CN101195741A - Zincium containing hydrotalcite with strong fluoresce and method for producing the same - Google Patents
Zincium containing hydrotalcite with strong fluoresce and method for producing the same Download PDFInfo
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- CN101195741A CN101195741A CNA2007101440140A CN200710144014A CN101195741A CN 101195741 A CN101195741 A CN 101195741A CN A2007101440140 A CNA2007101440140 A CN A2007101440140A CN 200710144014 A CN200710144014 A CN 200710144014A CN 101195741 A CN101195741 A CN 101195741A
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- zincium
- containing hydrotalcite
- hyperfluorescence
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- hydrotalcite
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Abstract
The invention relates to high fluorescent Zn-containing hydrotalcite (Zn-LLDHs) which has the following simplest formula of [M<2+>1-x-y Zn<2+>x Al<3+>y(OH)<-1>2] A<n->y/n Dx/mzB], and the preparation method. The magnesium zinc ion (Mg<2+>) in Al-hydrotalcite is replaced through an amount of magnesium zinc ion (Zn<2+>), and simultaneously are coordinated with ligands, such as 8-hydroxyquinoline dissolved or dispersing in lipophilic anions between layers, etc. The fluorescence quenching of (Zn<2+>) as the luminous center is effectively prevented, a special assembly structure formed by the ligandsor mixed ligands dissolved and mixed in the anions between layers, or (Zn<2+>) embedded on a panel layer improves the asymmetry of the coordinated (Zn<2+>) as the luminous center, simultaneously the heat stability of (Zn-LLDHs) is improved because of the protective function of the hydrotalcite layer structure, and therefore the novel high fluorescent Zn-containing hydrotalcite being different from the Zn-containing hydrotalcite which has no fluorescence usually and can emit corresponding zinc coordinate chelate intense fluorescence can be obtained.
Description
Technical field:
The present invention relates to a class and have Zincium containing hydrotalcite of hyperfluorescence and preparation method thereof
Background technology:
The simplest general formula is [M
2+ 1-xM
3+ x(OH)
2] A
N- X/n.yH
2O] hydrotalcite (layered double hydroxi-des, LDHs), M in its flaggy
2+Be divalent cations such as Mg, Ni, Cu or Zn, M
3+Be isomorphous Tricationic such as Al
3+Deng, A
N-Be interlayer anion such as CO
3 2-, Cl
-, SO
4 2-, NO
3 -Or other organic anion.Because M
2+Partly by M
3+Make the hydrotalcite flaggy positively charged behind the isomorphous substitution, the negatively charged ion between interposed layer links to each other with flaggy with weak chemical bond, with positive charge excessive on the balance flaggy, and is filled into interlayer with the water molecules of some amount.Because the cationic substitutability of flaggy of LDHs and the commutability of interlayer anion, can be with various inorganic with organic anion, with in many and the interposed layer such as heteropolyanion and title complex negatively charged ion, assembling obtains the stratiform thing of supramolecular structure, or Tricationic (Al
3+) be that other the isomorphous or nearly isomorphous Tricationic replaces, can obtain thus different series intercalation houghite material (hydrotalcite-like compound, LLDHs).So far, the various countries investigator is to synthetic, the preparation method of LDHs and LLDHs, and the broad research of having carried out at aspects such as ion-exchange, absorption, separation, catalysis, medicine is explored with using.
In recent years, the preparation of various functional houghites and characteristic research particularly receive publicity.Because the rare earth of special electron structure of tool and various multivalence, the transition metal that appraises at the current rate have functions such as various light, electricity, magnetic, catalysis, therefore rare earth and multivalence, the transition metal ion that appraises at the current rate are introduced in the hydrotalcite structure to obtain functional houghite, become one of focus of hydrotalcite research field.People such as Duan Xue in 2005 propose the patent application (number of patent application: 200510012245.7 of " having rare earth compounding intercalated houghite of fluorescent characteristic and preparation method thereof "; Publication number: CN1715365A), tie up to hydrotalcite layers and introduce the ammonia carboxylic title complex of rare earth ion such as Eu by ion-exchange to obtain the epipolic hydrotalcite of tool.In addition, L.Latterini etc. insert hydrotalcite layers with azo class and other dyestuff by ion-exchange, and acquisition has the hybrid material of light, electric work energy.
Summary of the invention:
The present invention relates to a class and have Zincium containing hydrotalcite of hyperfluorescence and preparation method thereof.
As everyone knows, has good thermostability, the oxine zinc (Znq of wide excitation band and high fluorescence efficiency
2) wait zinc coordination inner complex, fluorescence metal title complex as a class excellent combination property, be used for one of fluorescent material of luminous or display device by first-selection always, but it is difficult to problems such as big area film forming, cost height and is still its difficult problem of further using of puzzlement so far, and becomes the focus that the investigator pays close attention to.
Based on above research background, the present invention is with an amount of divalent zinc ion (Zn
2+) replace the divalence magnesium ion (Mg in the magnesium aluminum-hydrotalcite
2+), the parts such as oxine with metering are dissolved or dispersed in the lipophilicity negatively charged ion such as stearate radical of zinc-containing hydrotalcite interlayer simultaneously, make itself and the divalent zinc ion (Zn that is uniformly distributed on the metal hydroxides flaggy of hydrotalcite
2+) coordination, so, parts such as oxine because of with zine ion (Zn
2+) coordination and " suspension " on oxyhydroxide flaggy surface and each unit be fixed thereon by isolated, thereby assembling, a kind of special ligand complex structure that is different from zinc coordination inner complexs such as oxine zinc fully of formation, because this special construction has the bigger structural asymmetries of zinc coordination inner complex such as oxine zinc of specific ionization or " freedom ", thereby can improve the fluorescence efficiency of its luminescence center; In addition, because divalent zinc ion (Zn wherein
2+) be homodisperse, be fixed on the flaggy, thereby effectively prevent the possible quenching of fluorescence that each luminescence unit causes because of reunion; Simultaneously because the provide protection of such hydrotalcite layered structure improves its thermostability.Thereby obtain a class different and can send the novel high fluorescence Zincium containing hydrotalcite of corresponding zinc coordination inner complex intense fluorescence with common non-blooming magnesium aluminum-hydrotalcite or zinc-aluminium hydrotalcite.
Particular content of the present invention is as follows:
1. a class that the present invention relates to has the Zincium containing hydrotalcite (Zn-LLDHs) of hyperfluorescence, has following simplest formula: [M
2+ 1-x-yZn
2+ xAl
3+ y(OH)
-1 2] A
N- Y/nD
X/mZB],
M wherein
2+For removing zine ion (Zn
2+) in addition divalent metal such as magnesium, zinc, copper, nickel; Zn
2+Be divalent zinc ion (Zn
2+), x is Zn
2+/ (M
2++ Zn
2+) molar ratio; Al
3+Be trivalent aluminium ion, y=Al
3+/ (M
2++ Zn
2++ Al
3+) molar ratio, y=0.33 or 0.25; (OH)
-1Be monovalence hydroxide radical anion, A
N-Be negatively charged ion or mixed anion, its flat fare n=1～2; D is part or mixed ligand, its average coordination number m=2～3; B is the contained neutral molecule of houghite, and z is the neutral molecule number;
Zine ion (Zn wherein
2+) be scattered in the non-zinc layers of metal hydroxides plate of this houghite; A
N-Be interlayer anion; Part D is molten to be mixed in interlayer anion A
N-Among, and with laminate on Zn
2+Coordination.
2. the Zincium containing hydrotalcite (Zn-LLDHs) with hyperfluorescence of the present invention, its simplest formula
[M
2+ 1-x-yZn
2+ xAl
3+ y(OH)
-1 2] A
N- Y/nD
X/mZB] in Zn
2+Content x=0.5～0.005.
3. the Zincium containing hydrotalcite (Zn-LLDHs) with hyperfluorescence of the present invention, its [M
2+ 1-x-yZn
2+ xAl
3+ y(OH)
-1 2] A
N- Y/nD
X/mZB] in part D be oxine, 3,5 Dibromosalicylaldehydes contract 8 quinolylamines and 5 or 2 substitutive derivatives thereof; Methyl ethyl diketone (acac) and diphenylpropane-1,3-dione(DPPO) (DBM) beta-diketon class; Schiff's base, two Schiff's base and substitutive derivative thereof; Phenanthroline; Dipyridyl; Quercetin ((3,5,7,3 ', 4 '-pentahydroxyflavone, Quercetin) grade or its mixture.
4. the Zincium containing hydrotalcite (Zn-LLDHs) with hyperfluorescence of the present invention, wherein part D is the molten in advance C of being mixed in
12-20Sodium soap, C
12-20Fat sodium sulfonate, C
0-12Alkylbenzoic acid sodium, C
0-12In sodium alkyl benzene sulfonate, sodium salicylate or its mixture, mix in interlayer anion A thereby part D is molten in (Zn-LLDHs) that prepare by coprecipitation method
N-Among, simultaneously with the non-zinc layers of metal hydroxides of the divalence that is scattered in houghite plate on Zn
2+Coordination.
5. the Zincium containing hydrotalcite (Zn-LLDHs) with hyperfluorescence of the present invention, its [M
2+ 1-x-yZn
2+ xAl
3+ y(OH)
-1 2] A
N- Y/nD
X/mZB] in molten mixing in interlayer anion, as C
12-20Sodium soap, C
12-20Part D content in fat sodium sulfonate, Sodium Benzoate, benzene sulfonic acid sodium salt, sodium salicylate or its mixture is zine ion (Zn wherein
2+) molar content x 1/2nd to 1/3rd.
6. as mentioned above, be reduced to the zinc ion content (x) in the oxyhydroxide flaggy in the houghite a certain amount of, simultaneously part such as an amount of oxine or molten the mixing of its mixed ligand are scattered in the lipophilicity negatively charged ion of hydrotalcite or houghite interlayer, and with the zine ion (Zn that disperses to be embedded on the oxyhydroxide flaggy
2+) coordination, both prevented zine ion (Zn as luminescence center
2+) possible fluorescence essence go out and molten oxine part in interlayer anion or its mixed ligand and the divalent zinc ion (Zn that is embedded on the oxyhydroxide flaggy of mixing
2+) the specific group assembling structure that forms of coordination improved the coordination zine ion (Zn as luminescence center
2+) asymmetry, thereby obtain the novel high fluorescence Zincium containing hydrotalcite that a class different with common non-blooming zinc-containing hydrotalcite can be sent corresponding zinc coordination inner complex intense fluorescence.
7. has simplest formula [M
2+ 1-x-yZn
2+ xAl
3+ y(OH)
-1 2] A
N- Y/nD
X/mZB] the Zincium containing hydrotalcite (Zn-LLDHs) of hyperfluorescence, be to implement preparation by coprecipitation method.The concrete basic step that coprecipitation method preparation method takes is: prepare the aqueous solution (A) that the solubility that contains xmol contains zinc salt and an amount of NaOH; Preparation contains the aqueous solution (B) of (1-x) mol solubility magnesium salts; Preparation contains the lipophilicity organic acid sodium of (x/n) mol, the part of (x/m) mol or the aqueous solution (C) of mixed ligand.In violent stirring, or ultrasonic wave, or under the microwave action, dropwise add (C) solution with solution (A) and (B) simultaneously, the aqueous sodium hydroxide solution conditioned reaction mixed serum of using proper concn is to PH=9～13, in 60～80 ℃ of following ageings 6～12 hours, suction filtration, water washing filter Pie are to filtering PH=7 at night～8, suction filtration behind the throw out, filter Pie was dried 2 hours down in 100～110 ℃, obtained the Zincium containing hydrotalcite (Zn-LLDHs) of hyperfluorescence.
Embodiment:
Below Zincium containing hydrotalcite of high fluorescence of the present invention and preparation method thereof is described further, will helps understanding the present invention and advantage thereof with indefiniteness embodiment, and not as a limitation of the invention,
Embodiment 1.
Preparation contains 1.67 * 10
-3The NaAlO of mol
2With 0.835 * 10
-3The mol molNaOH aqueous solution (A); Preparation contains 5.01 * 10
-5The ZnCl of mol
2With 4.96 * 10
-3The MgCl of mol
2The aqueous solution (B); Preparation contains 5.0 * 10
-3Mol 16 carbon fatty acid sodium, 0.25 * 10
-5The alcohol-water mixing solutions (C) of mol oxine.Under the ultrasonic wave effect, simultaneously with solution (A) with (B) dropwise add (C) solution, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to PH=12, in 80 ℃ of following ageings 12 hours, suction filtration, water washing filter Pie are to filtering PH=7 at night～8, with suction filtration behind a small amount of soaked in absolute ethyl alcohol, the washing precipitate, filter Pie was dried 2 hours down in 105 ± 5 ℃, obtained the Zincium containing hydrotalcite sample (Zn-LLDH of hyperfluorescence
S).With ultraviolet excitation, send oxine zinc strong feature blue-greenish colour fluorescence (502nm), fluorescence intensity reaches 4.7 * 10
4(a.u.).
Embodiment 2.
Preparation contains 1.67 * 10
-3The NaAlO of mol
2With 0.835 * 10
-3The mol molNaOH aqueous solution (A); Preparation contains 2.5 * 10
-3The ZnCl of mol
2With 2.5 * 10
-3The MgCl of mol
2The aqueous solution (B); Preparation contains 1.67 * 10
-3Mol Sodium dodecylbenzene sulfonate, 0.25 * 10
-5The alcohol-water mixing solutions (C) of mol oxine.Under the ultrasonic wave effect, simultaneously with solution (A) with (B) dropwise add (C) solution, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to PH=12, in 80 ℃ of following ageings 12 hours, suction filtration, water washing filter Pie are to filtering PH=7 at night～8, with suction filtration behind a small amount of soaked in absolute ethyl alcohol, the washing precipitate, filter Pie was dried 2 hours down in 105 ± 5 ℃, obtained the Zincium containing hydrotalcite sample (Zn-LLDH of hyperfluorescence
S).With ultraviolet excitation, send oxine zinc feature blue-greenish colour fluorescence (502nm), fluorescence intensity reaches 0.5 * 10
3(a.u.).
Embodiment 3.
Preparation contains 1.67 * 10
-3The NaAlO of mol
2With 0.835 * 10
-3The mol molNaOH aqueous solution (A); Preparation contains 2.5 * 10
-5The ZnCl of mol
2With 5.0 * 10
-3The MgCl of mol
2The aqueous solution (B); Preparation contains 5.0 * 10
-3Mol sodium stearate, 0.125 * 10
-5The alcohol-water mixing solutions (C) of mol oxine.Under violent stirring, simultaneously with solution (A) with (B) dropwise add (C) solution, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to PH=12, in 80 ℃ of following ageings 12 hours, suction filtration, water washing filter Pie are to filtering PH=7 at night～8, with suction filtration behind a small amount of soaked in absolute ethyl alcohol, the washing precipitate, filter Pie was dried 2 hours down in 105 ± 5 ℃, obtained the Zincium containing hydrotalcite sample (Zn-LLDH of hyperfluorescence
S).With ultraviolet excitation, send oxine zinc strong feature blue-greenish colour fluorescence (502nm), fluorescence intensity reaches 3.9 * 10
5(a.u.).
Embodiment 4.
Preparation contains 1.67 * 10
-3The NaAlO of mol
2With 0.835 * 10
-3The mol molNaOH aqueous solution (A); Preparation contains 2.5 * 10
-5The ZnCl of mol
2With 5.0 * 10
-3The MgCl of mol
2The aqueous solution (B); Preparation contains 5.0 * 10
-3Mol sodium stearate, 0.125 * 10
-5Mol 3,5 dichloro-salicylaldehydes 8 quinolylamines ((DCSAQ)) the alcohol-water mixing solutionss (C) that contract.Under violent stirring, simultaneously with solution (A) with (B) dropwise add (C) solution, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to PH=12, in 80 ℃ of following ageings 12 hours, suction filtration, water washing filter Pie are to filtering PH=7 at night～8, with suction filtration behind a small amount of soaked in absolute ethyl alcohol, the washing precipitate, filter Pie was dried 2 hours down in 105 ± 5 ℃, obtained the Zincium containing hydrotalcite sample (Zn-LLDH of hyperfluorescence
S).With ultraviolet excitation, send oxine zinc strong feature blue-greenish colour fluorescence (508nm), fluorescence intensity reaches 7.2 * 10
5(a.u.).
Embodiment 5.
Preparation contains 1.67 * 10
-3The NaAlO of mol
2With 0.835 * 10
-3The mol molNaOH aqueous solution (A); Preparation contains 2.5 * 10
-5The ZnCl of mol
2With 5.0 * 10
-3The MgCl of mol
2The aqueous solution (B); Preparation contains 5.0 * 10
-3Mol sodium stearate, 0.125 * 10
-5Mol oxine-p-methyl phenol alcohol-water mixing solutions (C).Under the ultrasonic wave effect, simultaneously with solution (A) with (B) dropwise add (C) solution, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to PH=12, in 80 ℃ of following ageings 12 hours, suction filtration, water washing filter Pie are to filtering PH=7 at night～8, with suction filtration behind a small amount of soaked in absolute ethyl alcohol, the washing precipitate, filter Pie was dried 2 hours down in 105 ± 5 ℃, obtained the Zincium containing hydrotalcite sample (Zn-LLDH of hyperfluorescence
S).With ultraviolet excitation, send oxine zinc strong feature blue-greenish colour fluorescence (507-513nm), fluorescence intensity reaches 1.2 * 10
5(a.u.).
Embodiment 6.
Preparation contains 1.67 * 10
-3The NaAlO of mol
2With 0.835 * 10
-3The mol molNaOH aqueous solution (A); Preparation contains 2.5 * 10
-5The ZnCl of mol
2With 5.0 * 10
-3The MgCl of mol
2The aqueous solution (B); Preparation contains 5.0 * 10
-3Mol 12 carbon fatty acid sodium, 0.125 * 10
-5Mol six sulphur phenanthroline alcohol-water mixing solutionss (C).Under the ultrasonic wave effect, simultaneously with solution (A) with (B) dropwise add (C) solution, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to PH=12, in 80 ℃ of following ageings 12 hours, suction filtration, water washing filter Pie are to filtering PH=7 at night～8, with suction filtration behind a small amount of soaked in absolute ethyl alcohol, the washing precipitate, filter Pie was dried 2 hours down in 105 ± 5 ℃, obtained the Zincium containing hydrotalcite sample (Zn-LLDH of hyperfluorescence
S).With the 275nm ultraviolet excitation, send oxine zinc strong feature blue-fluorescence (470nm), fluorescence intensity reaches 5.8 * 10
4(a.u.).
Embodiment 7.
Preparation contains 1.67 * 10
-3The NaAlO of mol
2With 0.835 * 10
-3The mol molNaOH aqueous solution (A); Preparation contains 2.5 * 10
-5The ZnCl of mol
2With 5.0 * 10
-3The MgCl of mol
2The aqueous solution (B); Preparation contains 5.0 * 10
-3Mol 12 carbon benzene sulfonic acid sodium salts, 0.125 * 10
-5The mol Quercetin ((3,5,7,3 ' 4 '-pentahydroxyflavone) alcohol-water mixing solutions (C).Under the ultrasonic wave effect, simultaneously with solution (A) with (B) dropwise add (C) solution, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to PH=12, in 80 ℃ of following ageings 12 hours, suction filtration, water washing filter Pie are to filtering PH=7 at night～8, with suction filtration behind a small amount of soaked in absolute ethyl alcohol, the washing precipitate, filter Pie was dried 2 hours down in 105 ± 5 ℃, obtained the Zincium containing hydrotalcite sample (Zn-LLDH of hyperfluorescence
S).With the 275nm ultraviolet excitation, send oxine zinc strong feature blue-fluorescence (470nm), fluorescence intensity reaches 8.1 * 10
3(a.u.).
Claims (7)
1. a class has Zincium containing hydrotalcite of hyperfluorescence and preparation method thereof, it is characterized in that the Zincium containing hydrotalcite of high fluorescence of the present invention has following simplest formula:
[M
2+ 1-x-yZn
2+ xAl
3+ yOH)
-1 2]A
n- y/n?D
x/mzB]，
M wherein
2+For removing zine ion (Zn
2+) in addition divalent metal such as magnesium, zinc, copper, nickel; Zn
2+Be divalent zinc ion, x is Zn
2+/ (M
2++ Zn
2+) molar ratio; Al
3+Be trivalent aluminium ion, y=Al
3+/ (M
2++ Zn
2++ Al
3+) molar ratio, y=0.33 or 0.25; (OH)
-1Be monovalence hydroxide radical anion, A
N-Be negatively charged ion or mixed anion, its flat fare n=1～2; D is part or mixed ligand, its average coordination number m=2～3; B is the contained neutral molecule of houghite, and z is the neutral molecule number;
Wherein zine ion is scattered in the non-zinc layers of metal hydroxides plate of this houghite; A
N-Be interlayer anion; Part D is molten to be mixed in interlayer anion A
N-Among, and with laminate on Zn
2+Coordination.
2. by described Zincium containing hydrotalcite of claim 1 and preparation method thereof, it is characterized in that Zn wherein with hyperfluorescence
2+Content x=0.5～0.005.
3. by described Zincium containing hydrotalcite of claim 1 and preparation method thereof, it is characterized in that its [M with hyperfluorescence
2+ 1-x-yZn
2+ xAl
3+ y(OH)
-1 2] A
N- Y/nD
X/mZB] in part D be oxine, 3,5 Dibromosalicylaldehydes contract 8 quinolylamines and 5 or 2 substitutive derivatives thereof; Beta-diketon such as methyl ethyl diketone and diphenylpropane-1,3-dione(DPPO) class; Schiff's base, two Schiff's base and substitutive derivative thereof; Phenanthroline; Dipyridyl; Quercetin or its mixture.
4. by described Zincium containing hydrotalcite of claim 1 and preparation method thereof, it is characterized in that wherein part D is the molten in advance C of being mixed in hyperfluorescence
12-20Sodium soap, C
12-20Fat sodium sulfonate, C
0-12Alkylbenzoic acid sodium, C
0-12In sodium alkyl benzene sulfonate, sodium salicylate or its mixture, mix in interlayer anion A thereby part D is molten in the Zincium containing hydrotalcite for preparing by coprecipitation method
N-Among, simultaneously with the non-zinc layers of metal hydroxides of the divalence that is scattered in houghite plate on Zn
2+Coordination.
5. by described Zincium containing hydrotalcite of claim 1 and preparation method thereof, it is characterized in that its [M with hyperfluorescence
2+ 1-x-yZn
2+ xAl
3+ y(OH)
-1 2] A
N- Y/nD
X/mZB] in molten mixing in interlayer C
12-20Sodium soap, C
12-20Part D content in fat sodium sulfonate, Sodium Benzoate, benzene sulfonic acid sodium salt, sodium salicylate or its mixture negatively charged ion is zine ion (Zn wherein
2+) molar content x 1/2nd to 1/3rd.
6. by described Zincium containing hydrotalcite of claim 1 and preparation method thereof, it is characterized in that because the zine ion (Zn in its oxyhydroxide flaggy with hyperfluorescence
2+) content (x) be reduced to a certain amount of and with molten part or its mixture coordination that mixes in (Zn-LLDHs) interlayer lipophilicity negatively charged ion, both prevented divalent zinc ion (Zn
2+) fluorescence essence goes out, improved the asymmetry of luminescence center coordination zine ion again, and made (Zn-LLDHs) have hyperfluorescence.
7. a class has Zincium containing hydrotalcite of hyperfluorescence and preparation method thereof, it is characterized in that being to implement preparation by coprecipitation method.
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|---|---|---|---|---|
| CN101804358A (en) * | 2010-04-07 | 2010-08-18 | 山西大同大学 | Method for preparing metal complex and hydrotalcite composite material |
| CN101649198B (en) * | 2009-09-17 | 2012-10-31 | 北京化工大学 | Lucigen cation and brucite composite luminescence film and preparation method thereof |
| CN102796215A (en) * | 2012-08-09 | 2012-11-28 | 福建师范大学 | Preparation method of peeled-up yellow-light hydrotalcite like/polymer nanocomposite |
| CN103468244A (en) * | 2013-08-09 | 2013-12-25 | 山东农业大学 | Quinoline derivative intercalated hydrotalcite-like multicolor luminescent material and preparation method thereof |
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| CN106589219A (en) * | 2016-12-16 | 2017-04-26 | 咸阳师范学院 | Preparation method for fluorescent hydrotalcite/acrylic resin composite material |
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| CN101649198B (en) * | 2009-09-17 | 2012-10-31 | 北京化工大学 | Lucigen cation and brucite composite luminescence film and preparation method thereof |
| CN101804358A (en) * | 2010-04-07 | 2010-08-18 | 山西大同大学 | Method for preparing metal complex and hydrotalcite composite material |
| CN102796215A (en) * | 2012-08-09 | 2012-11-28 | 福建师范大学 | Preparation method of peeled-up yellow-light hydrotalcite like/polymer nanocomposite |
| CN103468244A (en) * | 2013-08-09 | 2013-12-25 | 山东农业大学 | Quinoline derivative intercalated hydrotalcite-like multicolor luminescent material and preparation method thereof |
| CN104130773A (en) * | 2014-08-25 | 2014-11-05 | 桂林理工大学 | Phosphor Zn2(hfoac)4(4, 4-pybi)2and its synthesis method |
| CN104130773B (en) * | 2014-08-25 | 2016-06-29 | 桂林理工大学 | Fluorescent material Zn2(hfoac)4(4,4-pybi)2And synthetic method |
| CN104449691A (en) * | 2014-10-21 | 2015-03-25 | 淄博职业学院 | Polyvinyl carbazole intercalated hydrotalcite fluorescent film and preparation method thereof |
| CN106589219A (en) * | 2016-12-16 | 2017-04-26 | 咸阳师范学院 | Preparation method for fluorescent hydrotalcite/acrylic resin composite material |
| CN107129597A (en) * | 2017-03-21 | 2017-09-05 | 北京化工大学 | A kind of uvioresistant composite of hydrotalcite confinement synthesis Schiff base molecule, preparation method and application |
| CN113736091A (en) * | 2021-09-06 | 2021-12-03 | 上海工程技术大学 | Method for detecting quercetin by using fluorescent micrometer probe and application |
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