CN103922409B - A kind of ellipsoid shape SmW 2o 6(OH) 3the preparation method of crystallite - Google Patents

A kind of ellipsoid shape SmW 2o 6(OH) 3the preparation method of crystallite Download PDF

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CN103922409B
CN103922409B CN201410155072.3A CN201410155072A CN103922409B CN 103922409 B CN103922409 B CN 103922409B CN 201410155072 A CN201410155072 A CN 201410155072A CN 103922409 B CN103922409 B CN 103922409B
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smw
ellipsoid shape
crystallite
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reaction kettle
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CN103922409A (en
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黄剑锋
李颖慧
李嘉胤
卢靖
曹丽云
欧阳海波
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 ellipsoid shape SmW 2o 6(OH) 3the preparation method of crystallite: by Na 2wO 4solution drops to Sm (NO 3) 3in solution, then constantly stir and obtain white suspension liquid, regulate pH to 2 ~ 5 to obtain hydro-thermal precursor liquid, in homogeneous reaction instrument, react 18 ~ 48h at 100 ~ 160 DEG C, product centrifugation, washing, drying, obtain ellipsoid shape SmW 2o 6(OH) 3crystallite, the present invention adopts wet chemistry method to prepare ellipsoid shape SmW 2o 6(OH) 3, 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 need to pyroreaction or atmosphere protection, without the need to subsequent disposal, can prepare highly purified ellipsoid shape SmW fast 2o 6(OH) 3.

Description

A kind of ellipsoid shape SmW 2o 6(OH) 3the preparation method of crystallite
Technical field
The present invention relates to a kind of SmW 2o 6(OH) 3preparation method, particularly one adopt hydrothermal method prepare ellipsoid shape SmW 2o 6(OH) 3the method of crystallite.
Background technology
Wolframic acid samarium is a kind of water-fast Exemplary rare earth metals tungstate material, paramagnetism, ferroelectric, the property such as piezoelectricity, pyroelectricity, non-linear electric susceptibility, negative expansion may be had, can be used as photocatalyst material, permanent magnet material, Solid Oxide Fuel Cells, ceramic capacitor material etc., be with a wide range of applications.
The preparation method of current rare earth metal tungstate is mainly 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 Qin Li have also synthesized Sm with solid reaction process 2wO 6crystal [Qin Li, Venkataraman Thangadurai.Novel Nd 2wo 6-type Sm 2-xa xm 1-yb yo 6-δ(A=Ca, Sr; M=Mo, W; B=Ce, Ni) mixed conductors.Journal of Power Sources, 196 (2011) 169-178].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 solvent-thermal method and hydrothermal method are the methods that report is maximum.Chen Lei etc. are by Bi (NO 3) 3, Na 2wO 4in alcohol water mixed solvent, make suspension respectively, after mixing under solvent thermal condition, surface reaction occurs and defines Bi 2wO 6hollow nano-sphere [Chen Lei, Wu great Xiong etc. prepare bismuth tungstate hollow nanostructures [J] in alcohol water mixed solvent. Qingdao University of Science and Technology's journal, 2012,33 (1): 9-12]; Xu Chun Song etc. has prepared molybdenum doping Bi by hydrothermal method 2wO 6three-dimensional layering microballoon [Song C X, Zheng Y F.Photocatalytic activities of Mo-doped Bi 2wO 6three-dimensional hierarchical microspheres [J] .J ournal of Hazardous Materials, 2011,192:186-191].Hydrothermal method have with short production cycle, technique is simple, parameter is easy to control, be convenient to the advantages such as doping vario-property.
Summary of the invention
The object of the present invention is to provide a kind of ellipsoid shape SmW 2o 6(OH) 3the preparation method of crystallite, the 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 ellipsoid shape SmW 2o 6(OH) 3.
For achieving the above object, present invention employs following technical scheme:
Step one: by Sm (NO 3) 36H 2o and Na 2wO 42H 2o adds in deionized water respectively, then stirs 5 ~ 15min and obtains Sm (NO 3) 3solution and Na 2wO 4solution;
Step 2: by Na 2wO 4solution drops to Sm (NO 3) 3in solution, then constantly stir (5 ~ 10 minutes) and obtain white suspension liquid, the mol ratio=0.5 ~ 2:1 of control Sm:W, and W 6+concentration be 0.02 ~ 0.1mol/L;
Step 3: pH to 2 ~ 5 regulating white suspension liquid with the HCl aqueous solution, and Keep agitation 30 ~ 60min, obtain hydro-thermal precursor liquid;
Step 4: loaded by hydro-thermal precursor liquid in hydrothermal reaction kettle, puts into homogeneous reaction instrument after then being sealed by hydrothermal reaction kettle, and react 18 ~ 48h at 100 ~ 160 DEG C, naturally cool to room temperature after reaction terminates;
Step 5: after step 4, opens hydrothermal reaction kettle, the product centrifugation be obtained by reacting is precipitated, and by precipitation successively with putting into vacuum drying oven after deionized water and absolute ethanol washing and drying at 40 ~ 60 DEG C, can obtain ellipsoid shape SmW 2o 6(OH) 3crystallite.
The packing ratio of described hydro-thermal precursor liquid in hydrothermal reaction kettle is 30 ~ 60%.
The concentration of the described HCl aqueous solution is 0.5 ~ 1.5mol/L.
Beneficial effect of the present invention:
The present invention adopts wet chemistry method to prepare ellipsoid shape SmW 2o 6(OH) 3, 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 need to pyroreaction or atmosphere protection, without the need to subsequent disposal, can prepare highly purified ellipsoid shape SmW fast 2o 6(OH) 3.The ellipsoid shape SmW that the inventive method is obtained 2o 6(OH) 3crystallite has larger specific surface area, has wide investigation and application to be worth in the field such as photochemical catalysis and photolysis water hydrogen.
Accompanying drawing explanation
Fig. 1 is SmW prepared by the embodiment of the present invention 1 2o 6(OH) 3x-ray diffraction (XRD) collection of illustrative plates of crystallite.
Fig. 2 is SmW prepared by the embodiment of the present invention 1 2o 6(OH) 3scanning electron microscope (SEM) photo of crystallite.
Fig. 3 is the degradation rate-time diagram of photocatalytic degradation Rh-B.
Embodiment
Below in conjunction with drawings and Examples, the present invention is elaborated.
Embodiment 1:
Step one: by analytical pure Sm (NO 3) 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(Sm (NO 3) 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 be 0.05mol/L;
Step 3: the pH=3 regulating white suspension liquid with the HCl aqueous solution that concentration is 1.0mol/L, and Keep agitation 30min, obtain hydro-thermal precursor liquid;
Step 4: loaded in hydrothermal reaction kettle by hydro-thermal precursor liquid, packing ratio is 40%, sealing hydrothermal reaction kettle, puts into homogeneous reaction instrument, at 160 DEG C, reacts 24h, naturally cools to room temperature after reaction terminates;
Step 5: open hydrothermal reaction kettle, 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 ellipsoid shape SmW 2o 6(OH) 3crystallite.
See Fig. 1, X-ray diffraction (XRD) the collection of illustrative plates display product of the present embodiment products therefrom is pure phase monocline SmW 2o 6(OH) 3, and crystallinity is good.See Fig. 2, scanning electron microscope (SEM) photo display product has the ellipse spherical morphology assembled by nanoplatelet.
Embodiment 2:
Step one: by analytical pure Sm (NO 3) 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(Sm (NO 3) 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 be 0.1mol/L;
Step 3: the pH=4 regulating white suspension liquid with the HCl aqueous solution that concentration is 1.5mol/L, and Keep agitation 60min, obtain hydro-thermal precursor liquid;
Step 4: loaded in hydrothermal reaction kettle by hydro-thermal precursor liquid, packing ratio is 50%, sealing hydrothermal reaction kettle, puts into homogeneous reaction instrument, at 160 DEG C, reacts 18h, naturally cools to room temperature after reaction terminates;
Step 5: open hydrothermal reaction kettle, 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 40 DEG C, can obtain ellipsoid shape SmW 2o 6(OH) 3crystallite.
Embodiment 3:
Step one: by analytical pure Sm (NO 3) 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(Sm (NO 3) 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=0.5:1(mol ratio), W 6+concentration is 0.0625mol/L;
Step 3: the pH=5 regulating white suspension liquid with the HCl aqueous solution that concentration is 0.5mol/L, and Keep agitation 30min, obtain hydro-thermal precursor liquid;
Step 4: loaded in hydrothermal reaction kettle by hydro-thermal precursor liquid, packing ratio is 60%, sealing hydrothermal reaction kettle, puts into homogeneous reaction instrument, at 140 DEG C, reacts 30h, naturally cools to room temperature after reaction terminates;
Step 5: open hydrothermal reaction kettle, 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 ellipsoid shape SmW 2o 6(OH) 3crystallite.
Embodiment 4:
Step one: by analytical pure Sm (NO 3) 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(Sm (NO 3) 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=1:1(mol ratio), W 6+concentration is 0.021mol/L;
Step 3: the pH=2 regulating white suspension liquid with the HCl aqueous solution that concentration is 1.5mol/L, and Keep agitation 40min, obtain hydro-thermal precursor liquid;
Step 4: loaded in hydrothermal reaction kettle by hydro-thermal precursor liquid, packing ratio is 30%, sealing hydrothermal reaction kettle, puts into homogeneous reaction instrument, at 100 DEG C, reacts 48h, naturally cools to room temperature after reaction terminates;
Step 5: open hydrothermal reaction kettle, 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 ellipsoid shape SmW 2o 6(OH) 3crystallite.
The present invention adopts hydrothermal method to prepare ellipsoid shape SmW innovatively 2o 6(OH) 3, equipment is simple, and easily control, temperature is low, and the cycle is short, can prepare pure phase ellipsoid shape SmW easily 2o 6(OH) 3.Ellipsoid shape SmW after testing prepared by embodiment 1-embodiment 4 2o 6(OH) 3there is obvious photocatalytic activity.Fig. 3 is the degradation rate-time diagram of photocatalytic degradation Rh-B, and S1-S4 represents the ellipsoid shape SmW prepared by embodiment 1-embodiment 4 respectively 2o 6(OH) 3.Visible under UV-irradiation, compared with detecting with blank, the ellipsoid shape SmW obtained by embodiment 1-embodiment 4 2o 6(OH) 3to Rh-B, there is obvious Photocatalytic activity.

Claims (3)

1. an ellipsoid shape SmW 2o 6(OH) 3the preparation method of crystallite, is characterized in that: comprise the following steps:
Step one: by Sm (NO 3) 36H 2o and Na 2wO 42H 2o adds respectively in deionized water and obtains Sm (NO 3) 3solution and Na 2wO 4solution;
Step 2: by Na 2wO 4solution drops to Sm (NO 3) 3in solution, then constantly stir and obtain white suspension liquid, the mol ratio=0.5 ~ 2:1 of control Sm:W, and W 6+concentration be 0.02 ~ 0.1mol/L;
Step 3: pH to 2 ~ 5 regulating white suspension liquid with the HCl aqueous solution, and Keep agitation 30 ~ 60min, obtain hydro-thermal precursor liquid;
Step 4: loaded by hydro-thermal precursor liquid in hydrothermal reaction kettle, puts into homogeneous reaction instrument after then being sealed by hydrothermal reaction kettle, and react 18 ~ 48h at 100 ~ 160 DEG C, naturally cool to room temperature after reaction terminates;
Step 5: after step 4, opens hydrothermal reaction kettle, the product centrifugation be obtained by reacting is precipitated, and by precipitation successively with putting into vacuum drying oven after deionized water and absolute ethanol washing and drying at 40 ~ 60 DEG C, can obtain ellipsoid shape SmW 2o 6(OH) 3crystallite.
2. a kind of ellipsoid shape SmW according to claim 1 2o 6(OH) 3the preparation method of crystallite, is characterized in that: the packing ratio of described hydro-thermal precursor liquid in hydrothermal reaction kettle is 30 ~ 60%.
3. a kind of ellipsoid shape SmW according to claim 1 2o 6(OH) 3the preparation method of crystallite, is characterized in that: the concentration of the described HCl aqueous solution is 0.5 ~ 1.5mol/L.
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* Cited by examiner, † Cited by third party
Title
"Luminescent metastable Y2WO6: Ln3+ (Ln = Eu, Er, Sm, andDy)microspheres with controllable morphology via self-assembly";Jiao Wang等;《Journal of Materials Chemistry》;20101018;第20卷;第10894-10900页 *
"NdWO4(OH)粉体的微波水热合成及其光催化性能";曹丽云等;《陕西科技大学学报》;20131231;第31卷(第6期);第54-57页 *
"pH值对ZnWO4粉体的微波水热法合成及光催化性能的影响";谈国强等;《硅酸盐学报》;20120630;第40卷(第6期);第833-834页 *
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