CN103922412B - A kind of microwave-hydrothermal method prepares sheet SmWO 4(OH) method - Google Patents

A kind of microwave-hydrothermal method prepares sheet SmWO 4(OH) method Download PDF

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CN103922412B
CN103922412B CN201410155185.3A CN201410155185A CN103922412B CN 103922412 B CN103922412 B CN 103922412B CN 201410155185 A CN201410155185 A CN 201410155185A CN 103922412 B CN103922412 B CN 103922412B
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smwo
hydrothermal
sheet
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CN103922412A (en
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黄剑锋
李颖慧
李嘉胤
卢靖
曹丽云
李翠艳
吴建鹏
孔新刚
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Yancheng julonghu Business Cluster Development Co.,Ltd.
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Shaanxi University of Science and Technology
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Abstract

The invention provides a kind of microwave-hydrothermal method and prepare sheet SmWO 4(OH) method: by Na 2wO 4solution drops to SmCl 3in solution, constantly stir and obtain white suspension liquid, regulate pH=6 ~ 9 of white suspension liquid to obtain microwave hydrothermal precursor liquid, in microwave hydrothermal reaction, react 60 ~ 90min at 180 ~ 220 DEG C, then centrifugation, washing, drying obtain sheet SmWO 4(OH) crystallite, the present invention adopts wet chemistry method to prepare sheet SmWO 4(OH), microwave-hydrothermal method technological process is simple, and temperature of reaction is lower, and the time is short, and processing parameter is easy to control, reacts for a long time or atmosphere protection without the need to high temperature, without the need to subsequent disposal, can prepare highly purified sheet SmWO fast 4(OH).

Description

A kind of microwave-hydrothermal method prepares sheet SmWO 4(OH) method
Technical field
The present invention relates to a kind of SmWO 4(OH) preparation method, particularly one adopts microwave-hydrothermal method to prepare sheet SmWO 4(OH) method.
Background technology
Wolframic acid samarium is a member in tungstate series, is a kind ofly very potentially but to study relatively less novel photocatalyst, all has a good application prospect in the field such as Degradation of Organo-pollutants in Water with Photo-catalysis and photolysis water hydrogen.To the exploitation of the preparation method of wolframic acid samarium, the theory of photocatalysis field and application aspect all significant.In addition, wolframic acid samarium also may have paramagnetism, ferroelectric, the property such as piezoelectricity, pyroelectricity, non-linear electric susceptibility, negative expansion, is with a wide range of applications.
At present mainly Bi is concentrated on to the report of tungstate 2wO 6, CaWO 4, FeWO 4, BaWO 4deng material, and also rarely found to the report of wolframic acid samarium and alkali formula wolframic acid samarium, and the preparation method adopted in existing report mostly is solid reaction process.
E.Tomaszewicz passes through solid reaction process, with Sm 2o 3and WO 3for Sm prepared by raw material 2wO 6crystal [E.Tomaszewicz.Reactivity in the solid state between CoWO 4and RE 2wO 6where RE=Sm, Eu, Gd.Thermochimica Acta, 447 (2006) 69-74].The people such as P.Urbanowicz have also synthesized Sm by similar approach 2wO 6crystal [P.Urbanowicz, E.Tomaszewicz, et al.Magnetic properties of R 2wO 6(where R=Nd, Sm, Eu, Gd, Dy and Ho) .Physica B, 404 (2009) 2213-2217].Solid reaction process prepares wolframic acid samarium, needs raw material Sm 2o 3and WO 3homogeneous phase mixing in proportion, is then heated to comparatively high temps (800 DEG C ~ 1200 DEG C), and insulation long period (12 ~ 24h), obtains product.This method has the advantages such as high yield, technique are simple, however reaction need at high temperature be carried out, preparation cycle compared with long, energy consumption large, do not meet and pursue green, environmental protection, energy-conservation, efficient trend at present.
About in the having been reported of tungstate, wet chemistry method becomes main flow preparation method, and as liquid phase reaction method, microemulsion method, solvent-thermal method, hydrothermal method etc., wherein hydrothermal method and microwave-hydrothermal method are the methods that report is maximum.Gao Chunmei etc. at 200 DEG C by Bi (NO 3) 35H 2o and Na 2wO 42H 2precursor liquid prepared by O carries out hydro-thermal reaction 20h, has prepared Bi 2wO 6powder [Gao C M, Wang Z Y.Effect of pH Values on Photocatalytic Properties of Bi 2wO 6synthesized by Hydrothermal Method.Journal of Wuhan University of Technology-Mater.Sci.Ed, 24 (2009): 533-536]; Yi Huangs etc. use Bi (NO 3) 35H 2o and Na 2wO 42H 2o prepares precursor liquid, 180 DEG C react 2 respectively, 4,6,12,24,36,48h, obtain Bi 2wO 6powder [Yi Huang, Shen Yue. flower-shaped Bi 2wO 6the preparation and property research of photocatalyst. functional materials, 2010, increase I (41): 52-56].
Summary of the invention
A kind of microwave-hydrothermal method is the object of the present invention is to provide to prepare sheet SmWO 4(OH) method, this method technological process is simple, and parameter is easy to control, and temperature is low, and the production time is short, can prepare highly purified sheet SmWO 4(OH).
For achieving the above object, present invention employs following technical scheme:
Step one: by SmCl 36H 2o and Na 2wO 42H 2o adds in deionized water respectively, then stirs 5 ~ 15min and obtains SmCl 3solution and Na 2wO 4solution;
Step 2: by Na 2wO 4solution drops to SmCl 3in solution, constantly stir (5 ~ 10 minutes) and obtain white suspension liquid, the mol ratio=1.5 ~ 2.5:1 of control Sm:W, and W 6+concentration is 0.01 ~ 0.06mol/L;
Step 3: pH to 6 ~ 9 regulating white suspension liquid with the NaOH aqueous solution, and Keep agitation 10 ~ 30min, obtain microwave hydrothermal precursor liquid;
Step 4: loaded by microwave hydrothermal precursor liquid in tetrafluoroethylene reactor, puts into microwave hydrothermal reaction after then being sealed by tetrafluoroethylene reactor, and react 60 ~ 90min at 180 ~ 220 DEG C, naturally cool to room temperature after reaction terminates;
Step 5: after step 4, open tetrafluoroethylene reactor, the product centrifugation be obtained by reacting is precipitated, by precipitation successively with putting into vacuum drying oven after deionized water and absolute ethanol washing and drying at 50 ~ 60 DEG C, can sheet SmWO be obtained 4(OH) crystallite.
The concentration of the described NaOH aqueous solution is 0.2 ~ 1mol/L.
The packing ratio of described microwave hydrothermal precursor liquid in tetrafluoroethylene reactor is 20 ~ 50%.
Beneficial effect of the present invention is embodied in:
The present invention adopts wet chemistry method to prepare sheet SmWO 4(OH), microwave-hydrothermal method technological process is simple, and temperature of reaction is lower, and the time is short, and processing parameter is easy to control, reacts for a long time or atmosphere protection without the need to high temperature, without the need to subsequent disposal, can prepare highly purified sheet SmWO fast 4(OH) SmWO, using the inventive method obtained 4(OH) powder has wide investigation and application to be worth in the field such as photocatalysis degradation organic contaminant and photolysis water hydrogen.
Accompanying drawing explanation
Fig. 1 is SmWO prepared by the embodiment of the present invention 1 4(OH) X-ray diffraction (XRD) collection of illustrative plates of crystallite.
Fig. 2 is SmWO prepared by the embodiment of the present invention 1 4(OH) scanning electron microscope (SEM) photo of crystallite.
Fig. 3 is the degradation rate-time diagram of Rh-B of degrading under uv irradiating, and S1-S4 is corresponding embodiment 1-embodiment 4 respectively.
Embodiment
Below in conjunction with drawings and Examples, the present invention is elaborated.
Embodiment 1:
Step one: by analytical pure SmCl 36H 2o and Na 2wO 42H 2o adds in a certain amount of deionized water respectively, magnetic stirring apparatus stirs 5min and obtains clear solution A(SmCl 3solution) and clear solution B(Na 2wO 4solution);
Step 2: slowly dropped to by clear solution B in clear solution A, constantly stirs and obtains white suspension liquid, control Sm:W=2:1(mol ratio), W 6+concentration is 0.05mol/L;
Step 3: the pH=7 regulating white suspension liquid with the NaOH aqueous solution that concentration is 0.5mol/L, and Keep agitation 30min, obtain microwave hydrothermal precursor liquid;
Step 4: loaded in tetrafluoroethylene reactor by microwave hydrothermal precursor liquid, packing ratio is 40%, sealing tetrafluoroethylene reactor, puts into microwave hydrothermal reaction, at 220 DEG C, reacts 90min, naturally cool to room temperature after reaction terminates;
Step 5: open tetrafluoroethylene reactor, is precipitated the product centrifugation be obtained by reacting, and successively by deionized water and absolute ethanol washing precipitation, the precipitation after washing is put into vacuum drying oven and dries at 60 DEG C, can obtain sheet SmWO 4(OH) crystallite.
See Fig. 1, it is pure phase SmWO that X-ray diffraction (XRD) collection of illustrative plates shows the present embodiment products therefrom 4(OH), crystallinity is better.See Fig. 2, from scanning electron microscope (SEM) photo, the present embodiment products therefrom has the microscopic appearance of irregular sheet.
Embodiment 2:
Step one: by analytical pure SmCl 36H 2o and Na 2wO 42H 2o adds in a certain amount of deionized water respectively, magnetic stirring apparatus stirs 5min and obtains clear solution A(SmCl 3solution) and clear solution B(Na 2wO 4solution);
Step 2: slowly dropped to by clear solution B in clear solution A, constantly stirs and obtains white suspension liquid, control Sm:W=1.5:1(mol ratio), W 6+concentration is 0.06mol/L;
Step 3: the pH=8 regulating white suspension liquid with the NaOH aqueous solution that concentration is 0.8mol/L, and Keep agitation 10min, obtain microwave hydrothermal precursor liquid;
Step 4: loaded in tetrafluoroethylene reactor by microwave hydrothermal precursor liquid, packing ratio is 50%, sealing tetrafluoroethylene reactor, puts into microwave hydrothermal reaction, at 220 DEG C, reacts 60min, naturally cool to room temperature after reaction terminates;
Step 5: open tetrafluoroethylene reactor, is precipitated the product centrifugation be obtained by reacting, and successively by deionized water and absolute ethanol washing precipitation, the precipitation after washing is put into vacuum drying oven and dries at 50 DEG C, can obtain sheet SmWO 4(OH) crystallite.
Embodiment 3:
Step one: by analytical pure SmCl 36H 2o and Na 2wO 42H 2o adds in a certain amount of deionized water respectively, magnetic stirring apparatus stirs 15min and obtains clear solution A(SmCl 3solution) and clear solution B(Na 2wO 4solution);
Step 2: slowly dropped to by clear solution B in clear solution A, constantly stirs and obtains white suspension liquid, control Sm:W=2.5:1(mol ratio), W 6+concentration is 0.025mol/L;
Step 3: the pH=9 regulating white suspension liquid with the NaOH aqueous solution that concentration is 1mol/L, and Keep agitation 15min, obtain microwave hydrothermal precursor liquid;
Step 4: loaded in tetrafluoroethylene reactor by microwave hydrothermal precursor liquid, packing ratio is 20%, sealing tetrafluoroethylene reactor, puts into microwave hydrothermal reaction, at 180 DEG C, reacts 90min, naturally cool to room temperature after reaction terminates;
Step 5: open tetrafluoroethylene reactor, is precipitated the product centrifugation be obtained by reacting, and successively by deionized water and absolute ethanol washing precipitation, the precipitation after washing is put into vacuum drying oven and dries at 60 DEG C, can obtain sheet SmWO 4(OH) crystallite.
Embodiment 4:
Step one: by analytical pure SmCl 36H 2o and Na 2wO 42H 2o adds in a certain amount of deionized water respectively, magnetic stirring apparatus stirs 10min and obtains clear solution A(SmCl 3solution) and clear solution B(Na 2wO 4solution);
Step 2: slowly dropped to by clear solution B in clear solution A, constantly stirs and obtains white suspension liquid, control Sm:W=1.5:1(mol ratio), W 6+concentration is 0.03mol/L;
Step 3: the pH=6 regulating white suspension liquid with the NaOH aqueous solution that concentration is 0.2mol/L, and Keep agitation 10min, obtain microwave hydrothermal precursor liquid;
Step 4: loaded in tetrafluoroethylene reactor by microwave hydrothermal precursor liquid, packing ratio is 30%, sealing tetrafluoroethylene reactor, puts into microwave hydrothermal reaction, at 180 DEG C, reacts 60min, naturally cool to room temperature after reaction terminates;
Step 5: open tetrafluoroethylene reactor, is precipitated the product centrifugation be obtained by reacting, and successively by deionized water and absolute ethanol washing precipitation, the precipitation after washing is put into vacuum drying oven and dries at 60 DEG C, can obtain sheet SmWO 4(OH) crystallite.
The present invention adopts microwave hydrothermal method innovatively, at a lower temperature synthesizing flaky SmWO 4(OH), equipment is simple, and easily control, the cycle is short, can Fast back-projection algorithm SmWO 4(OH).Sheet SmWO after testing prepared by embodiment 1-embodiment 4 4(OH) there is obvious photocatalytic activity.Fig. 3 is the degradation rate-time diagram of Rh-B of degrading under UV-irradiation, as can be seen from Figure 3, compared with testing with blank, and the sheet SmWO that embodiment 1-embodiment 4 is prepared 4(OH) to Rh-B, there is obvious Photocatalytic activity.

Claims (3)

1. a microwave-hydrothermal method prepares sheet SmWO 4(OH) method, is characterized in that: comprise the following steps:
Step one: by SmCl 36H 2o and Na 2wO 42H 2o adds in deionized water respectively and obtains SmCl 3solution and Na 2wO 4solution;
Step 2: by Na 2wO 4solution drops to SmCl 3in solution, constantly stir and obtain white suspension liquid, the mol ratio=1.5 ~ 2.5:1 of control Sm:W, and W 6+concentration is 0.01 ~ 0.06mol/L;
Step 3: pH to 6 ~ 9 regulating white suspension liquid with the NaOH aqueous solution, and Keep agitation 10 ~ 30min, obtain microwave hydrothermal precursor liquid;
Step 4: loaded by microwave hydrothermal precursor liquid in tetrafluoroethylene reactor, puts into microwave hydrothermal reaction after then being sealed by tetrafluoroethylene reactor, and react 60 ~ 90min at 180 ~ 220 DEG C, naturally cool to room temperature after reaction terminates;
Step 5: open tetrafluoroethylene reactor, is precipitated the product centrifugation be obtained by reacting, and by precipitation successively with putting into vacuum drying oven after deionized water and absolute ethanol washing and drying at 50 ~ 60 DEG C, can obtain sheet SmWO 4(OH) crystallite.
2. a kind of microwave-hydrothermal method prepares sheet SmWO according to claim 1 4(OH) method, is characterized in that: the concentration of the described NaOH aqueous solution is 0.2 ~ 1mol/L.
3. a kind of microwave-hydrothermal method prepares sheet SmWO according to claim 1 4(OH) method, is characterized in that: the packing ratio of described microwave hydrothermal precursor liquid in tetrafluoroethylene reactor is 20 ~ 50%.
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CN105016372B (en) * 2015-07-27 2017-03-01 陕西科技大学 A kind of self assembly wheat head shape SmCO3(OH) preparation method of nano material
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CN106735166B (en) * 2016-12-12 2018-10-12 南京工业大学 A kind of EuWO4(OH) preparation method of nanobelt and its composite material
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