such as pattern is controlled, with low cost, the wolframic acid manganese monocrystal nanowire that the present invention prepares has very high length-to-diameter ratio, effectively improve its physical and chemical performance, there is extraordinary industrial applications prospect.
The technical solution adopted in the present invention is: a kind of preparation method of wolframic acid manganese monocrystal nanowire, comprises the following steps:
Step 1, prepare respectively the deionized water solution of Manganous chloride tetrahydrate, Seignette salt and salt of wormwood;
Step 2, get Manganous chloride tetrahydrate deionized water solution and the Seignette salt deionized water solution that step 1 makes and mix according to equimolar amount, obtain manganous tartrate precipitation solution as reaction precursor, for subsequent use;
Step 3, to the salt of wormwood deionized water solution of mole step 1 preparations such as adding in the manganous tartrate precipitation solution obtaining in step 2, after mixing, join 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, to add in this hydrothermal reaction kettle with step 2 in the sodium wolframate powder of Manganous chloride tetrahydrate equimolar amount, 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 filtering, drying, obtain wolframic acid manganese monocrystal nanowire.
The purity of described sodium wolframate, Manganous chloride tetrahydrate, salt of wormwood, Seignette salt is all not less than chemical pure.
The concentration of the deionized water solution of Manganous chloride tetrahydrate, Seignette salt and the salt of wormwood of preparing in described step 1 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 wolframic acid manganese monocrystal nanowire that the present invention makes has high length-diameter ratio, its length-to-diameter ratio has reached 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 hydro-thermal reaction twice, through the precursor manganous carbonate that hydro-thermal reaction generates first, not only can effectively obtain wolframic acid manganese monocrystal nanowire, and make the nano wire product quality that obtains good, the hydro-thermal reaction time of the present invention is 4 ~ 12 hours, effectively avoid the time too shortly can not prepare required product, overlong time causes the problem of energy dissipation.
Brief description of the drawings
Fig. 1 is the XRD figure spectrum of the synthetic wolframic acid manganese monocrystal nanowire of the present invention;
Fig. 2 is the transmission electron microscope picture of the synthetic wolframic acid manganese monocrystal nanowire of the present invention;
Fig. 3 is the electron-diffraction diagram of the synthetic wolframic acid manganese monocrystal nanowire of the present invention.
Embodiment
As shown in the figure, a kind of preparation method of wolframic acid manganese monocrystal nanowire, comprises the following steps:
Step 1, prepare respectively the deionized water solution of Manganous chloride tetrahydrate, Seignette salt and salt of wormwood;
Step 2, get Manganous chloride tetrahydrate deionized water solution and the Seignette salt deionized water solution that step 1 makes and mix according to equimolar amount, obtain manganous tartrate precipitation solution as reaction precursor, for subsequent use;
Step 3, to the salt of wormwood deionized water solution of mole step 1 preparations such as adding in the manganous tartrate precipitation solution obtaining in step 2, after mixing, join 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, to add in this hydrothermal reaction kettle with step 2 in the sodium wolframate powder of Manganous chloride tetrahydrate equimolar amount, 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 filtering, drying, obtain wolframic acid manganese monocrystal nanowire.
The purity of described sodium wolframate, Manganous chloride tetrahydrate, salt of wormwood, Seignette salt is all not less than chemical pure.
The concentration of the deionized water solution of Manganous chloride tetrahydrate, Seignette salt and the salt of wormwood of preparing in described step 1 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%.
Further illustrate the present invention below in conjunction with embodiment.
Embodiment 1
Step 1, Manganous chloride tetrahydrate is dissolved in to deionized water, forms 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 to deionized water, forms soluble tartrate sodium water solution, the concentration of the Seignette salt in regulator solution is 0.1mol/L;
Step 3, salt of wormwood is dissolved in to deionized water, forms wet chemical, the concentration of the salt of wormwood in regulator solution is 0.1mol/L;
The potassium sodium tartrate solution that step 4, the manganese chloride solution that step 1 is made and step 2 make according to etc. mole mixing, obtain manganous tartrate precipitation as reaction precursor;
The manganous tartrate precipitation solution that step 5, the solution of potassium carbonate that step 3 is made make with step 4 according to etc. mole 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, the reactor inner bag that step 5 is equipped with to reaction mass are placed in reactor, and sealing is incubated 4 hours and carries out hydrothermal treatment consists at 120 DEG C, then allows reactor naturally cool to room temperature;
Step 7, the reactor of cool to room temperature in step 6 is opened after, in reactor inner bag, put into and the equimolar sodium wolframate powder of manganous carbonate;
Step 8, the reactor inner bag that step 7 is equipped with to reaction mass are placed in reactor, sealing, at 120 DEG C, be incubated 4 hours and carry out hydrothermal treatment consists, then allow reactor naturally cool to room temperature, unload after still, by distilled water repetitive scrubbing reaction product, after filtering, drying, obtain well-crystallized's wolframic acid manganese monocrystal nanowire.The length of wolframic acid manganese 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 wolframic acid manganese nano wire that the present invention prepares has single crystal structure.
Embodiment 2
Step 1, Manganous chloride tetrahydrate is dissolved in to deionized water, forms 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 to deionized water, forms soluble tartrate sodium water solution, the concentration of the Seignette salt in regulator solution is 2.1mol/L;
Step 3, salt of wormwood is dissolved in to deionized water, forms wet chemical, the concentration of the salt of wormwood in regulator solution is 2.1mol/L;
The potassium sodium tartrate solution that step 4, the manganese chloride solution that step 1 is made and step 2 make according to etc. mole mixing, obtain manganous tartrate precipitation as reaction precursor;
The manganous tartrate precipitation solution that step 5, the solution of potassium carbonate that step 3 is made make with step 4 according to etc. mole 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, the reactor inner bag that step 5 is equipped with to reaction mass are placed in reactor, and sealing is incubated 12 hours and carries out hydrothermal treatment consists at 160 DEG C, then allows reactor naturally cool to room temperature;
Step 7, the reactor of cool to room temperature in step 6 is opened after, in reactor inner bag, put into and the equimolar sodium wolframate powder of manganous carbonate;
Step 8, the reactor inner bag that step 7 is equipped with to reaction mass are placed in reactor, sealing, at 200 DEG C, be incubated 6 hours and carry out hydrothermal treatment consists, then allow reactor naturally cool to room temperature, unload after still, by distilled water repetitive scrubbing reaction product, after filtering, drying, obtain wolframic acid manganese monocrystal nanowire.
Embodiment 3
Step 1, Manganous chloride tetrahydrate is dissolved in to deionized water, forms 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 to deionized water, forms soluble tartrate sodium water solution, the concentration of the Seignette salt in regulator solution is 3.0mol/L;
Step 3, salt of wormwood is dissolved in to deionized water, forms wet chemical, the concentration of the salt of wormwood in regulator solution is 3.0mol/L;
The potassium sodium tartrate solution that step 4, the manganese chloride solution that step 1 is made and step 2 make 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 that step 3 is made make with step 4 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, the reactor inner bag that step 5 is equipped with to reaction mass are placed in reactor, and sealing is incubated 6 hours and carries out hydrothermal treatment consists at 200 DEG C, then allows reactor naturally cool to room temperature;
Step 7, the reactor of cool to room temperature in step 6 is opened after, in reactor inner bag, put into and the equimolar sodium wolframate powder of manganous carbonate;
Step 8, the reactor inner bag that step 7 is equipped with to reaction mass are placed in reactor, sealing, at 160 DEG C, be incubated 12 hours and carry out hydrothermal treatment consists, then allow reactor naturally cool to room temperature, unload after still, by distilled water repetitive scrubbing reaction product, after filtering, drying, obtain wolframic acid manganese monocrystal nanowire.
Claims (3)
1. a preparation method for wolframic acid manganese monocrystal nanowire, is characterized in that: comprise the following steps:
Step 1, prepare respectively the deionized water solution of Manganous chloride tetrahydrate, Seignette salt and salt of wormwood;
Step 2, get Manganous chloride tetrahydrate deionized water solution and the Seignette salt deionized water solution that step 1 makes and mix according to equimolar amount, obtain manganous tartrate precipitation solution as reaction precursor, for subsequent use;
Step 3, to the salt of wormwood deionized water solution of mole step 1 preparations such as adding in the manganous tartrate precipitation solution obtaining in step 2, after mixing, join 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, to add in this hydrothermal reaction kettle with step 2 in the sodium wolframate powder of Manganous chloride tetrahydrate equimolar amount, 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 filtering, drying, obtain wolframic acid manganese monocrystal nanowire.
2. the preparation method of a kind of wolframic acid manganese 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.
3. the preparation method of a kind of wolframic acid manganese monocrystal nanowire as claimed in claim 1, it is characterized in that: the concentration of the deionized water solution of Manganous chloride tetrahydrate, Seignette salt and the salt of wormwood of preparing in described step 1 is 0.1 ~ 3.0mol/L, 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.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673439A (en) * | 2016-12-28 | 2017-05-17 | 蒙娜丽莎集团股份有限公司 | Glaze composition prepared from manganese tungstate as active material and having photocatalytic function and preparation method of glaze composition |
| 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 |
| CN111704169A (en) * | 2020-07-01 | 2020-09-25 | 洛阳理工学院 | Preparation method of manganese molybdate nanosheet crystal |
| CN115634686A (en) * | 2022-09-09 | 2023-01-24 | 齐鲁工业大学 | Photocatalytic material MWO capable of responding to visible light, near infrared light and selective degradation thereof 4 And preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009071862A2 (en) * | 2007-11-30 | 2009-06-11 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Purified powder of nanometric particles |
| 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 |
| CN102951685A (en) * | 2012-11-14 | 2013-03-06 | 陕西科技大学 | Preparation method of rod-like manganese tungstate microcrystal |
| CN102951686A (en) * | 2012-11-14 | 2013-03-06 | 陕西科技大学 | Preparation method for granular manganese tungstate nanocrystals |
-
2014
- 2014-08-29 CN CN201410432109.2A patent/CN104192914B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009071862A2 (en) * | 2007-11-30 | 2009-06-11 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Purified powder of nanometric particles |
| 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 |
| CN102951685A (en) * | 2012-11-14 | 2013-03-06 | 陕西科技大学 | Preparation method of rod-like manganese tungstate microcrystal |
| CN102951686A (en) * | 2012-11-14 | 2013-03-06 | 陕西科技大学 | Preparation method for granular manganese tungstate nanocrystals |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673439A (en) * | 2016-12-28 | 2017-05-17 | 蒙娜丽莎集团股份有限公司 | Glaze composition prepared from manganese tungstate as active material and having photocatalytic function and preparation method of glaze composition |
| 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 |
| CN111704169A (en) * | 2020-07-01 | 2020-09-25 | 洛阳理工学院 | Preparation method of manganese molybdate nanosheet crystal |
| CN111704169B (en) * | 2020-07-01 | 2022-09-30 | 洛阳理工学院 | Preparation method of manganese molybdate nanosheet crystal |
| CN115634686A (en) * | 2022-09-09 | 2023-01-24 | 齐鲁工业大学 | Photocatalytic material MWO capable of responding to visible light, near infrared light and selective degradation thereof 4 And preparation method and application thereof |
| CN115634686B (en) * | 2022-09-09 | 2024-04-16 | 齐鲁工业大学 | Photocatalytic material MWO capable of responding to visible light and near infrared light and selectively degrading 4 Preparation method and application thereof |
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