CN101049969A - Method for preparing Nano material of lead tungstate - Google Patents
Method for preparing Nano material of lead tungstate Download PDFInfo
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- CN101049969A CN101049969A CN 200710040483 CN200710040483A CN101049969A CN 101049969 A CN101049969 A CN 101049969A CN 200710040483 CN200710040483 CN 200710040483 CN 200710040483 A CN200710040483 A CN 200710040483A CN 101049969 A CN101049969 A CN 101049969A
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- tungstate
- deionized water
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 9
- NKTZYSOLHFIEMF-UHFFFAOYSA-N dioxido(dioxo)tungsten;lead(2+) Chemical compound [Pb+2].[O-][W]([O-])(=O)=O NKTZYSOLHFIEMF-UHFFFAOYSA-N 0.000 title claims description 14
- 239000000047 product Substances 0.000 claims abstract description 47
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012467 final product Substances 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical class [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims 1
- 238000004876 x-ray fluorescence Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 6
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005424 photoluminescence Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000004611 spectroscopical analysis Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Abstract
本发明属于无机纳米材料领域，涉及一种制备钨酸盐纳米材料的合成方法。将钨酸钠和铅盐分别置于容器中，以去离子水为溶剂，加入添加剂，在常温下反应40－60分钟，移入反应釜中，向釜中加入去离子水至釜容积的60％－70％，密封，然后在120－160℃温度下反应3－12小时，将反应釜自然冷却至室温，将产物取出，洗涤，离心分离干燥，将最终产物分散于无水乙醇中，即得所需产物。本发明原料易得，成本低廉，工艺简单，仪器设备简便，制备产物纯度高，后处理方便，不产生杂质污染物，为纳米材料的控制合成提供了新的途径。The invention belongs to the field of inorganic nanometer materials, and relates to a synthesis method for preparing tungstate nanomaterials. Put sodium tungstate and lead salt in containers respectively, use deionized water as solvent, add additives, react at room temperature for 40-60 minutes, move into the reaction kettle, add deionized water to the kettle to 60% of the volume of the kettle -70%, seal, then react at 120-160°C for 3-12 hours, cool the reactor to room temperature naturally, take out the product, wash, centrifuge and dry, and disperse the final product in absolute ethanol to obtain desired product. The invention has easy-to-obtain raw materials, low cost, simple process, simple equipment, high-purity prepared products, convenient post-treatment, no impurity pollutants, and provides a new approach for the controlled synthesis of nanometer materials.
Description
Technical field
The invention belongs to technical field of inorganic nanometer material, be specifically related to a kind of preparation method of Nano material of lead tungstate.
Background technology
In recent years, along with the development of high energy physics, find that PbWO4 (PWO) crystal has special advantage in exploring novel scintillator, it has high-density (8.3g/cm especially
3), short irradiation length (0.89cm), fast luminescence decay time (90% luminescence decay time is less than 20ns) and lower-price characteristic and be elected to be compact type IU meson spiral detector in the Large Hadron Collider (LHC) (compact muon solenoid, core component electromagnetic calorimeter scintillator material CMS) by CERN.
Crystal of lead tungstate has caused people's concern widely owing to its characteristics of luminescence and potential using value as a kind of luminescent material.There are some researches show that under certain excitation wavelength, crystal of lead tungstate shows the band absorption of blueness, green, redness, but its research is mainly concentrated on the crystal aspect, but relatively more rare to the research of its preparation and performance.
Hydrothermal method is as a kind of main method of preparation nano material, its principle is in special closed reaction vessel (autoclave) lining, adopt the aqueous solution as reaction medium, by reaction vessel is heated, create a high temperature, reaction under high pressure environment, make common indissoluble or insoluble substance dissolves and recrystallization.With respect to other preparation method, the nanocrystal of Hydrothermal Preparation have grow complete, granularity is little and be evenly distributed, particle agglomeration is light, can use more cheap raw material, advantages such as stoichiometry thing that is easy to get suitable and crystalline form.And crystal grain thing phase, dimension and pattern can be controlled by the control hydrothermal reaction condition; Especially hydrothermal method can prepare the nanocrystalline of complete crystallization and not need high-temperature calcination to handle, and powder hard aggregation, the defective having avoided causing in the calcination process form and the impurity introducing, and therefore, prepared powder has greater activity.
The synthetic report of the hydro-thermal of relevant plumbous tungstate material is more rare, and the prepared tungstate material that goes out is mostly with sphere, and long clavate is main, and its diameter does not wait from the nanometer to the micron order.The performance of Nano material of lead tungstate and the appearance structure of its particle are closely related, so the pattern research of Nano material of lead tungstate is become the key point for preparing the high-performance luminescent material.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of Nano material of lead tungstate.
The preparation method of a kind of Nano material of lead tungstate that the present invention proposes, concrete steps are as follows:
Sodium wolframate and lead salt are placed container respectively, are solvent with the deionized water, add additive, normal temperature stirred 40-60 minute down, moved in the reactor, added the 60%-70% of deionized water to reactor volume in reactor, sealing, reaction is 3-12 hour under 120-160 ℃ of temperature.Reactor is naturally cooled to room temperature, the gained throw out is taken out, washing, centrifugation is also dry, and final product is scattered in the dehydrated alcohol, and this final product is required product; Wherein, the mol ratio of sodium wolframate and lead salt is (0.8-1.2): 1.
Among the present invention, described lead salt is Pb (NO
3)
2, PbAc
2Or PbCl
2Deng in any.
Among the present invention, described additive be among CTAB (cetyl trimethylammonium bromide) or the SDS (sodium lauryl sulphate) etc. any, the additive add-on be the sodium wolframate molar weight 1-2 doubly.
Among the present invention, washing adopts deionized water and dehydrated alcohol to clean 3-8 time respectively.
Among the present invention, utilize the inventive method products therefrom can pass through scanning electronic microscope (SEM), X-ray powder diffraction (XRD) and fluorescence property characterize.
Among the present invention, XRD result shows product pure (consistent with the JCPDS card).Scanning electronic microscope (SEM) shows uniform particle diameter, good dispersity.Show that in the fluorescent spectroscopy result product has photoluminescence performance.
The present invention has following advantage:
1, the present invention under hydrothermal condition, utilize first conditions such as additive, temperature, pH value, reaction times change system studied the pattern and the fluorescence property thereof of prepared tungstate crystal.The appearance of nano material rule for preparing among the present invention, uniform particle diameter, degree of crystallinity is high and have a good fluorescence property.
2. technology of the present invention is simple, and reactant is basic inorganics, and raw material obtains very convenient, cheap, and the processing of product is more convenient, can carry out commercial scale production by amplification.
3, the present invention has certain toxicity except that lead salt in the process of preparation, the equal nontoxicity of other selected reagent, and tensio-active agent major part in place, back phase reason process can obtain reclaiming, and reaches the effect of economical environment-protective.
4, compare the method for solid state reaction, the hydrothermal method mild condition, easily by the temperature, pressure in the control still to reach the effect of control product pattern, structure and performance, better repeatability is arranged.
Description of drawings
Fig. 1 is scanning electronic microscope (SEM) figure in the embodiment of the invention.Wherein, a is a product shape appearance figure (5000X) among the embodiment 1, and b is a product shape appearance figure (2500X) among the embodiment 2, and c is a product shape appearance figure (20000X) among the embodiment 3.
Fig. 2 is the structure iron that the X-ray powder diffraction (XRD) of product in the embodiment of the invention obtains.Wherein, a is the XRD figure of product among the embodiment 1, and b is the XRD figure of product among the embodiment 2, and c is the XRD figure of product among the embodiment 3.
Fig. 3 is the fluorescence emission spectrogram of product in the embodiment of the invention.Wherein, a is the fluorescence spectrum figure of product among the embodiment 1, and b is the fluorescence spectrum figure of product among the embodiment 2, and c is the fluorescence spectrum figure of product among the embodiment 3.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1
(1) prepares the Pb (NO of 1mol/L respectively
3)
2Aqueous solution 100ml and 1mol/L NaWO
4Aqueous solution 100ml (reagent of employing all is to analyze alcohol).Respectively get in the 1ml adding 100ml beaker and mix, add 0.001molCTAB (cetyl trimethylammonium bromide) then, add a certain amount of deionized water and stir about 1 hour at normal temperatures again, move into then in 50 milliliters of tetrafluoroethylene reactors, in reactor, add the 60%-65% of deionized water to reactor volume, sealing was reacted 3 hours down in 120 ℃.Reactor is naturally cooled to room temperature.
(2) product is taken out, use deionized water and absolute ethanol washing 7-8 time, centrifugation is also dry, final product is dispersed in promptly gets required product in the dehydrated alcohol.
Use scanning electronic microscope (SEM) and x-ray powder diffraction instrument (XRD) that the pattern and the structure of product are characterized respectively, visible TEM shows that product is the PbWO of diameter 400 nanometers, the about 3-4 micron of length from Fig. 1 (a)
4The accurate nanometer rod of spirrillum, visible XRD result shows product pure (consistent with the JCPDS card) from Fig. 2 (a).As seen, fluorescent spectroscopy is the result show from Fig. 3 (a), and product has photoluminescence performance.
Embodiment 2
Prepare the PbAc of 1mol/L respectively
2Aqueous solution 100ml and 1mol/LNaWO
4Aqueous solution 100ml (reagent of employing all is to analyze alcohol).Respectively get in the 1ml adding 100ml beaker and mix, add 0.002molSDS (cetyl trimethylammonium bromide) then, add a certain amount of deionized water and stir about 1 hour at normal temperatures again, move into then in 50 milliliters of tetrafluoroethylene reactors, add the 65%-70% of deionized water in the reactor to reactor volume, sealing was reacted 6 hours down in 140 ℃.Reactor is naturally cooled to room temperature.Product is taken out, use deionized water and absolute ethanol washing 3-6 time, centrifugation is also dry, final product is dispersed in promptly gets required product in the dehydrated alcohol.The product that obtains is pagoda shape PbWO
4Accurate nano material, the crystallographic system of product is identical with embodiment 1.The product purity height, degree of crystallinity is good, and optical property is similar substantially to embodiment 1.Visible TEM shows that product is diameter 300 nanometers, the about 3.5 microns PbWO of length from Fig. 1 (b)
4The accurate nanometer rod of spirrillum, visible XRD result shows product pure (consistent with the JCPDS card) from Fig. 2 (b).As seen, fluorescent spectroscopy is the result show from Fig. 3 (b), and product has photoluminescence performance.
Embodiment 3
Prepare the PbCl of 1mol/L respectively
2Aqueous solution 100m and 1mol/L NaWO
4Aqueous solution 100ml (reagent of employing all is to analyze alcohol).Get 0.8mlPbCl respectively
2The aqueous solution and 1ml NaWO
4The aqueous solution adds in the 100ml beaker, add 0.0015molCTAB (cetyl trimethylammonium bromide) then, add a certain amount of deionized water and stir about 1 hour at normal temperatures again, move into then in 50 milliliters of tetrafluoroethylene reactors, add the 60%-63% of deionized water in the reactor to reactor volume, sealing was reacted 12 hours down in 160 ℃.Reactor is naturally cooled to room temperature.Product is taken out, and with deionized water and absolute ethanol washing, centrifugation is also dry, final product is dispersed in promptly gets required product in the dehydrated alcohol., the PbWO of the about 150nm of product diameter that obtains
4Nanoparticle, the crystallographic system of product is identical with embodiment 1.The product purity height, degree of crystallinity and optical property are good.Optical property is similar substantially to embodiment 1.Visible TEM shows that product is the nanoparticle about diameter 150 nanometers from Fig. 1 (c), and visible XRD result shows product pure (consistent with the JCPDS card) from Fig. 2 (c).As seen, fluorescent spectroscopy is the result show from Fig. 3 (c), and product has photoluminescence performance.
Embodiment 4
Prepare the PbCl of 1mol/L respectively
2Aqueous solution 100ml and 1mol/LNaWO
4Aqueous solution 100ml (reagent of employing all is to analyze alcohol).Get 1.2mlPbCl respectively
2The aqueous solution and 1ml NaWO
4The aqueous solution adds in the 100ml beaker, add 0.002molCTAB (cetyl trimethylammonium bromide) then, add a certain amount of deionized water and stir about 50 minutes at normal temperatures again, move into then in 50 milliliters of tetrafluoroethylene reactors, in reactor, add the 60%-70% of deionized water to reactor volume, sealing was reacted 12 hours down in 160 ℃.Reactor is naturally cooled to room temperature.Product is taken out, and with deionized water and absolute ethanol washing, centrifugation is also dry, final product is dispersed in promptly gets required product in the dehydrated alcohol.
Product structure is similar substantially to embodiment 3 to performance.
Claims (5)
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| CN 200710040483 CN101049969A (en) | 2007-05-10 | 2007-05-10 | Method for preparing Nano material of lead tungstate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502845A (en) * | 2011-10-24 | 2012-06-20 | 浙江理工大学 | Preparation method of monoclinic-phase lead tungstate |
| CN103964508A (en) * | 2014-04-29 | 2014-08-06 | 西南科技大学 | Preparation method for ginkgo-shaped lead tungstate |
| CN103993357A (en) * | 2014-05-08 | 2014-08-20 | 洛阳理工学院 | Preparation method of lead tungstate spindle-shaped crystals |
-
2007
- 2007-05-10 CN CN 200710040483 patent/CN101049969A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502845A (en) * | 2011-10-24 | 2012-06-20 | 浙江理工大学 | Preparation method of monoclinic-phase lead tungstate |
| CN102502845B (en) * | 2011-10-24 | 2013-11-06 | 浙江理工大学 | Preparation method of monoclinic-phase lead tungstate |
| CN103964508A (en) * | 2014-04-29 | 2014-08-06 | 西南科技大学 | Preparation method for ginkgo-shaped lead tungstate |
| CN103993357A (en) * | 2014-05-08 | 2014-08-20 | 洛阳理工学院 | Preparation method of lead tungstate spindle-shaped crystals |
| CN103993357B (en) * | 2014-05-08 | 2016-04-13 | 洛阳理工学院 | A kind of preparation method of plumbous tungstate fusiform crystal |
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