CN102951686A - Preparation method for granular manganese tungstate nanocrystals - Google Patents

Preparation method for granular manganese tungstate nanocrystals Download PDF

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CN102951686A
CN102951686A CN2012104581743A CN201210458174A CN102951686A CN 102951686 A CN102951686 A CN 102951686A CN 2012104581743 A CN2012104581743 A CN 2012104581743A CN 201210458174 A CN201210458174 A CN 201210458174A CN 102951686 A CN102951686 A CN 102951686A
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solution
granular
hydrothermal reaction
microwave hydrothermal
deionized water
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曹丽云
周森
黄剑锋
张婷
张振伟
卢靖
李翠艳
吴建鹏
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Abstract

A preparation method for granular manganese tungstate nanocrystals includes the following steps: tetrahydrate manganese chloride is dissolved into deionized water, so that solution A is obtained; sodium tungstate dehydrate is dissolved into deionized water, so that solution B is obtained; the solution A is slowly added into the solution B, so that solution C is obtained; the pH of the solution C is regulated to 4.0 to 6.0 by hydrochloric acid solution, so that solution D is obtained; the solution D is poured into a microwave hydrothermal reaction kettle, and the filling factor is controlled at 50 to 60 percent; the microwave hydrothermal reaction kettle is then sealed and put into a temperature and pressure controlling microwave hydrothermal reaction instrument; a pressure control mode is selected to carry out reaction, and after reaction is finished, the temperature is naturally cooled to room temperature; product is centrifugally collected, deionized water and absolute ethanol are respectively adopted to wash the product, and after drying, the granular manganese tungstate nanocrystals as final product are obtained. Without needing template, the preparation method can prepare the granular MnWO4 nanocrystals, the morphology of which is complete and the sizes of which are uniform, and moreover, by controlling the temperature and time of microwave reaction, the size can be controlled between 10nm and 40nm. Furthermore, the reaction period is short, the repeatability is good, the preparation method is convenient to operate, the materials are easy to obtain, and the preparation cost is low.

Description

The nanocrystalline preparation method of a kind of granular wolframic acid manganese
Technical field
The present invention relates to a kind of preparation method of wolframic acid manganese, particularly the nanocrystalline preparation method of a kind of granular wolframic acid manganese.
Background technology
Wolframic acid manganese (MnWO 4) crystal is a kind of direct band-gap semicondictor material, has larger band gap width (approximately 2.8eV).Because it has special optics, electricity and magnetic property, the fields such as photoluminescence, optical fiber, scintillator, humidity sensor, magneticsubstance and photocatalyst have been widely used in.The synthetic extensive concern that has caused researcher of nano material in recent years, because nano material uniqueness dimensionally, cause its performance to be higher than common size material far away, so the research of nano material has become a good direction that improves material property.Therefore caused the great interest of researcher as synthesizing of a kind of very promising semiconductor material-nanometer wolframic acid manganese.
Prepare at present MnWO 4The method of crystal mainly contains: hydrothermal method [ZHANG Lei, LU Canzhong, WANGYuansheng, et al.Hydrothermal synthesis and characterization of MnWO 4Nanoplates and their ionic conductivity[J] .Mater Chem Phys, 2007,103 (2-3): 433-436.], solvent-thermal method [CHEN Shujian, CHEN Xuetai, XUE Ziling, et al.Morphologycontrol of MnWO 4Nanocrystals by a solvothermal route[J] .J Mater Chem, 2003,13:1132-1135.], the precipitator method [HE H Y, HUANG J F, CAO L Y, et al.Photodegradation of methylorange aqueous on MnWO 4Powder under different light resources and initial pH[J] .Desalination, 2010,252:66-70.] and circulation microwave assistant spray synthesis method [THONGTEMSomchai, WANNAPOP Surangkana, PHURUANGRAT Anukorn, et al.Cyclicmicrowave-assisted spray synthesis of nanostructured MnWO 4[J] .Mater Lett, 2009,63:833-836.] etc.Yet, above-mentioned several method has certain limitation, such as: the common long reaction time of the hot method of hydrothermal/solvent, reaction efficiency is low and need to add organic solvent etc., the precipitator method not only need higher thermal treatment temp usually, and the grain-size after the calcining is difficult to control etc., circulation microwave assistant spray synthesis method need to be carried out pre-treatment and strict control processing condition etc. to substrate usually, therefore, prepares efficiently the controlled MnWO of particle diameter within lower temperature and shorter time 4Nanocrystalline synthesis technique seems and is even more important.
Summary of the invention
The object of the present invention is to provide that a kind of temperature of reaction is low, the cycle is short, energy consumption is low, and cost is low, and simple to operate, and good reproducibility is fit to the nanocrystalline preparation method of granular wolframic acid manganese of scale operation.
For achieving the above object, the technical solution used in the present invention is:
1) with analytically pure tetrahydrate manganese chloride (MnCl 24H 2O) join in the deionized water, and constantly stir, be mixed with Mn 2+Concentration is the clear solution A of 0.04～0.4mol/L;
2) with analytically pure tungstate dihydrate acid sodium (Na 2WO 42H 2O) join in the deionized water, and constantly stir, be mixed with WO 4 2-Concentration is the clear solution B of 0.04～0.4mol/L;
3) with solution A and the solution B volume ratio by 1: 2～2: 1 the slow ground of solution A is joined in the solution B slowly, and constantly stir, form precursor precipitation solution C;
4) pH that regulates precursor precipitation solution C with hydrochloric acid soln 4.0～6.0 obtains solution D;
5) solution D is poured in the microwave hydrothermal reaction kettle, compactedness is controlled at 50～60%; Then seal microwave hydrothermal reaction kettle, put it in the warm-pressing double-control microwave hydrothermal reaction; Select voltage-controlled pattern to react, Hydro-thermal pressure is controlled at 0.6MPa～3.5MPa, reaction times 60～100min, and reaction naturally cools to room temperature after finishing;
6) open microwave hydrothermal reaction kettle, then product adopts respectively deionized water, absolute ethanol washing 3～5 times by centrifugal collection, dry that the granular wolframic acid manganese of final product is nanocrystalline at 80～100 ℃.
The concentration of described hydrochloric acid soln is 0.5～0.8mol/L.
Described warm-pressing double-control microwave hydrothermal reaction adopts M DS-8 type warm-pressing double-control microwave hydrothermal reaction.
The described dry electric drying oven with forced convection that adopts.
The present invention adopts simple microwave hydrothermal synthesis technique, prepares diameter and be 10～40nm, and the wolframic acid manganese with granular pattern is nanocrystalline.The nanocrystalline complete shape and appearance of granular wolframic acid manganese of gained, size uniform is repeatable high.
Useful effect:
This method does not need to add template can prepare granular MnWO 4Nanocrystalline complete shape and appearance, size is even, and can control size between 10～40nm by control microwave reaction temperature and time.
This technique prepares granular MnWO 4Nanocrystalline reaction time is short, good reproducibility.
This technique preparation is simple, and easy to operate, raw material is easy to get, and preparation cost is lower.
Description of drawings
Fig. 1 is nanocrystalline X-ray diffraction (XRD) collection of illustrative plates of granular wolframic acid manganese of embodiment 1 preparation.
Fig. 2 is nanocrystalline transmission electron microscope (TEM) photo of granular wolframic acid manganese of embodiment 1 preparation.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
Embodiment 1:
1) with analytically pure tetrahydrate manganese chloride (MnCl 24H 2O) join in the deionized water, and constantly stir, be mixed with Mn 2+Concentration is the clear solution A of 0.2mol/L;
2) with analytically pure tungstate dihydrate acid sodium (Na 2WO 42H 2O) join in the deionized water, and constantly stir, be mixed with WO 4 2-Concentration is the clear solution B of 0.2mol/L;
3) with solution A and the solution B volume ratio by 1:1 the slow ground of solution A is joined in the solution B slowly, and constantly stir, form precursor precipitation solution C;
4) pH that regulates precursor precipitation solution C with the hydrochloric acid soln of 0.8mol/L 5.0 obtains solution D;
5) solution D is poured in the microwave hydrothermal reaction kettle, compactedness is controlled at 50%; Then seal microwave hydrothermal reaction kettle, put it in the MDS-8 type warm-pressing double-control microwave hydrothermal reaction; Select voltage-controlled pattern to react, Hydro-thermal pressure is controlled at 1MPa, reaction times 60min, and reaction naturally cools to room temperature after finishing;
6) open microwave hydrothermal reaction kettle, then product adopts respectively deionized water, absolute ethanol washing 3～5 times by centrifugal collection, dry that the granular wolframic acid manganese of final product is nanocrystalline in 80 ℃ at electric drying oven with forced convection.
As can be seen from Figure 1 all diffraction peaks and standard card JCPDS No.80-0133 meet fully, illustrate that prepared powder is MnWO 4Crystalline material.
As can be seen from Figure 2, prepared powder is good granular nanocrystalline of crystal property, and average grain size is about 30nm.
Embodiment 2:
1) with analytically pure tetrahydrate manganese chloride (MnCl 24H 2O) join in the deionized water, and constantly stir, be mixed with Mn 2+Concentration is the clear solution A of 0.4mol/L;
2) with analytically pure tungstate dihydrate acid sodium (Na 2WO 42H 2O) join in the deionized water, and constantly stir, be mixed with WO 4 2-Concentration is the clear solution B of 0.4mol/L;
3) with solution A and the solution B volume ratio by 1:1 the slow ground of solution A is joined in the solution B slowly, and constantly stir, form precursor precipitation solution C;
4) pH that regulates precursor precipitation solution C with the hydrochloric acid soln of 0.6mol/L 6.0 obtains solution D;
5) solution D is poured in the microwave hydrothermal reaction kettle, compactedness is controlled at 50%; Then seal microwave hydrothermal reaction kettle, put it in the MDS-8 type warm-pressing double-control microwave hydrothermal reaction; Select voltage-controlled pattern to react, Hydro-thermal pressure is controlled at 2MPa, reaction times 60min, and reaction naturally cools to room temperature after finishing;
6) open microwave hydrothermal reaction kettle, then product adopts respectively deionized water, absolute ethanol washing 3～5 times by centrifugal collection, dry that the granular wolframic acid manganese of final product is nanocrystalline in 80 ℃ at electric drying oven with forced convection.
Embodiment 3:
1) with analytically pure tetrahydrate manganese chloride (MnCl 24H 2O) join in the deionized water, and constantly stir, be mixed with Mn 2+Concentration is the clear solution A of 0.1mol/L;
2) with analytically pure tungstate dihydrate acid sodium (Na 2WO 42H 2O) join in the deionized water, and constantly stir, be mixed with WO 4 2-Concentration is the clear solution B of 0.1mol/L;
3) with solution A and the solution B volume ratio by 1:2 the slow ground of solution A is joined in the solution B slowly, and constantly stir, form precursor precipitation solution C;
4) pH that regulates precursor precipitation solution C with the hydrochloric acid soln of 0.8mol/L 5.0 obtains solution D;
5) solution D is poured in the microwave hydrothermal reaction kettle, compactedness is controlled at 55%; Then seal microwave hydrothermal reaction kettle, put it in the MDS-8 type warm-pressing double-control microwave hydrothermal reaction; Select voltage-controlled pattern to react, Hydro-thermal pressure is controlled at 0.6MPa, reaction times 100min, and reaction naturally cools to room temperature after finishing;
6) open microwave hydrothermal reaction kettle, then product adopts respectively deionized water, absolute ethanol washing 3～5 times by centrifugal collection, dry that the granular wolframic acid manganese of final product is nanocrystalline in 90 ℃ at electric drying oven with forced convection.
Embodiment 4:
1) with analytically pure tetrahydrate manganese chloride (MnCl 24H 2O) join in the deionized water, and constantly stir, be mixed with Mn 2+Concentration is the clear solution A of 0.04mol/L;
2) with analytically pure tungstate dihydrate acid sodium (Na 2WO 42H 2O) join in the deionized water, and constantly stir, be mixed with WO 4 2-Concentration is the clear solution B of 0.04mol/L;
3) with solution A and the solution B volume ratio by 2:1 the slow ground of solution A is joined in the solution B slowly, and constantly stir, form precursor precipitation solution C;
4) pH that regulates precursor precipitation solution C with the hydrochloric acid soln of 0.5mol/L 4.0 obtains solution D;
5) solution D is poured in the microwave hydrothermal reaction kettle, compactedness is controlled at 60%; Then seal microwave hydrothermal reaction kettle, put it in the MDS-8 type warm-pressing double-control microwave hydrothermal reaction; Select voltage-controlled pattern to react, Hydro-thermal pressure is controlled at 3.5MPa, reaction times 80min, and reaction naturally cools to room temperature after finishing;
6) open microwave hydrothermal reaction kettle, then product adopts respectively deionized water, absolute ethanol washing 3～5 times by centrifugal collection, dry that the granular wolframic acid manganese of final product is nanocrystalline in 100 ℃ at electric drying oven with forced convection.

Claims (4)

1. nanocrystalline preparation method of granular wolframic acid manganese is characterized in that:
1) with analytically pure tetrahydrate manganese chloride (MnCl 24H 2O) join in the deionized water, and constantly stir, be mixed with Mn 2+Concentration is the clear solution A of 0.04～0.4mol/L;
2) with analytically pure tungstate dihydrate acid sodium (Na 2WO 42H 2O) join in the deionized water, and constantly stir, be mixed with WO 4 2-Concentration is the clear solution B of 0.04～0.4mol/L;
3) with solution A and the solution B volume ratio by 1: 2～2: 1 the slow ground of solution A is joined in the solution B slowly, and constantly stir, form precursor precipitation solution C;
4) pH that regulates precursor precipitation solution C with hydrochloric acid soln 4.0～6.0 obtains solution D;
5) solution D is poured in the microwave hydrothermal reaction kettle, compactedness is controlled at 50～60%; Then seal microwave hydrothermal reaction kettle, put it in the warm-pressing double-control microwave hydrothermal reaction; Select voltage-controlled pattern to react, Hydro-thermal pressure is controlled at 0.6M Pa～3.5M Pa, reaction times 60～100min, and reaction naturally cools to room temperature after finishing;
6) open microwave hydrothermal reaction kettle, then product adopts respectively deionized water, absolute ethanol washing 3～5 times by centrifugal collection, dry that the granular wolframic acid manganese of final product is nanocrystalline at 80～100 ℃.
2. the nanocrystalline preparation method of granular wolframic acid manganese according to claim 1, it is characterized in that: the concentration of described hydrochloric acid soln is 0.5～0.8mol/L.
3. the nanocrystalline preparation method of granular wolframic acid manganese according to claim 1 is characterized in that: described warm-pressing double-control microwave hydrothermal reaction employing MDS-8 type warm-pressing double-control microwave hydrothermal reaction.
4. the nanocrystalline preparation method of granular wolframic acid manganese according to claim 1 is characterized in that: the described dry electric drying oven with forced convection that adopts.
CN2012104581743A 2012-11-14 2012-11-14 Preparation method for granular manganese tungstate nanocrystals Pending CN102951686A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104192914A (en) * 2014-08-29 2014-12-10 洛阳理工学院 Preparation method of manganese tungsten single-crystalline nanowire
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
CN107032406A (en) * 2017-05-08 2017-08-11 陕西科技大学 A kind of micro-nano beam of manganese molybdate and preparation method thereof
CN107433202A (en) * 2017-09-22 2017-12-05 常州大学 A kind of preparation method of phosphorus doping manganese tungstate
CN108754526A (en) * 2018-04-12 2018-11-06 中国科学院合肥物质科学研究院 A kind of manganese tungstate nanometer sheet material and the preparation method and application thereof
CN110357163A (en) * 2019-08-16 2019-10-22 陕西科技大学 A kind of manganese tungstate carbon composite nano ball and preparation method thereof
CN110451566A (en) * 2019-08-16 2019-11-15 陕西科技大学 A kind of wolframic acid europium carbon composite nano ball and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101182028A (en) * 2007-11-23 2008-05-21 陕西科技大学 Method for preparing ZnO nano rod
CN101319371A (en) * 2008-05-14 2008-12-10 陕西科技大学 Production method of spindle-shaped nano ZnO monocrystal

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101182028A (en) * 2007-11-23 2008-05-21 陕西科技大学 Method for preparing ZnO nano rod
CN101319371A (en) * 2008-05-14 2008-12-10 陕西科技大学 Production method of spindle-shaped nano ZnO monocrystal

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
周森等: "pH值对微波水热法制备MnWO4微晶形貌的影响", 《硅酸盐学报》 *
张晓薇等: "微波水热时间对ZnWO4纳米晶形貌及光学性能的影响", 《硅酸盐学报》 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104192914A (en) * 2014-08-29 2014-12-10 洛阳理工学院 Preparation method of manganese tungsten single-crystalline nanowire
CN104192914B (en) * 2014-08-29 2016-04-13 洛阳理工学院 A kind of preparation method of manganese tungstate monocrystal nanowire
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
CN107032406A (en) * 2017-05-08 2017-08-11 陕西科技大学 A kind of micro-nano beam of manganese molybdate and preparation method thereof
CN107433202A (en) * 2017-09-22 2017-12-05 常州大学 A kind of preparation method of phosphorus doping manganese tungstate
CN108754526A (en) * 2018-04-12 2018-11-06 中国科学院合肥物质科学研究院 A kind of manganese tungstate nanometer sheet material and the preparation method and application thereof
CN110357163A (en) * 2019-08-16 2019-10-22 陕西科技大学 A kind of manganese tungstate carbon composite nano ball and preparation method thereof
CN110451566A (en) * 2019-08-16 2019-11-15 陕西科技大学 A kind of wolframic acid europium carbon composite nano ball and preparation method thereof
CN110451566B (en) * 2019-08-16 2021-08-20 陕西科技大学 Europium tungstate carbon composite nanospheres and preparation method thereof
CN110357163B (en) * 2019-08-16 2021-10-29 陕西科技大学 Manganese tungstate-carbon composite nanospheres and preparation method thereof

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Application publication date: 20130306