CN103922413B - Method for preparing pyramid-shaped Cr2WO6 microcrystalline by hydrothermal-assisted low-temperature calcination - Google Patents

Method for preparing pyramid-shaped Cr2WO6 microcrystalline by hydrothermal-assisted low-temperature calcination Download PDF

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CN103922413B
CN103922413B CN201410155242.8A CN201410155242A CN103922413B CN 103922413 B CN103922413 B CN 103922413B CN 201410155242 A CN201410155242 A CN 201410155242A CN 103922413 B CN103922413 B CN 103922413B
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crystallite
cr2wo6
microcrystalline
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CN103922413A (en
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黄剑锋
周文敏
李嘉胤
曹丽云
卢靖
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 method for preparing pyramid-shaped Cr2WO6 microcrystalline by hydrothermal-assisted low-temperature calcinations. The method comprises the following steps of adding Cr(NO3)3 solution to Na2WO4 solution, adjusting pH value to 7.0-12.0, pouring the solution to a hydrothermal reaction kettle, reacting for 1-24h at hydrothermal temperature of 100-200 DEG C, centrifuging the product, washing, drying and calcining for 2-4h in a muffle furnace at 400-650 DEG C to obtain Cr2WO6 microcrystalline. The method has the advantages that the raw materials used for preparing Cr2WO6 microcrystalline are easily available, the yield is high, the time of low-temperature calcination is short, the reaction temperature is low, the reaction energy consumption is low, the cost is saved, the prepared Cr2WO6 microcrystalline develops completely and has high purity, even size and good dispersity, is suitable for large-scale production and has a bright development prospect.

Description

The method of pyramid-shaped Cr2WO6 crystallite is prepared in a kind of hydro-thermal assisted cryogenic calcining
Technical field
The invention belongs to tungstate nano field of material technology, be specifically related to a kind of hydro-thermal assisted cryogenic calcining preparation pyramid-shaped Cr 2wO 6the method of crystallite.
Background technology
Tungstate has the features such as kind is many, performance good, crystal morphology is changeable, high added value, by means of optics, the electric property of its excellence, tungstate not only obtains application in sensor, optics, scintillation crystal, laser host, acoustic fiber field, and has potential application in fields such as inhibition, electrode, catalysis, photo cathode, photoabsorption, coating.Chromium tungstate (Cr 2wO 6) be one in tungstate series, because it has special optics, electricity and magnetic performance, be considered to there is potential application in fields such as optical fiber, scintillator, humidity sensor, magneticsubstance and ferroelectric materials; Research finds that its energy gap is about 2.52eV, and Cr 2wO 6to visible ray, there is very strong absorption, be the very potential novel photocatalysis material of one, have broad application prospects in catalyzed degradation organic pollutants and photolysis water hydrogen.
At present mainly Bi is concentrated on to the report of tungstate 2wO 6, ZnWO 4, CaWO 4, FeWO 4deng material, and also rarely found to the report of chromium tungstate, the method adopted in existing report mainly solid reaction process.
G.Bayer adopts high temperature solid-state method, uses Cr 2o 3and WO 3for raw material mixes with 1:1, at 600 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, calcine 20h respectively, find Cr 2wO 6start to be formed at 850 DEG C, just form complete [G.Bayer.Cr at 950 DEG C 2wO 6, New Trirutile Compound [J] .Journal of The American Ceramic Society, 1960:495-496.]; K.T.JACOB also adopts high temperature solid-state method, with Cr 2o 3and WO 3for raw material has prepared Cr at the temperature lower calcination 24h of 1000 DEG C 2wO 6powder [K.T.JACOB.Phase relationships in the system Cr-W-O and thermodynamic properties of CrWO 4and Cr 2wO 6[J] .Journal of Materials Science, 1980,15:2167-2174.]; Therefore, Cr is prepared with high temperature solid-state method 2wO 6, need by heating raw materials to high temperature, and want long-time heat preservation, just can obtain product.This method not only consumes a large amount of energy, and the particle size of the sample prepared is large, and the specific surface area of catalyzer reduces greatly, though can realize visible light-responded, photocatalysis efficiency is unsatisfactory.
Up to the present the synthetic method of tungstate is varied, and Lee adopts hydrothermal method to prepare sheet Bi at 160 DEG C 2wO 6nanocrystalline [Wen-Lian William Lee, Shiuh-Tsuen Huang, et al.Photodegradation of CV over nanocrystalline bismuth tungstate prepared by hydrothermal synthesis [J] .J.Mol.Catal.A:Chem, 2012,361-362:80-90.]; M.A.P.Almeid adopts microwave-hydrothermal method to prepare pure FeWO at 170 DEG C 4nano-powder [M.A.P.Almeida, L.S.Cavalcante, C.Morilla-Santos, et al.Electronic structure and magnetic properties of FeWO 4nanocrystals synthesized by the microwave-hydrothermal method [J] .Mater.Charact, 2012,73:124-129.]; Fan Dong adopts ultrasonic spray pyrolysis to prepare hollow PbWO 4microballoon [Fan Dong, Yu Huang, Shichun Zou, Jiang Liu, and S.C.Lee.Ultrasonic spray pyrolysis fabrication of solid and hollow PbWO 4spheres with structure-directed photocatalytic activity [J] .J.Phys.Chem.C, 2011,115 (1): 241-247]; In addition sol-gel method, microemulsion method, solvent-thermal method etc. are also had.Low temperature liquid phase synthetic method has the many merits such as condition is controlled, with low cost, environment is gentle, be considered to the synthetic method of nearly Green Chemistry, and low temperature liquid phase synthetic method is to inorganic reaction and the size of inorganic photocatalyst material that generates thus, pattern, structure, crystallinity presents special effect, and the tungstate photocatalysis material of therefore low temperature liquid phase method synthesis shows the more superior photocatalysis performance of the photocatalyst material of the same race prepared than other technologies of preparing.
Summary of the invention
A kind of hydro-thermal assisted cryogenic is the object of the present invention is to provide to calcine preparation pyramid-shaped Cr 2wO 6the method of crystallite, Cr prepared by this method 2wO 6crystallite pattern is complete, size uniform, size tunable, and temperature of reaction is low, reproducible, is applicable to scale operation.
For achieving the above object, present invention employs following technical scheme:
Step one: by Cr (NO 3) 39H 2o joins in deionized water, and constantly stirs, and is mixed with Cr 3+concentration is the clear solution A (Cr (NO of 0.2 ~ 0.6mol/L 3) 3solution);
Step 2: by Na 2wO 42H 2o joins in deionized water, and constantly stirs, and is mixed with WO 4 2-concentration is the clear solution B (Na of 0.2 ~ 0.6mol/L 2wO 4solution);
Step 3: in clear solution A: the volume ratio of clear solution B is the ratio of 1:2 ~ 2:1, is joined in clear solution B by clear solution A, and form green precursor suspension liquid by stirring (about 30 minutes);
Step 4: regulate the pH of described precursor suspension liquid 7.0 ~ 12.0 to obtain mixture with aqueous sodium hydroxide solution;
Step 5: be poured into by mixture in hydrothermal reaction kettle, puts into homogeneous reaction instrument after then being sealed by hydrothermal reaction kettle, and reacts 1 ~ 24h at control hydrothermal temperature is 100 ~ 200 DEG C, naturally cools to room temperature after reaction terminates;
Step 6: after step 5, opens hydrothermal reaction kettle, and the product be obtained by reacting is carried out centrifugal must precipitation, will precipitate and adopt after deionized water and absolute ethanol washing at 50 ~ 80 DEG C of dry 2-4h successively, and obtain intermediate product;
Step 7: intermediate product is put into retort furnace at 400 ~ 650 DEG C of calcining 2-4h, obtain Cr 2wO 6crystallite.
The concentration of described aqueous sodium hydroxide solution is 0.5 ~ 1mol/L.
In described step 5, the compactedness of hydrothermal reaction kettle controls 40 ~ 60%.
Beneficial effect of the present invention is embodied in:
1) in the present invention, precursor reaction completes in the liquid phase, simple to operate, then obtained throw out is carried out low temperature calcination, is a kind of hydro-thermal assisted cryogenic calcining synthesis pyramid-shaped Cr 2wO 6the method of crystallite, expands Cr 2wO 6the synthetic technology scope of crystallite;
2) the present invention prepares Cr 2wO 6the raw material of crystallite is easy to get, and the low temperature calcination time is short, and temperature of reaction is low, and energy consumption of reaction is little, has saved cost;
3) by the pyramid-shaped Cr of the inventive method gained 2wO 6crystallite is grown complete, and purity is higher, and size is even, better dispersed, and particle size is controlled;
4) the present invention prepares pyramid-shaped Cr 2wO 6the repeatability of crystallite is high, pollutes little, is suitable for scale operation, have vast potential for future development.
Accompanying drawing explanation
Fig. 1 is Cr prepared by embodiment 1 2wO 6the XRD figure spectrum of crystallite, product corresponding standard JCPDS card numbering No.35-0791;
Fig. 2 is Cr prepared by embodiment 1 2wO 6the SEM photo of crystallite.
Embodiment
Below in conjunction with drawings and Examples, the present invention is elaborated.
Embodiment 1:
Step one: by analytically pure for 6mmol Cr (NO 3) 39H 2o joins in 15mL deionized water, and constantly stirs, and is mixed with clear solution A;
Step 2: by analytically pure for 3mmol Na 2wO 42H 2o joins in 15mL deionized water, and constantly stirs, and is mixed with clear solution B;
Step 3: in clear solution A: the volume ratio of clear solution B is the ratio of 2:1, is joined slowly in clear solution B by clear solution A, and uses magnetic stirrer 30min, forms green precursor suspension liquid;
Step 4: regulate the pH of green precursor suspension liquid 8.0 to obtain mixture with 0.8mol/L aqueous sodium hydroxide solution;
Step 5: mixture is poured in hydrothermal reaction kettle, compactedness controls 40%; Then seal hydrothermal reaction kettle, put into homogeneous reaction instrument, controlling hydrothermal temperature is 160 DEG C of reaction 12h, naturally cools to room temperature after reaction terminates;
Step 6: open hydrothermal reaction kettle, carries out centrifugal must precipitation by the product be obtained by reacting, and then adopts deionized water, absolute ethanol washing to precipitate successively 3 ~ 5 times, will to be deposited in electric drying oven with forced convection in 60 DEG C of dry 2h after washing, to obtain intermediate product;
Step 7: intermediate product is put into retort furnace at 650 DEG C of calcining 2h, obtain final product Cr 2wO 6crystallite.
As can be seen from Figure 1, prepared Cr 2wO 6microcrystallization is good, and purity is higher.As can be seen from Figure 2, prepared Cr 2wO 6crystallite is grown complete, in pyramid-shaped, and Cr 2wO 6crystallite diameter is about 1 μm.
Embodiment 2:
Step one: by analytically pure for 8mmol Cr (NO 3) 39H 2o joins in 15mL deionized water, and constantly stirs, and is mixed with clear solution A;
Step 2: by analytically pure for 4mmol Na 2wO 42H 2o joins in 15mL deionized water, and constantly stirs, and is mixed with clear solution B;
Step 3: in clear solution A: the volume ratio of clear solution B is the ratio of 1:1, is joined slowly in clear solution B by clear solution A, and uses magnetic stirrer 30min, forms green precursor suspension liquid;
Step 4: regulate the pH of green precursor suspension liquid 7.0 to obtain mixture with 1mol/L aqueous sodium hydroxide solution;
Step 5: mixture is poured in hydrothermal reaction kettle, compactedness controls 40%; Then seal hydrothermal reaction kettle, put into homogeneous reaction instrument, controlling hydrothermal temperature is 180 DEG C of reaction 12h, naturally cools to room temperature after reaction terminates;
Step 6: open hydrothermal reaction kettle, carries out centrifugal must precipitation by the product be obtained by reacting, and then adopts deionized water, absolute ethanol washing to precipitate successively 3 ~ 5 times, will to be deposited in electric drying oven with forced convection in 60 DEG C of dry 2h after washing, to obtain intermediate product;
Step 7: intermediate product is put into retort furnace at 600 DEG C of calcining 2h, obtain final product Cr 2wO 6crystallite.Cr 2wO 6crystallite diameter is about 1 μm.
Embodiment 3:
Step one: by analytically pure for 6mmol Cr (NO 3) 39H 2o joins in 20mL deionized water, and constantly stirs, and is mixed with clear solution A;
Step 2: by analytically pure for 6mmol Na 2wO 42H 2o joins in 20mL deionized water, and constantly stirs, and is mixed with clear solution B;
Step 3: in clear solution A: the volume ratio of clear solution B is the ratio of 1:2, is joined slowly in clear solution B by clear solution A, and uses magnetic stirrer 30min, forms green precursor suspension liquid;
Step 4: regulate the pH of green precursor suspension liquid 10.0 to obtain mixture with 1mol/L aqueous sodium hydroxide solution;
Step 5: mixture is poured in hydrothermal reaction kettle, compactedness controls 50%; Then seal hydrothermal reaction kettle, put into homogeneous reaction instrument, controlling hydrothermal temperature is 170 DEG C of reaction 24h, naturally cools to room temperature after reaction terminates;
Step 6: open hydrothermal reaction kettle, carries out centrifugal must precipitation by the product be obtained by reacting, and then adopts deionized water, absolute ethanol washing to precipitate successively 3 ~ 5 times, will to be deposited in electric drying oven with forced convection in 70 DEG C of dry 2h after washing, to obtain intermediate product;
Step 7: intermediate product is put into retort furnace at 650 DEG C of calcining 2h, obtain final product Cr 2wO 6crystallite.Cr 2wO 6crystallite diameter is about 1 μm.
Embodiment 4:
Step one: by analytically pure for 6mmol Cr (NO 3) 39H 2o joins in 20mL deionized water, and constantly stirs, and is mixed with clear solution A;
Step 2: by analytically pure for 12mmol Na 2wO 42H 2o joins in 20mL deionized water, and constantly stirs, and is mixed with clear solution B;
Step 3: in clear solution A: the volume ratio of clear solution B is the ratio of 1:1, is joined slowly in clear solution B by clear solution A, and uses magnetic stirrer 30min, forms green precursor suspension liquid;
Step 4: regulate the pH of green precursor suspension liquid 9.0 to obtain mixture with 1mol/L aqueous sodium hydroxide solution;
Step 5: mixture is poured in hydrothermal reaction kettle, compactedness controls 50%; Then seal hydrothermal reaction kettle, put into homogeneous reaction instrument, controlling hydrothermal temperature is 180 DEG C of reaction 12h, naturally cools to room temperature after reaction terminates;
Step 6: open hydrothermal reaction kettle, carries out centrifugal must precipitation by the product be obtained by reacting, and then adopts deionized water, absolute ethanol washing to precipitate successively 3 ~ 5 times, will to be deposited in electric drying oven with forced convection in 80 DEG C of dry 2h after washing, to obtain intermediate product;
Step 7: intermediate product is put into retort furnace at 600 DEG C of calcining 2h, obtain final product Cr 2wO 6crystallite.Cr 2wO 6crystallite diameter is about 1 μm.

Claims (3)

1. a hydro-thermal assisted cryogenic calcining preparation pyramid-shaped Cr 2wO 6the method of crystallite, is characterized in that: comprise the following steps:
Step one: by Cr (NO 3) 39H 2o joins in deionized water, is mixed with Cr 3+concentration is the clear solution A of 0.2 ~ 0.6mol/L;
Step 2: by Na 2wO 42H 2o joins in deionized water, is mixed with WO 4 2-concentration is the clear solution B of 0.2 ~ 0.6mol/L;
Step 3: in clear solution A: the volume ratio of clear solution B is the ratio of 1:2 ~ 2:1, is joined in clear solution B by clear solution A, and form green precursor suspension liquid by stirring;
Step 4: regulate the pH of described precursor suspension liquid 7.0 ~ 12.0 to obtain mixture with aqueous sodium hydroxide solution;
Step 5: be poured into by mixture in hydrothermal reaction kettle, puts into homogeneous reaction instrument after then being sealed by hydrothermal reaction kettle, and reacts 1 ~ 24h at control hydrothermal temperature is 100 ~ 200 DEG C, naturally cools to room temperature after reaction terminates;
Step 6: open hydrothermal reaction kettle, carries out centrifugal must precipitation by the product be obtained by reacting, and will precipitate and adopt after deionized water and absolute ethanol washing at 50 ~ 80 DEG C of dry 2-4h successively, and obtain intermediate product;
Step 7: intermediate product is put into retort furnace at 400 ~ 650 DEG C of calcining 2-4h, obtain Cr 2wO 6crystallite.
2. pyramid-shaped Cr is prepared in a kind of hydro-thermal assisted cryogenic calcining according to claim 1 2wO 6the method of crystallite, is characterized in that: the concentration of described aqueous sodium hydroxide solution is 0.5 ~ 1mol/L.
3. pyramid-shaped Cr is prepared in a kind of hydro-thermal assisted cryogenic calcining according to claim 1 2wO 6the method of crystallite, is characterized in that: in described step 5, and the compactedness of hydrothermal reaction kettle controls 40 ~ 60%.
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