CN104591267A - Multifunctional neodymium stannate nanosphere composite oxide material with single-phase pyrochlore structure - Google Patents
Multifunctional neodymium stannate nanosphere composite oxide material with single-phase pyrochlore structure Download PDFInfo
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- CN104591267A CN104591267A CN201510059287.XA CN201510059287A CN104591267A CN 104591267 A CN104591267 A CN 104591267A CN 201510059287 A CN201510059287 A CN 201510059287A CN 104591267 A CN104591267 A CN 104591267A
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- neodymium
- stannic acid
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Abstract
The invention discloses a multifunctional neodymium stannate nanosphere composite oxide material with a single-phase pyrochlore structure. The chemical structural formula of the oxide is Nd2Sn2O7; the oxide is a composite oxide material with a single-phase pyrochlore structure synthesized by taking PEG as a crosslinking agent and using a hydrothermal method; the synthesis process is free of high-temperature roasting to recrystallize, simple in process, easy to control, free of pollution and low in cost; the obtained sample has a spherical morphology which is relatively large in specific surface area, uniform in particle distribution and relatively small in particle size. The neodymium stannate nanosphere composite oxide material with the pyrochlore structure has obvious luminescence peaks at the wavelengths 408 nm and 438 nm of a visible region, so that the application of the neodymium stannate nanosphere composite oxide material with the pyrochlore structure in the field of photoluminescence is expanded; meanwhile, the material can be used for catalytically removing the diesel vehicle tail gas and photocatalytic treatment wastewater, so that the material is a multifunctional neodymium stannate nanosphere composite oxide material with a single-phase pyrochlore structure.
Description
Technical field
The present invention relates to the stannic acid neodymium nanometer ball composite oxide material of the single-phase pyrochlore constitution of a kind of multifunctional type, belong to rare earth material preparation and application technical field.
Background technology
The general structure formula of pyrrhite is A
2b
2o
7(wherein A, B are+3 valencys and+4 valency positively charged ions respectively), belongs to cube center of area crystallographic system, O
h 7(i.e. Fd3m) spacer, this structure can think the positively charged ion (A by two kinds of different radiis
3+, B
4+) and 1/8 anion vacancy composition fluorite type structure.Pyrrhite composite oxides due to its at high temperature excellent thermostability and catalytic activity and by extensive concern, and have been applied in the process reactions such as CO oxidation, methyl hydride combustion, CO-NO reaction, photochemical catalysis.
Preparation method for pyrochlore type multiple oxide material is mainly divided three classes: vapor phase process, solid phase method and liquid phase method, wherein vapor phase process is higher to preparing required equipment requirement, and solid phase method is poor to the controlling of component when calcining, easily cause component segregation, the product obtained often contains impurity, pattern is irregular, particle is comparatively large, size-grade distribution is wide, and liquid phase method is more satisfactory preparation method comparatively speaking.And liquid phase method also comprises multiple, wherein hydrothermal synthesis method has that raw material is easy to get, synthesis condition is gentle, product purity is high, grain development is complete, particle diameter is little and distribution uniform, become the more general method preparing pyrochlore type multiple oxide material of use without advantages such as obviously reunion, morphology controllable.
The stannic acid neodymium nanometer ball composite oxide material of single-phase pyrochlore constitution, the chemical structural formula of this oxide compound is Nd
2sn
2o
7, because it has typical pyrochlore constitution, thus there is excellent photocatalytic activity, become the study hotspot of people in recent years gradually.In prior art, Wang Hao, Zhang Tingting etc. adopt common hydrothermal synthesis method, using NaOH as mineralizer, do not add the Nd that any complexing agent or synthesis of surfactant go out to have single-phase pyrochlore constitution
2sn
2o
7, but this material does not have the character of photoluminescence, limits its application in photoluminescence field.Yao Kuihong, Yu Guixia etc. adopt the Nd with single-phase pyrochlore constitution of common water heat transfer
2sn
2o
7material does not have obvious photoluminescence in visible region, thus defines its application yet.And Chunjie Wang etc. adopt hydrothermal method and add polyoxyethylene glycol (PEG) as synthesis of surfactant a kind of Nd
2zr
2o
7composite oxide material, but this kind of material require of synthesis just has pyrochlore constitution after 1100 DEG C of high-temperature roastings, thus wastes a large amount of energy.
Summary of the invention
For problems of the prior art, the invention provides the stannic acid neodymium nanometer ball composite oxide material of the single-phase pyrochlore constitution of a kind of multifunctional type.
The present invention is by the following technical solutions:
A stannic acid neodymium nanometer ball composite oxide material for the single-phase pyrochlore constitution of multifunctional type, it is characterized in that, it is prepared by following steps:
(1) equivalent takes neodymium nitrate and the tin tetrachloride solid of 0.005mol ~ 0.025mol respectively, is dissolved in deionized water being also at room temperature stirred to dissolving completely; Taking 20g ~ 60gPEG is dissolved in deionized water, slowly pours in mixing salt solution, stirs 1-12h.
(2) under whipped state, in the solution that step (1) obtains, slowly drip sodium hydroxide solution, make solution ph finally remain on 8-12, obtain suspension liquid.
(3) suspension liquid that step (2) obtains is carried out insulation at 60-100 DEG C aging, continue 2-24h, obtain reaction mixture.
(4) reaction mixture that step (3) obtains is transferred in reactor, sealing, at 150-250 DEG C, be incubated 6-48h carry out hydro-thermal reaction, after question response still naturally cools to room temperature, take out reactant, filter, and clean successively with deionized water and ethanol, dry, namely obtain the stannic acid neodymium nanometer ball composite oxides of single-phase pyrochlore constitution.
The polymerization degree of the PEG in described step (1) is 2000-6000.
Described composite oxide material specific surface area is 47.4m
2/ g-81.5m
2/ g.
Described composite oxide material median size is 117nm-181nm.
Described composite oxide material is 7500-13500cps in the photoluminescence strength of signal at 408nm place.
The invention has the beneficial effects as follows: the present invention utilizes PEG to synthesize the stannic acid neodymium nanometer ball composite oxides of the single-phase pyrochlore constitution of a kind of multifunctional type as linking agent assisting alcohol-hydrothermal method, without the need to high-temperature roasting recrystallization process, technique is simple, be easy to control, pollution-free, cost is low, and gained sample has larger specific surface area, even particle distribution, spherical morphology that particle diameter is less.Obvious glow peak is there is in the stannic acid neodymium nanometer ball composite oxide material of this pyrochlore constitution at visible region 408nm and 438nm wavelength place, expand the application of stannic acid neodymium nanometer ball composite oxide material in photoluminescence field of pyrochlore constitution, this material can also be used for catalytic elimination exhaust gas from diesel vehicle and photocatalysis treatment of waste water simultaneously, because of but a kind of stannic acid neodymium nanometer ball composite oxide material of single-phase pyrochlore constitution of multifunctional type.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of embodiment 1 pyrochlore constitution stannic acid neodymium;
Fig. 2 is the stereoscan photograph of embodiment 1 pyrochlore constitution stannic acid neodymium;
Fig. 3 is the DLS sreen analysis histogram of embodiment 1 pyrochlore constitution stannic acid neodymium;
Fig. 4 is the conversion rate curve of embodiment 1-3 stannic acid neodymium nano material catalysis carbon-smoke combustion;
Fig. 5 is the effect curve of embodiment 1-3 stannic acid neodymium nanomaterial photocatalytic degradation methylene blue;
Fig. 6 is the nano material photo-induced luminous spectrogram of embodiment 1-3 stannic acid neodymium.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
(1) take neodymium nitrate and the tin tetrachloride of 0.005mol respectively, be dissolved in deionized water and be at room temperature stirred to and dissolve completely; Take 20g PEG2000 and be dissolved in deionized water, slowly pour in mixing salt solution, stir 1h.
(2) under whipped state, in the solution that step (1) obtains, slowly drip sodium hydroxide solution, make solution ph finally remain on 10, obtain suspension liquid.
(3) suspension liquid that step (2) obtains is carried out insulation at 60 DEG C aging, stir 24h, obtain reaction mixture.
(4) reaction mixture that step (3) obtains is transferred in reactor, sealing, at 200 DEG C, be incubated 18h carry out hydro-thermal reaction, after question response still naturally cools to room temperature, take out reactant, filter, and clean successively with deionized water and ethanol, dry, obtain pyrochlore constitution stannic acid neodymium.
The sample obtained to the present embodiment carries out XRD detection, and scanning electron microscope is according to collection of illustrative plates and DLS sreen analysis, and its result is shown in Fig. 1-3 respectively.As can be seen from Figure 1, the single pyrochlore-type stannic acid neodymium of crystalline phase of the method synthesis, its specific surface area is 47.4m
2/ g; As can be seen from Figure 2, product pattern is be evenly distributed spherical; As can be seen from Figure 3, the median size of product is 117nm.By contrast, co-precipitation is 11.2m in conjunction with the specific surface area of high-temperature roasting method gained stannic acid neodymium oxides
2/ g, present fine and close sheet structure, its median size is 470 nm.
Embodiment 2
(1) take neodymium nitrate and the tin tetrachloride of 0.015mol respectively, be dissolved in deionized water and be at room temperature stirred to and dissolve completely; Taking 40g PEG4000 is dissolved in deionized water, slowly pours in mixing salt solution, stirs 6h.
(2) under whipped state, in the solution that step (1) obtains, slowly drip sodium hydroxide solution, make solution ph finally remain on 8, obtain suspension liquid.
(3) suspension liquid that step (2) obtains is carried out insulation at 80 DEG C aging, stir 12h, obtain reaction mixture.
(4) reaction mixture that step (3) obtains is transferred in reactor, sealing, at 150 DEG C, be incubated 48h carry out hydro-thermal reaction, after question response still naturally cools to room temperature, take out reactant, filter, and clean successively with deionized water and ethanol, dry, obtain pyrochlore constitution stannic acid neodymium.
The single pyrochlore-type stannic acid neodymium of crystalline phase of this embodiment synthesis, its specific surface area is 73.4 m after tested
2/ g, much larger than coprecipitation method gained stannic acid neodymium; Its pattern is be evenly distributed spherical, and its median size is 131 nm, much smaller than coprecipitation method gained stannic acid neodymium.
Embodiment 3
(1) take neodymium nitrate and the tin tetrachloride of 0.025mol respectively, be dissolved in deionized water being also at room temperature stirred to and dissolve completely; Taking 60g PEG6000 is dissolved in deionized water, slowly pours in mixing salt solution, stirs 12h.
(2) under whipped state, in the solution that step (1) obtains, slowly drip sodium hydroxide solution, make solution ph finally remain on 12, obtain suspension liquid.
(3) suspension liquid that step (2) obtains is carried out insulation at 100 DEG C aging, stir 2h, obtain reaction mixture.
(4) reaction mixture that step (3) obtains is transferred in reactor, sealing, at 250 DEG C, be incubated 6h carry out hydro-thermal reaction, after question response still naturally cools to room temperature, take out reactant, filter, and clean successively with deionized water and ethanol, dry, obtain pyrochlore constitution stannic acid neodymium.
The single pyrrhite of crystalline phase of this embodiment synthesis, its specific surface area is 81.5 m2/g after tested, much larger than coprecipitation method gained stannic acid neodymium; Its pattern is that distribution is homogeneous spherical, and its median size is 181nm, much smaller than coprecipitation method gained stannic acid neodymium.
Embodiment 4
Get above-mentioned embodiment 1,2 and 3 gained stannic acid neodymium catalyst respectively, simulation diesel engine truck exhaust atmosphere, with the soot particulate that the Printex-U carbon black diesel oil substitute machine of German Degussa company discharges, adopt the soot catalytic combustion activity of temperature programmed oxidation(TPO) technological assessment catalyzer.As shown in Figure 4, record the combustion initiation temperature of carbon-smoke combustion on catalyzer according to the raw conversion rate curve of carbon-smoke combustion reaction and be generally 310 ~ 350 DEG C, generate CO
2selectivity nearly 100%, CO can not be generated and cause secondary pollution.SiO in Fig. 4
2represent the conversion rate curve of soot noncatalytic combustion when not adding catalyzer, combustion initiation temperature is 480 DEG C; And the combustion initiation temperature of the carbon-smoke combustion of coprecipitation method gained stannic acid neodymium catalyst is 410 DEG C, generate CO
2selectivity be 75%, also have 25% CO generate.Thus gained stannic acid neodymium nano material catalytic activity of the present invention is good, and selectivity is high, this with its larger specific surface area, less particle diameter is relevant with globosity.
Embodiment 5
Get above-mentioned embodiment 1,2 and 3 gained stannic acid neodymium catalyst respectively, dye wastewater is discharged, to degrade under ultra violet lamp the methylene blue dye of 10mg/l, dark reaction is illumination 1 hour again after 1 hour, degradation effect as shown in Figure 5, dye degrades rate under three catalyst actions all reaches more than 90%, and the catalyst degradation rate that wherein prepared by embodiment 1 all reaches 100%.Under the same terms, adopt the TiO of German Degussa company
2(P25) degradation rate of business photocatalyst is 85%.Gained stannic acid neodymium nano material photocatalytic activity of the present invention is good, and it is relevant that this globosity less with its particle diameter produces more Lacking oxygen.
Embodiment 6
Get above-mentioned embodiment 1,2 and 3 gained stannic acid neodymium composite oxide material respectively, adopt Edinburgh, Britain instrument company FLS920 type built-up type transient state/steady-state fluorescence spectrograph to test its photoluminescence performance.As shown in Figure 6, under the optical excitation of 280nm wavelength, three kinds of materials have the utilizing emitted light spectrogram that shape is similar and intensity is different, at 360nm, 408nm and 438nm wavelength there is obvious glow peak in place, this can belong to the luminescence center that material surface Lacking oxygen produces, and wherein the peak intensity at visible region 408nm place is maximum.And the stannic acid neodymium material of general hydrothermal method gained does not have photoluminescence signal in visible region, thus gained stannic acid neodymium nano material of the present invention has expanded its application in photoluminescence field, its stronger photoluminescence performance is with its grain size is less and more Lacking oxygen that is that produce is relevant, generally speaking identical nanometer oxide material particle diameter is formed less, the Lacking oxygen produced is more, and photoluminescence signal is stronger.
Claims (5)
1. a stannic acid neodymium nanometer ball composite oxide material for the single-phase pyrochlore constitution of multifunctional type, it is characterized in that, it is prepared by following steps:
(1) equivalent takes neodymium nitrate and the tin tetrachloride solid of 0.005mol ~ 0.025mol respectively, is dissolved in deionized water being also at room temperature stirred to dissolving completely; Taking 20g-60g PEG is dissolved in deionized water, slowly pours in mixing salt solution, stirs 1-12h;
(2) under whipped state, in the solution that step (1) obtains, slowly drip sodium hydroxide solution, make solution ph finally remain on 8-12, obtain suspension liquid;
(3) suspension liquid that step (2) obtains is carried out insulation at 60-100 DEG C aging, continue 2-24h, obtain reaction mixture;
(4) reaction mixture that step (3) obtains is transferred in reactor, sealing, at 150-250 DEG C, be incubated 6-48h carry out hydro-thermal reaction, after question response still naturally cools to room temperature, take out reactant, filter, and clean successively with deionized water and ethanol, dry, namely obtain the stannic acid neodymium nanometer ball composite oxides of single-phase pyrochlore constitution.
2. the stannic acid neodymium nanometer ball composite oxide material of the single-phase pyrochlore constitution of multifunctional type according to claim 1, is characterized in that, the polymerization degree of the PEG in described step (1) is 2000-6000.
3. the stannic acid neodymium nanometer ball composite oxide material of the single-phase pyrochlore constitution of multifunctional type according to claim 1, it is characterized in that, described composite oxide material specific surface area is 47.4m
2/ g-81.5m
2/ g.
4. the stannic acid neodymium nanometer ball composite oxide material of the single-phase pyrochlore constitution of multifunctional type according to claim 1, it is characterized in that, described composite oxide material median size is 117nm-181nm.
5. the stannic acid neodymium nanometer ball composite oxide material of the single-phase pyrochlore constitution of the multifunctional type according to any one of claim 1-4, is characterized in that, described composite oxide material is 7500-13500 cps in the photoluminescence strength of signal at 408nm place.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105565371A (en) * | 2016-02-19 | 2016-05-11 | 浙江大学 | Method for preparing high-purity neodymium-stannate nanometer powder |
| CN109453771A (en) * | 2018-11-13 | 2019-03-12 | 中国科学技术大学先进技术研究院 | The preparation of a kind of pyrochlore materials and its application in electro-catalysis production oxygen |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041458A (en) * | 2007-03-02 | 2007-09-26 | 浙江理工大学 | Universal synthesizing method for lanthanide series rare earth stannate nano powder |
| CN101693520A (en) * | 2009-10-21 | 2010-04-14 | 济南大学 | Industrialized process for preparing cerium oxide nano-rods doped with rare earth elements |
| CN101879445A (en) * | 2010-07-15 | 2010-11-10 | 济南大学 | Composite rear earth pyrochlore-type oxide catalyst for catalyzing burning for removing soot of diesel vehicle and preparation method thereof |
| WO2014058553A1 (en) * | 2012-10-10 | 2014-04-17 | Baker Hughes Incorporated | Nanoparticle modified fluids and methods of manufacture thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041458A (en) * | 2007-03-02 | 2007-09-26 | 浙江理工大学 | Universal synthesizing method for lanthanide series rare earth stannate nano powder |
| CN101693520A (en) * | 2009-10-21 | 2010-04-14 | 济南大学 | Industrialized process for preparing cerium oxide nano-rods doped with rare earth elements |
| CN101879445A (en) * | 2010-07-15 | 2010-11-10 | 济南大学 | Composite rear earth pyrochlore-type oxide catalyst for catalyzing burning for removing soot of diesel vehicle and preparation method thereof |
| WO2014058553A1 (en) * | 2012-10-10 | 2014-04-17 | Baker Hughes Incorporated | Nanoparticle modified fluids and methods of manufacture thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105565371A (en) * | 2016-02-19 | 2016-05-11 | 浙江大学 | Method for preparing high-purity neodymium-stannate nanometer powder |
| CN109453771A (en) * | 2018-11-13 | 2019-03-12 | 中国科学技术大学先进技术研究院 | The preparation of a kind of pyrochlore materials and its application in electro-catalysis production oxygen |
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