CN107057698A - A kind of order mesoporous zinc oxide composites of La/Eu and preparation method thereof - Google Patents
A kind of order mesoporous zinc oxide composites of La/Eu and preparation method thereof Download PDFInfo
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- CN107057698A CN107057698A CN201610322132.5A CN201610322132A CN107057698A CN 107057698 A CN107057698 A CN 107057698A CN 201610322132 A CN201610322132 A CN 201610322132A CN 107057698 A CN107057698 A CN 107057698A
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- zinc oxide
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- mesoporous
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7784—Chalcogenides
- C09K11/7785—Chalcogenides with zinc or cadmium
Abstract
The present invention relates to order mesoporous zinc oxide composites of a kind of La/Eu and preparation method thereof.The present invention prepares the order mesoporous ZnO nano material of can-like using template；Doping La/Eu phosphate, prepares the order mesoporous zinc oxide composites of La/Eu in the ZnO of preparation.This material occurs in that Eu transition transmitting under the exciting of 465 nanometers of light；When being excited with 414 nanometers of light, ZnO transmitting is occurred in that, by different excitations, the transmitting light of different colours is obtained, realizes photochromic adjustable.Because ZnO at 469 nanometers has transmitting, and Eu has absorption at 465 nanometers, and both just have superposition, so ZnO can effectively transfer energy to Eu, and then improve Eu luminous efficiency.The present invention is in fluorescent material, photocatalysis, and the direction such as display material is with a wide range of applications.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, in particular relate to a kind of order mesoporous zinc oxide of La/Eu- and be combined
Material and preparation method thereof.
Background technology
Mesoporous material generally refers to aperture for 2-50nm, and porosity is more than 40% orderly pore passage structure material, for many
Hole nano material, after total void volume (porosity) reaches certain value, if pore volume is sufficiently small, can also show the size portalled
Effect and skin effect, so as to produce a series of different properties with body phase.Ordered mesoporous material is that 1990s is emerging rapidly
The novel nano structure material for rising and developing, it is some other many that the tempting part compared with general porous material is that it has
Excellent properties not available for Porous materials：Have with specific surface area is big, duct is uniform in size, aperture is adjustable and pore passage structure is regular
The features such as sequence, thus in functional material, Industrial Catalysis, offal treatment, absorption and separation and the research of gas sensor etc.
Field shows important application value and potential application prospect.Many different orderly semiconductor materials have been worked out at present
Material, such as indium oxide.But yet there are no the report of the doping on synthesizing ordered mesoporous zinc oxide and its rare earth material.
ZnO is a kind of relatively good ultraviolet absorption material, when ultraviolet lighting is mapped on sample surfaces, in composite
ZnO lattice will soon absorb the energy of the ultraviolet light as excitation source, and store, then by these storages
Energy passes to rare earth ion again, so that the 4f electronics of excitation rare-earth ion, makes it produce transition, further result in rare earth ion
Produce red emission.So ZnO may be used as the matrix material of rare earth luminescent material, to improve the luminous efficiency of rare earth ion.
Li ionic radius is very small, can be easier to enter in ZnO interstitial void, so LiOH is a kind of good sensitizer,
LiOH addition can be such that rare earth ion more preferably, more effectively solid solution and penetrates into the lattice dot matrix of zno-based body.Also exactly because
For in this way, in the preparation of composite, Li+Play a part of charge compensation.ZnO crystal has a unique two-dimensional layer
Structure.So, the cross-relaxation between rare earth ion can be limited in the adjacent node in the approximately the same plane in ZnO crystal
On.Due to Li+Ionic radius it is very small, preparation contain Li+Composite in, work as Li+Enter ZnO lattice dot matrix
When middle, Li+Tend to enter in the cation defect between layer and layer.At the same time, due to charge-compensation effects
In the presence of Li+It is more likely to close to rear earth ions distribution, and forms cation pair, balances negative electrical charge.Li+Doping can hinder
Hinder or limit the friendship closed between the high level excitation state electronics of rare earth ion and lower level excitation state electronics or ground state electron
Pitch relaxation.The presence of these factors can improve the transition probability of rare earth ion transition process, strengthen the jump of the excitation state of electronics
Move transmitting.
The rare earth doped phosphate of mesoporous material is a kind of preferable fluorescent material, is that, using mesoporous material as substrate, inserting can
The luminescent materials such as dissolubility RE phosphate, make phosphate fluophor solidify in mesopore orbit, so as to obtain composite luminescent material.
While La3+For Eu3+Illumination effect have a certain impact, when europium lanthanum mol ratio be 1: 1 when, complex fluorescence hair
Peak intensity is penetrated relatively low, with La3+Addition increase, Eu3+The reduction of amount, Eu3+Fluorescent emission intensity do not reduce not only,
Increase on the contrary.This is due to La3+Addition reduce europium ion concentration, inhibit concentration quenching, make energy transmission more abundant.
Also it is La3+Addition make Eu3+The enhancing of characteristic fluorescence emissive porwer may be relevant with intramolecular charge-transfer transition, and part absorbs purple
After outer light, its excited singlet state is transitted to, and triplet energy level is relaxed towards with radiationless.La3+Without 4f electronics, its excitation energy is higher than
The triplet energy level of part, therefore fluorescence can not be sent, and the part being coordinated with lanthanum ion passes through La after absorbing energy3+By bridging
Part passes to Eu3+,Eu3+Absorption energy increases thus luminous intensity strengthens.
In view of ZnO self-characteristic and the intrinsic advantage of mesoporous material, some scholars are directed to studying mesoporous oxygen in recent years
Change the synthesis of zinc, also there are some related achievement in research reports [for example：J.Rao,A.Yu,C.L.Shao,
X.F.Zhou.Construction of Hollow and Mesoporous ZnO Microsphere:A Facile
Synthesis and Sensing Property[J],ACS Appl.Mater.Interfaces,2012,4(10):5346–
5352.], at present, reported in terms of order mesoporous zinc oxide synthesis less, and be all to use hard template method, that is,
Using the classical titanium dioxide silicon substrate ordered mesoporous material such as SBA-15 as template, the method for then being washed off template with sodium hydroxide, this
The mesoporous zinc oxide that kind of method is obtained is closer to zinc oxide nano-wire array.Because zinc oxide is relatively active, using soft template
The synthesising mesoporous zinc oxide of method is there is not yet complete report.
In addition, the mesoporous zinc oxide material synthesized at present is used for photocatalysis and air-sensitive field, especially it is ordered into mesoporous
Mesoporous zinc oxide is used as the research of the main body of rare earth luminescent material there is not yet relevant report.
The content of the invention
A kind of order mesoporous zinc oxide material of can-like is synthesized, the present invention is achieved in that and closed first using soft template method
Into going out order mesoporous zinc oxide material, the material in addition to regular meso-hole structure, meanwhile, the material also has can-like
Grain structure, that is to say, that the material is that can-like zinc oxide particle surfaces are dispersed with orderly mesopore orbit.
A kind of order mesoporous zinc oxide composites of La/Eu- are prepared for, the present invention is the order mesoporous zinc oxide with synthesis
For main body, RE phosphate is assembled in its duct, it is characterised in that the mesoporous zinc oxide material surface distributed of can-like is order mesoporous
Duct, the La/Eu phosphate by being doped with lighting function synthesizes a kind of order mesoporous oxygen of La/Eu- into the duct of matrix
Change zinc composite.The material has the good characteristics of luminescence, while under the exciting of different wavelengths of light, can respectively obtain Eu
With lighting for ZnO, the adjustable of glow color is realized.
A kind of preparation method of the order mesoporous zinc oxide of can-like, it is characterised in that using soft template method synthesis, with bromination ten
Six alkane trimethyl ammonium powder are template, and acetic acid dihydrate zinc is zinc source, prepare the order mesoporous zinc oxide of product, and mesoporous with what is synthesized
Zinc oxide is carrier, Eu and La RE phosphates are assembled in its duct using high temperature solid-state method, prepares rare earth/zinc oxide and is situated between
Hole composite luminescent material, its step is：
(1) soft template method prepares order mesoporous ZnO
1g cetyl trimethyl ammonium powder is dissolved in 480ml water, and stirred at 80 DEG C, in the solution
The acetic acid dihydrate zinc for adding 1.68g continues to be stirred to uniformly, is slowly added into lithium hydroxide, while testing pH with pH test paper, directly
To solution in slightly alkalescence, mixture stirs 2h at 80 DEG C, obtained mixed solution filtering, filters out product；Dry at room temperature
24h, crucible is put into by dried powdered product, 500 DEG C in Muffle furnace, is calcined 4 hours, is taken out product, is obtained mesoporous oxygen
Change zinc.
(2) high temperature solid phase synthesis meso-porous ZnO europium doped and lanthanum RE composite
Take a certain amount of Eu2O3(a little more, with standby) is poured into the beaker for filling hydrochloric acid, and stirring makes it simultaneously for heating
Sufficiently dissolving.It is put into drying box and is dried one day afterwards, beaker must be sealed.Beaker is taken out, Europium chloride powder is obtained
End.Mesoporous zinc oxide made from 0.1/0.2g is weighed, a certain amount of Europium chloride, nitric hydrate lanthanum, ammonium di-hydrogen phosphate mixing is added
It is ground into agate mortar, until medicine is in glue-like.Medicine is added in crucible, is put into Muffle furnace, is first heated
To 500 DEG C, two days are incubated；900 DEG C are heated to, 2h is incubated.Medicine is taken out, meso-porous ZnO europium doped is obtained and is answered with lanthanum rare earth
Compound.
Order mesoporous zinc oxide composites of prepared La/Eu- in above process, its individual particle size exists
200nm or so, by transmission electron microscope and opening size test, obtains order mesoporous zinc oxide.When europium ion content is 8%, lanthanum ion
Content is 16%, and the material of preparation has most strong absworption peak, realizes goal of the invention.
Brief description of the drawings
Fig. 1 is the order mesoporous ZnO of can-like TEM photos；
Fig. 2 is the order mesoporous ZnO of can-like SEM photograph；
Fig. 3 is (Eu-La)/ZnO XRD spectra；
Fig. 4 is (Eu-La)/ZnO FI-IR spectrograms；
Fig. 5 is 8%Eu3+16%La3+, the 8%Eu3+0%La3+The nitrogen adsorption-desorption figure of sample and meso-porous ZnO.
Fig. 6 is (Eu-La)/ZnO La3+Content is 4%, changes Eu3+Content launching light spectrogram；
Fig. 7 is (Eu-La)/ZnO Eu3+Content is 8%, changes La3+Content exciting light spectrogram；
Fig. 8 is (Eu-La)/ZnO Eu3+Content is 8%, changes La3+Content, the transmitting excited with 465nm wavelength
Spectrogram；
Fig. 9 is (Eu-La)/ZnO Eu3+Content is 8%, changes La3+Content, the transmitting excited with 414nm wavelength
Spectrogram；
Embodiment
Selected cetyl trimethylammonium bromide (CTAB) of the invention, absolute ethyl alcohol, europium oxide, nitric hydrate lanthanum, phosphorus
Acid dihydride ammonia, sulfosalicylic acid, hydrochloric acid, lithium hydroxide is commercially available analysis net product, the self-control of deionized water laboratory；Used
Glass apparatus and equipment are the instrument and equipments commonly used in laboratory.
Embodiment：1g cetyl trimethyl ammonium powder is dissolved in 480ml water, and stirred at 80 DEG C,
The acetic acid dihydrate zinc for adding 1.68g in the solution continues to be stirred to uniformly, is slowly added into lithium hydroxide, while being surveyed with pH test paper
PH is tried, until solution is in slightly alkalescence, mixture stirs 2h at 80 DEG C, obtained mixed solution filtering filters out product；At room temperature
24h is dried, dried powdered product is put into crucible, 500 DEG C in Muffle furnace, calcines 4 hours, takes out product, the product
With regular mesopore orbit structure, as shown in Figure 1.Material is prepared as seen from Figure 2 except the well-regulated duct knot of tool
Outside structure, it macroscopically has can-like pattern.
Take a certain amount of Eu2O3(a little more, with standby) is poured into the beaker for filling hydrochloric acid, and stirring makes it simultaneously for heating
Sufficiently dissolving.It is put into drying box and is dried one day afterwards, beaker must be sealed.Beaker is taken out, Europium chloride powder is obtained
End.Mesoporous zinc oxide made from 0.2g is weighed, a certain amount of Europium chloride, nitric hydrate lanthanum, ammonium di-hydrogen phosphate is mixed to join agate
It is ground in Nao grinding bodies, until medicine is in glue-like.Medicine is added in crucible, is put into Muffle furnace, 500 are first to heat to
DEG C, it is incubated two days；900 DEG C are heated to, 2h is incubated.Medicine is taken out, meso-porous ZnO europium doped and lanthanum RE composite is obtained.
Prepared (Eu-La)/ZnO nano composite has good crystallinity, the d values and relative intensity and ZnO of its diffraction maximum
PDF standard cards (79-0206) listed by d values it is consistent with relative intensity, belong to buergerite phase, as shown in Figure 3A.It is prepared
(Eu-La)/ZnO there is obvious small-angle diffraction peak, show that preparing material has mesoporous pore passage structure (such as Fig. 3 B).Fig. 4
What is provided is the infrared spectrogram for preparing material, the presence of ZnO skeletons is can see from figure, while with the presence of phosphate radical.Nitrogen
Adsorption-desorption (such as Fig. 5) shows that preparing material has the duct of cylinder.La is shown in Fig. 63+Content is 4%, changes europium
It has been shown that, with the increase of europium ion content, light stronger in the launching light spectrogram of the amount sample of ion, figure.When europium ion content
For 8% when, light most strong, afterwards, with the increase of europium ion content, luminescent decay.This, which is attributed to, there occurs concentration quenching.Fig. 7
It is shown that europium ion content is 8%, change the exciting light spectrogram of the amount of lanthanum ion.Europium ion has most strong hair at 618nm
Light.Prepared sample has three and 465nm of characteristic peak 395,414.395nm excitation peak is due to europium ion7F0-5L6The energy level transition of track.At 465nm is because europium ion7F0-5D2The transition of track.414 be zinc oxide from valence band to
The energy jump of conduction band.Fig. 8 is the launching light spectrogram of the sample obtained in the case where 465nm light is excited, and as can be seen from Fig., sample is most
Strong transmitting in 618nm, be attributed to europium ion (5D0→7F2) transition, sample has two characteristic emissions, respectively in 579nm,
At 595nm, it is attributed to respectively5D0→7F0With5D0→7F1Transition, when La concentration reaches 16%, prepares the luminescent properties of material
Most preferably.Emission spectrum of the material in the case where 414nm light is excited is prepared as shown in figure 9, what is now mainly presented is the luminous of ZnO.Extremely
This, material prepared by the present invention can produce different transmittings, it is possible to achieve photochromic is adjustable under the exciting of different wavelengths of light.
The research has synthesized the order mesoporous zinc oxide of can-like, and is entrained in europium ion and lanthanum ion by high temperature solid-state method
In zinc oxide, lanthanum ion improves the luminous intensity of the system as the rare earth luminous ion of incorporation, but is also required to certain
Optimal proportion.When europium ion content is 8%, lanthanum ion content is 16%, and the sample has most strong transmitting.The emission peak of zinc oxide
469, lanthanum ion has absorption at 465nm, and the emission band of zinc oxide is with the PLE of europium ion with overlapping a, energy
Just europium ion can be passed to from zinc oxide, so as to add luminous intensity.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of appended claims of the invention should all be belonged to.
Claims (3)
1. a kind of order mesoporous zinc oxide composites of La/Eu-, it is characterised in that can-like ZnO particle surface distributed, which, uniformly to be had
The mesopore orbit of sequence, La/Eu phosphate is distributed in mesopore orbit, and prepare material has most strong in the case where 465nm light is excited 618
Transmitting, the most strong transmitting of lower presentation zinc oxide is excited in 414nm light, can be realized with this photochromic adjustable.
2. a kind of pure zinc oxide ordered mesoporous material as claimed in claim 1, it is characterised in that the material has the shape of can-like
Looks, meanwhile, uniform ordered mesoporous pore canals are dispersed with the wall of can-like structure.
3. a kind of preparation method of pure zinc oxide ordered mesoporous material as claimed in claim 1, it is characterised in that use soft mode
Plate method, template, Zn (CH are used as with CTAB3COO)2As zinc source, product is prepared for pure zinc oxide ordered mesoporous material, simultaneously
Material has the pattern of can-like.Its step is：
(1) the cetyl trimethyl ammonium powder for weighing 1g is dissolved in 480ml water, and is stirred at 80 DEG C；
(2) the acetic acid dihydrate zinc for adding 1.68g continues to be stirred to uniformly；
(3) lithium hydroxide is slowly added into, while PH is tested with PH test paper, until solution is in slightly alkaline；
(4) mixture stirs 2h at 80 DEG C；
(5) the mixed solution filtering obtained, filters out product；
(6) it is drying for one day at 60 DEG C in drying box；
(7) dried powdered product is put into crucible, 500 DEG C in Muffle furnace, calcined 4 hours；
(8) product is taken out, mesoporous zinc oxide is obtained.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108328644A (en) * | 2018-05-04 | 2018-07-27 | 长春理工大学 | A kind of rodlike porous Er/Eu-ZnO composite material and preparation methods of rule |
| CN108467056A (en) * | 2018-05-04 | 2018-08-31 | 长春理工大学 | A kind of chalina structure C exOy- ZnO composite material and preparation methods |
| CN108620054A (en) * | 2018-05-04 | 2018-10-09 | 长春理工大学 | A kind of coralliform Zn-ZnO composite material and preparation methods |
-
2016
- 2016-05-16 CN CN201610322132.5A patent/CN107057698B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 吴莉莉等: "La、Ce掺杂ZnO纳米晶的发光特性", 《发光学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108328644A (en) * | 2018-05-04 | 2018-07-27 | 长春理工大学 | A kind of rodlike porous Er/Eu-ZnO composite material and preparation methods of rule |
| CN108467056A (en) * | 2018-05-04 | 2018-08-31 | 长春理工大学 | A kind of chalina structure C exOy- ZnO composite material and preparation methods |
| CN108620054A (en) * | 2018-05-04 | 2018-10-09 | 长春理工大学 | A kind of coralliform Zn-ZnO composite material and preparation methods |
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