CN103922412A - Method for preparing flaky SmWO4(OH) with microwave hydrothermal method - Google Patents

Method for preparing flaky SmWO4(OH) with microwave hydrothermal method Download PDF

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CN103922412A
CN103922412A CN201410155185.3A CN201410155185A CN103922412A CN 103922412 A CN103922412 A CN 103922412A CN 201410155185 A CN201410155185 A CN 201410155185A CN 103922412 A CN103922412 A CN 103922412A
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microwave
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microwave hydrothermal
smwo
hydrothermal
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CN103922412B (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 method for preparing flaky SmWO4(OH) with a microwave hydrothermal method. The method comprises the following steps: dripping Na2WO4 solution into SmCl3 solution; continuously stirring to obtain white suspension; regulating the pH of the white suspension to 6-9 to obtain microwave hydrothermal precursor solution; reacting at the temperature of 180-220DEG C for 60-90min in a microwave hydrothermal reactor; then, carrying out centrifugal separation, washing and drying to obtain flaky SmWO4(OH) microcrystal. According to the method, flaky SmWO4(OH) is prepared with a wet chemistry method. The microwave hydrothermal method has the advantages of simple technical process, low reaction temperature, short time and easily-controlled technical parameter, high-temperature long-time reaction or atmosphere protection is omitted, subsequent processing is omitted, and the high-purity flaky SmWO4(OH) can be quickly prepared.

Description

A kind of microwave-hydrothermal method is prepared sheet SmWO 4(OH) method
Technical field
The present invention relates to a kind of SmWO 4(OH) preparation method, particularly a kind of microwave-hydrothermal method that adopts is prepared sheet SmWO 4(OH) method.
Background technology
Wolframic acid samarium is a member in tungstate series, is the relatively less novel photocatalyst of a kind of very potential but research, all has a good application prospect in the field such as Degradation of Organo-pollutants in Water with Photo-catalysis and photolysis water hydrogen.The exploitation of preparation method to wolframic acid samarium, all significant in theory and the application aspect of photocatalysis field.In addition, wolframic acid samarium also may have the properties such as paramagnetism, ferroelectric, piezoelectricity, pyroelectricity, non-linear electric susceptibility, negative expansion, is with a wide range of applications.
At present the report of tungstate is mainly concentrated on to Bi 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, the preparation method who adopts in existing report mostly is solid reaction process.
E.Tomaszewicz is by solid reaction process, with Sm 2o 3and WO 3for raw material has been prepared Sm 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 is prepared wolframic acid samarium, need to be by raw material Sm 2o 3and WO 3evenly mix in proportion, be then heated to comparatively high temps (800 DEG C～1200 DEG C), 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 is large, does not meet current pursuit green, environmental protection, energy-conservation, efficient trend.
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, reacts respectively 2,4,6,12,24,36,48h at 180 DEG C, obtains 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
The object of the present invention is to provide a kind of microwave-hydrothermal method 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, the present invention has adopted following technical scheme:
Step 1: by SmCl 36H 2o and Na 2wO 42H 2o adds respectively in deionized water, 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, control mol ratio=1.5～2.5:1 of Sm:W, and W 6+concentration is 0.01～0.06mol/L;
Step 3: regulate pH to 6～9 of white suspension liquid with the NaOH aqueous solution, and continue to stir 10～30min, obtain microwave hydrothermal precursor liquid;
Step 4: microwave hydrothermal precursor liquid is packed in tetrafluoroethylene reactor, then will put into microwave hydrothermal reaction after the sealing of tetrafluoroethylene reactor, and react 60～90min at 180～220 DEG C, naturally cool to room temperature after reaction finishes;
Step 5: after step 4, open tetrafluoroethylene reactor, the product centrifugation that reaction is obtained is precipitated, and precipitation, successively with putting into vacuum drying oven after deionized water and absolute ethanol washing and drying at 50～60 DEG C, can be obtained to sheet SmWO 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, without the long-time reaction of high temperature or atmosphere protection, without subsequent disposal, can prepare fast highly purified sheet SmWO 4(OH) SmWO that, uses the inventive method to make 4(OH) powder has wide research and using value in the field such as photocatalysis degradation organic contaminant and photolysis water hydrogen.
Brief description of the drawings
Fig. 1 is SmWO prepared by the embodiment of the present invention 1 4(OH) X-ray diffraction of crystallite (XRD) collection of illustrative plates.
Fig. 2 is SmWO prepared by the embodiment of the present invention 1 4(OH) scanning electron microscope of crystallite (SEM) photo.
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 1: by analytical pure SmCl 36H 2o and Na 2wO 42H 2o adds respectively in a certain amount of deionized water, stirs 5min and obtain clear solution A(SmCl on magnetic stirring apparatus 3solution) and clear solution B(Na 2wO 4solution);
Step 2: clear solution B is slowly dropped in clear solution A, constantly stir and obtain white suspension liquid, control Sm:W=2:1(mol ratio), W 6+concentration is 0.05mol/L;
Step 3: the NaOH aqueous solution that is 0.5mol/L by concentration regulates the pH=7 of white suspension liquid, and continue to stir 30min, microwave hydrothermal precursor liquid obtained;
Step 4: microwave hydrothermal precursor liquid is packed in tetrafluoroethylene reactor, and packing ratio is 40%, sealing tetrafluoroethylene reactor, puts into microwave hydrothermal reaction, at 220 DEG C, reacts 90min, after reaction finishes, naturally cools to room temperature;
Step 5: open tetrafluoroethylene reactor, the product centrifugation that reaction is obtained is precipitated, by deionized water and absolute ethanol washing precipitation, puts into vacuum drying oven by the precipitation after washing and dries at 60 DEG C successively, can obtain sheet SmWO 4(OH) crystallite.
Referring to Fig. 1, X-ray diffraction (XRD) collection of illustrative plates shows that the present embodiment products therefrom is pure phase SmWO 4(OH), crystallinity is better.Referring to Fig. 2, from scanning electron microscope (SEM) photo, the present embodiment products therefrom has the microscopic appearance of irregular sheet.
Embodiment 2:
Step 1: by analytical pure SmCl 36H 2o and Na 2wO 42H 2o adds respectively in a certain amount of deionized water, stirs 5min and obtain clear solution A(SmCl on magnetic stirring apparatus 3solution) and clear solution B(Na 2wO 4solution);
Step 2: clear solution B is slowly dropped in clear solution A, constantly stir and obtain white suspension liquid, control Sm:W=1.5:1(mol ratio), W 6+concentration is 0.06mol/L;
Step 3: the NaOH aqueous solution that is 0.8mol/L by concentration regulates the pH=8 of white suspension liquid, and continue to stir 10min, microwave hydrothermal precursor liquid obtained;
Step 4: microwave hydrothermal precursor liquid is packed in tetrafluoroethylene reactor, and packing ratio is 50%, sealing tetrafluoroethylene reactor, puts into microwave hydrothermal reaction, at 220 DEG C, reacts 60min, after reaction finishes, naturally cools to room temperature;
Step 5: open tetrafluoroethylene reactor, the product centrifugation that reaction is obtained is precipitated, by deionized water and absolute ethanol washing precipitation, puts into vacuum drying oven by the precipitation after washing and dries at 50 DEG C successively, can obtain sheet SmWO 4(OH) crystallite.
Embodiment 3:
Step 1: by analytical pure SmCl 36H 2o and Na 2wO 42H 2o adds respectively in a certain amount of deionized water, stirs 15min and obtain clear solution A(SmCl on magnetic stirring apparatus 3solution) and clear solution B(Na 2wO 4solution);
Step 2: clear solution B is slowly dropped in clear solution A, constantly stir and obtain white suspension liquid, control Sm:W=2.5:1(mol ratio), W 6+concentration is 0.025mol/L;
Step 3: the NaOH aqueous solution that is 1mol/L by concentration regulates the pH=9 of white suspension liquid, and continue to stir 15min, microwave hydrothermal precursor liquid obtained;
Step 4: microwave hydrothermal precursor liquid is packed in tetrafluoroethylene reactor, and packing ratio is 20%, sealing tetrafluoroethylene reactor, puts into microwave hydrothermal reaction, at 180 DEG C, reacts 90min, after reaction finishes, naturally cools to room temperature;
Step 5: open tetrafluoroethylene reactor, the product centrifugation that reaction is obtained is precipitated, by deionized water and absolute ethanol washing precipitation, puts into vacuum drying oven by the precipitation after washing and dries at 60 DEG C successively, can obtain sheet SmWO 4(OH) crystallite.
Embodiment 4:
Step 1: by analytical pure SmCl 36H 2o and Na 2wO 42H 2o adds respectively in a certain amount of deionized water, stirs 10min and obtain clear solution A(SmCl on magnetic stirring apparatus 3solution) and clear solution B(Na 2wO 4solution);
Step 2: clear solution B is slowly dropped in clear solution A, constantly stir and obtain white suspension liquid, control Sm:W=1.5:1(mol ratio), W 6+concentration is 0.03mol/L;
Step 3: the NaOH aqueous solution that is 0.2mol/L by concentration regulates the pH=6 of white suspension liquid, and continue to stir 10min, microwave hydrothermal precursor liquid obtained;
Step 4: microwave hydrothermal precursor liquid is packed in tetrafluoroethylene reactor, and packing ratio is 30%, sealing tetrafluoroethylene reactor, puts into microwave hydrothermal reaction, at 180 DEG C, reacts 60min, after reaction finishes, naturally cools to room temperature;
Step 5: open tetrafluoroethylene reactor, the product centrifugation that reaction is obtained is precipitated, by deionized water and absolute ethanol washing precipitation, puts into vacuum drying oven by the precipitation after washing and dries at 60 DEG C successively, 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, easily controls, and the cycle is short, can synthesize fast SmWO 4(OH).The prepared sheet SmWO of embodiment 1-embodiment 4 after testing 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 blank contrast test, the sheet SmWO that embodiment 1-embodiment 4 prepares 4(OH) Rh-B is had to obvious Photocatalytic activity.

Claims (3)

1. a microwave-hydrothermal method is prepared sheet SmWO 4(OH) method, is characterized in that: comprise the following steps:
Step 1: by SmCl 36H 2o and Na 2wO 42H 2o adds respectively and in deionized water, 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, control mol ratio=1.5～2.5:1 of Sm:W, and W 6+concentration is 0.01～0.06mol/L;
Step 3: regulate pH to 6～9 of white suspension liquid with the NaOH aqueous solution, and continue to stir 10～30min, obtain microwave hydrothermal precursor liquid;
Step 4: microwave hydrothermal precursor liquid is packed in tetrafluoroethylene reactor, then will put into microwave hydrothermal reaction after the sealing of tetrafluoroethylene reactor, and react 60～90min at 180～220 DEG C, naturally cool to room temperature after reaction finishes;
Step 5: open tetrafluoroethylene reactor, the product centrifugation that reaction is obtained is precipitated, 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 by precipitation 4(OH) crystallite.
2. a kind of microwave-hydrothermal method is prepared 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 is prepared 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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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105016372A (en) * 2015-07-27 2015-11-04 陕西科技大学 Preparation method of self-assembly wheat-ear-like Sm2CO3 (OH) nanomaterial
CN106587152A (en) * 2016-12-12 2017-04-26 南京工业大学 Rare-earth two-dimensional material EuMoO4(OH) nanosheet as well as preparation method and application thereof
CN106735166A (en) * 2016-12-12 2017-05-31 南京工业大学 A kind of EuWO4(OH) preparation method of nanobelt and its composite
CN111874959A (en) * 2020-08-18 2020-11-03 王星星 SmMoO4(OH)-Ni(OH)2Preparation method of nanosheet

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JIAO WANG等: ""Luminescent metastable Y2WO6:Ln3+ (Ln = Eu, Er, Sm, and Dy)microspheres with controllable morphology via self-assembly"", 《JOURNAL OF MATERIALS CHEMISTRY》, vol. 20, 18 October 2010 (2010-10-18), pages 10894 - 10900 *
李夏: ""稀土化合物纳米材料的溶剂热合成及性质研究"", 《河南师范大学硕士学位论文》, 1 February 2010 (2010-02-01), pages 21 - 31 *
谈国强等: ""pH值对ZnWO4粉体的微波水热法合成及光催化性能的影响"", 《硅酸盐学报》, vol. 40, no. 6, 30 June 2012 (2012-06-30), pages 832 - 838 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105016372A (en) * 2015-07-27 2015-11-04 陕西科技大学 Preparation method of self-assembly wheat-ear-like Sm2CO3 (OH) nanomaterial
CN106587152A (en) * 2016-12-12 2017-04-26 南京工业大学 Rare-earth two-dimensional material EuMoO4(OH) nanosheet as well as preparation method and application thereof
CN106735166A (en) * 2016-12-12 2017-05-31 南京工业大学 A kind of EuWO4(OH) preparation method of nanobelt and its composite
CN111874959A (en) * 2020-08-18 2020-11-03 王星星 SmMoO4(OH)-Ni(OH)2Preparation method of nanosheet
CN111874959B (en) * 2020-08-18 2024-01-30 王星星 SmMoO 4 (OH)-Ni(OH) 2 Preparation method of nano-sheet

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