CN101649198B - Lucigen cation and brucite composite luminescence film and preparation method thereof - Google Patents
Lucigen cation and brucite composite luminescence film and preparation method thereof Download PDFInfo
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- CN101649198B CN101649198B CN200910092536XA CN200910092536A CN101649198B CN 101649198 B CN101649198 B CN 101649198B CN 200910092536X A CN200910092536X A CN 200910092536XA CN 200910092536 A CN200910092536 A CN 200910092536A CN 101649198 B CN101649198 B CN 101649198B
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- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000001768 cations Chemical class 0.000 title claims abstract description 9
- 238000004020 luminiscence type Methods 0.000 title abstract description 7
- 229910052599 brucite Inorganic materials 0.000 title abstract 7
- 239000000243 solution Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 17
- 150000001450 anions Chemical class 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 46
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 46
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 44
- KNJDBYZZKAZQNG-UHFFFAOYSA-N lucigenin Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.C12=CC=CC=C2[N+](C)=C(C=CC=C2)C2=C1C1=C(C=CC=C2)C2=[N+](C)C2=CC=CC=C12 KNJDBYZZKAZQNG-UHFFFAOYSA-N 0.000 claims description 36
- 150000002500 ions Chemical class 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 28
- 239000010408 film Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000010410 layer Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000005357 flat glass Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 229940001516 sodium nitrate Drugs 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 230000000712 assembly Effects 0.000 abstract 1
- 238000000429 assembly Methods 0.000 abstract 1
- 239000000084 colloidal system Substances 0.000 abstract 1
- 239000002356 single layer Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 3
- 229910001051 Magnalium Inorganic materials 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- -1 hydrotalcite compound Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- GXYLXFITCXXCQV-UHFFFAOYSA-N 10-methylacridin-10-ium Chemical group C1=CC=C2[N+](C)=C(C=CC=C3)C3=CC2=C1 GXYLXFITCXXCQV-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
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Abstract
The invention discloses a lucigen cation and brucite composite luminescence composite green-light luminescence material and a preparation method thereof, belonging to the field of inorganic and organic composite luminescence materials. The preparation method briefly comprises the following steps: preparing lucigen cation and polymer anion mixed solution according to certain proportions; preparing brucite colloid solution stripped by formamide solvent; and using a substrate after hydrophilic treatment to carry out a plurality of alternating assemblies in two solutions to obtain the lucigen cation and brucite multilayer composite film. The invention breaks down the wrong region that brucite nanometer sheets can only be assembled or compounded with anions, realizes the sequential assembly of cation functional molecules and the brucite nanometer sheets for the first time, and broadens the application field of brucite materials. The invention has the advantages that the preparation processes of the film are simple, the operability is strong, the film luminescence strength can be controlled by changing assembling times, and the thickness of the single-layer film is in nanometer magnitude order.
Description
Technical field
The invention belongs to inorganic organic composite luminescent material field, a kind of lucigenin positively charged ion and hydrotalcite nano piece compound green light-emitting film material and preparation method thereof particularly are provided.
Background technology
The bimetal complex hydroxide is called hydrotalcite (Layered Double Hydroxides again; Be abbreviated as LDHs) be a kind of multi-functional anionic type laminated material; It is adjustable that it has the laminate metallic element; Multiple characteristics such as interlayer ion is commutative, through rational design, the researchist uses the whole bag of tricks hundreds of negatively charged ion with functional performance to be incorporated into hydrotalcite layers; Formed anionic intercalation configuration material, be with a wide range of applications in the storage and the multiple fields such as release, photoelectricity conversion of catalysis, medicine with different performance.Yet because hydrotalcite laminate itself is positively charged, determined it to assemble with negatively charged ion, and the assembling of hydrotalcite and cationic molecule does not also have report so far, this has greatly limited the development of hydrotalcite stratified material.
Very big characteristics of hydrotalcite material are can be in organic solvent to peel off into the individual layer nanometer sheet of high dispersing through mechanical stirring or under influence of surfactant; Through the method for static assembling, can the polymer anion of hydrotalcite laminate of peeling off and difference in functionality characteristic be assembled the thin-film material that becomes ordered arrangement.
Characteristics such as lucigenin is one type of photovaltaic material that has application prospect, and its photoelectric activity component is a N-methylacridine cationoid, has fluorescence quantum efficiency high, and electrochemical activity is strong are widely used in the chemoluminescence field at present.This compounds is assembled into thin-film material, can be its further functionalization and device realized and pave the way.
Summary of the invention
The object of the present invention is to provide a kind of lucigenin positively charged ion, promptly two-(N-methylacridine) with hydrotalcite compound green luminescence ultrathin membrane and preparation method thereof.The present invention is applied to hydrotalcite and the lucigenin assembling with photoelectric functional characteristic as a kind of type material, for hydrotalcite material and cationic assembling provide feasible scheme.
Technical scheme of the present invention is that the lucigenin positively charged ion and the polymer anion that have positive charge are formed mixing solutions with certain proportion; Can make the lucigenin cation-adsorption in the polymer anion surface through electrostatic force; Form the pair ion of positively charged ion and polyanion; This pair ion has cationic functional performance, and net charge still is a negative charge simultaneously; This pair ion and the hydrotalcite nano piece of in organic solvent, peeling off are replaced assembling, form structurally ordered lucigenin and hydrotalcite compound ultrathin membrane material, realized photoelectric functional positively charged ion aligning and homodisperse on molecular scale.
The preparation process of lucigenin positively charged ion of the present invention and hydrotalcite composite light-emitting film is following:
1. interlayer is the preparation of the hydrotalcite precursor of nitrate radical:
Ion exchange method:
A. obtain solution A is with solubility divalent metal M
2+With solubility trivalent metal cation M
3+Nitrate soln, press M
2+With M
3+Mol ratio be that 2-4 mixes, M wherein
2+Concentration be 0.1-1M, M
2+Be selected from Mg
2+, Co
2+, Ni
2+, Ca
2+, Cu
2+, Fe
2+And Mn
2+In a kind of, M
3+Be selected from Al
3+, Cr
3+, Ga
3+, In
3+, Co
3+, Fe
3+And V
3+In a kind of;
B. prepare urea soln, the mole number of urea is M in the solution A of step a preparation
2+And M
3+The mole summation 3-5 doubly;
C. solution A and urea soln were reacted 12-36 hour under 100-150 ℃ of condition in the pressure reacting container of polytetrafluoroethylsubstrate substrate, adopt de-ionized hot water centrifuge washing to neutral, 50-100 ℃ dry 12-24 hour, obtain the carbonate intercalated houghite;
D. be 200 with mass ratio: 1-500: 1 SODIUMNITRATE and carbonate intercalated houghite carried out the normal temperature ion exchange reaction 12-24 hour under nitrogen protection, adopted and removed CO
2De-ionized hot water centrifuge washing to neutral, 50-100 ℃ dry 12-24 hour, obtain the nitrate radical intercalated houghite;
Coprecipitation method:
A. obtain solution A is with solubility divalent metal M
2+With solubility trivalent metal cation M
3+Nitrate soln, press M
2+With M
3+Mol ratio be that 2-4 mixes, M wherein
2+Concentration be 0.1-1M, M
2+Be selected from Mg
2+, Co
2+, Ni
2+, Ca
2+, Cu
2+, Fe
2+And Mn
2+In a kind of, M
3+Be selected from Al
3+, Cr
3+, Ga
3+, In
3+, Co
3+, Fe
3+And V
3+In a kind of;
B. prepare NaOH or KOH solution, the mole number of NaOH or KOH is M among the step a
2+And M
3+The mole summation 2-2.5 doubly;
C. the nitrate mixed solution with step a preparation slowly is added drop-wise under the condition of nitrogen protection in the alkali lye of step b preparation, stirs, the NaOH that utilizes 1-5mol/L with the pH value range regulation of slurries to 7-10,60 ℃-70 ℃ crystallization 12-24 hour, adopt except that CO
2De-ionized hot water centrifuge washing to neutral, 50-100 ℃ dry 12-24 hour, obtain the nitrate radical intercalated houghite;
With the nitrate radical intercalated houghite with 1: 3000-1: the mass volume ratio of 500 (g/ml) is scattered in peels off 12-36 hour in the formamide solvent; Stirring velocity is 3000-5000 rev/min; Hydrotalcite solution centrifugal with after peeling off discards throw out, obtains clear colloidal solution B;
3. prepare the blend solution C of lucigenin and polymer anion P, wherein the concentration range of lucigenin is 100 μ mol/L-0.05mol/L, and the total mole number of the monomeric unit of polymer anion is 5-20 a times of lucigenin mole number;
4. will use dense H
2SO
4Soaked 30-50 minute; And quartz plate, silicon chip, sheet mica or sheet glass after fully cleaning with deionized water soaked in solution B 10-20 minute; After fully cleaning with deionized water; Place in the solution C, soaked 10-20 minute and fully cleaning, obtain round-robin lucigenin positively charged ion and hydrotalcite composite light-emitting film;
5. repeating step 4, obtain the lucigenin positively charged ion and the hydrotalcite composite light-emitting film of multilayer assembling.
The described polymer anion P of step 3 is polyvinyl sulfonic acid root or polystyrolsulfon acid root negatively charged ion.
The invention has the advantages that: utilize the space confinement effect of hydrotalcite stratified material and the interaction between the Subjective and Objective; Realized of the orderly assembling of photoelectric activity positively charged ion gloss essence with hydrotalcite nano piece; The immobilization and the filmization of lucigenin molecule have been realized; The existence of polymer anion simultaneously makes lucigenin at the hydrotalcite layers homodisperse, has reduced effectively owing to the fluorescent quenching phenomenon that causes is assembled in the too high generation of lucigenin partial concn.
Description of drawings
Fig. 1 is that the assembling number of plies that the embodiment of the invention 1 obtains is 4 to 32 layers the lucigenin positively charged ion and the uv absorption spectra of hydrotalcite composite light-emitting film, tests for whenever carrying out a UV spectrum at a distance from 4 layers among the figure.
Fig. 2 is the changing conditions that 265 and 371 nanometers absorbancys increase with the assembling number of plies among Fig. 1.
Fig. 3 is that the lucigenin positively charged ion that obtains of the embodiment of the invention 2 and the hydrotalcite composite light-emitting film assembling number of plies are 16 layers fluorescence emission spectrogram.
Embodiment
Embodiment 1:
1. be the hydrotalcite precursor of nitrate radical between the ion exchange method prepared layer:
A. with the solid Mg (NO of 0.010mol
3)
26H
2Solid Al (the NO of O and 0.005mol
3)
39H
2O and 0.06mol urea are dissolved in the deionized water of 70mL, and in 90 milliliters tetrafluoroethylene pressure reacting container, crystallization is 24 hours under 100 ℃ of conditions, are about 7,70 ℃ of dry 12h with the deionized water centrifuge washing to pH, obtain the carbonate hydrotalcite;
B. get above-mentioned carbonate hydrotalcite 0.3g and solid NaNO
3Remove CO 63.75g be dissolved in 300mL
2Deionized water in, behind the homodisperse, add behind the 0.07mL concentrated nitric acid at 25 ℃, stir under the nitrogen atmosphere condition, carry out ion exchange reaction after 12 hours with removing CO
2De-ionized hot water centrifuge washing be about 7,70 ℃ of dry 18h to pH, obtain magnalium type nitrate radical intercalated hydrotalcite composite material;
2. get the above-mentioned nitrate radical intercalated houghite of 0.1g, under the nitrogen atmosphere condition, stirred 24 hours in 100 milliliters of formamide solvent, stirring velocity is 4000 rev/mins, and the hydrotalcite solution centrifugal with after peeling off discards throw out, obtains clear colloidal solution A;
3. prepare the lucigenin of 500 μ mol/L and the anionic blend solution C of polyvinyl sulfonic acid root of 0.075g/L;
4. will use dense H
2SO
4Soaked 35 minutes; And the quartz plate after fully cleaning with deionized water soaked in solution A 15 minutes, after fully cleaning with deionized water, placed in the solution B; Soaked 15 minutes and fully clean, obtain round-robin lucigenin positively charged ion and hydrotalcite composite light-emitting film;
5. repeating step 4, obtain the lucigenin positively charged ion and the hydrotalcite composite light-emitting film of multilayer assembling.
Film is characterized: can know by Fig. 1; Lucigenin positively charged ion and hydrotalcite composite light-emitting film are along with the increase of the assembling number of plies; The maximum absorption band of its uv absorption spectrum presents continuous rising tendency; As shown in Figure 2, the absorbancy and the assembling number of plies are near linear relationship, and the lucigenin amount that shows each assembling is a fixed value.
Embodiment 2:
1. coprecipitation method prepares nitrate radical hydrotalcite precursor:
A. with the solid Mg (NO of 0.03mol
3)
26H
2Solid Al (the NO of O and 0.01mol
3)
39H
2O is dissolved in 50mL and removes CO
2Deionized water in;
B. 0.06mol NaOH is dissolved in 50mL and removes CO
2Deionized water in;
C. the alkaline solution with step b preparation places four-hole bottle, at N
2Under the condition of gas shiled, on one side vigorous stirring, the salts solution with step a preparation slowly drips in the four-hole bottle on one side, and about 0.5h drips off, and after being added dropwise to complete, with the NaOH solution of 5mol/L its pH value is adjusted to 8,60 ℃ of water-bath 24h, uses except that CO
2De-ionized hot water centrifuge washing be about 7,70 ℃ of dry 24h to pH, obtain magnalium type nitrate radical intercalated hydrotalcite composite material;
2. get the above-mentioned nitrate radical intercalated houghite of 0.1g and in 100 milliliters of formamide solvent, stirred 24 hours, stirring velocity is 3000 rev/mins, and the hydrotalcite solution centrifugal with after peeling off discards throw out, obtains clear colloidal solution A;
3. prepare the lucigenin of 1000 μ mol/L and the anionic blend solution C of polyvinyl sulfonic acid root of 0.15g/L;
4. will use dense H
2SO
4Soaked 45 minutes; And the quartz plate after fully cleaning with deionized water soaked in solution A 10 minutes, after fully cleaning with deionized water, placed in the solution B; Soaked 10 minutes and fully clean, obtain round-robin lucigenin positively charged ion and hydrotalcite composite light-emitting film;
5. repeating step 4, obtain the lucigenin positively charged ion and the hydrotalcite composite light-emitting film of multilayer assembling.
To the assembling number of plies is that 16 layers film characterizes: being characterized by the fluorescence emission spectrum of Fig. 3 and can know that the emission wavelength of lucigenin and the orderly component film of hydrotalcite laminate is 510 nanometers, is that green luminescence is regional.
Claims (2)
1. lucigenin positively charged ion and hydrotalcite composite light-emitting film; It is characterized in that; Said thin-film material is a green light-emitting film, pair ion that it is formed by photoelectric activity material lucigenin and polyvinyl sulfonic acid root or polystyrolsulfon acid root negatively charged ion and inorganic component hydrotalcite nano piece three-dimensional space layer by layer alternately assembling form, have tangible laminate structure characteristic; According to the difference of the assembling number of plies, film thickness can be in several nanometers to evenly regulation and control between the hundreds of nanometer simultaneously.
2. the preparation method of lucigenin positively charged ion and hydrotalcite composite light-emitting film is characterized in that its concrete operations step is following:
1) interlayer is the preparation of the hydrotalcite precursor of nitrate radical:
Ion exchange method:
A. obtain solution A is with solubility divalent metal M
2+With solubility trivalent metal cation M
3+Nitrate soln, press M
2+With M
3+Mol ratio be that 2-4 mixes, M wherein
2+Concentration be 0.1-1M;
B. prepare urea soln, the mole number of urea is M in the solution A
2+And M
3+The mole summation 3-5 doubly;
C. solution A and urea soln were reacted 12-36 hour under 100-150 ℃ of condition in the pressure reacting container of polytetrafluoroethylsubstrate substrate, adopt de-ionized hot water centrifuge washing to neutral, 50-100 ℃ dry 12-24 hour, obtain the carbonate intercalated houghite;
D. be 200 with mass ratio: 1-500: 1 SODIUMNITRATE and carbonate hydrotalcite carried out the normal temperature ion exchange reaction 12-24 hour under nitrogen protection, adopted and removed CO
2De-ionized hot water centrifuge washing to neutral, 50-100 ℃ dry 12-24 hour, obtain the nitrate radical intercalated houghite;
Coprecipitation method:
A. obtain solution A is with solubility divalent metal M
2+With solubility trivalent metal cation M
3+Nitrate soln, press M
2+With M
3+Mol ratio be that 2-4 mixes, M wherein
2+Concentration be 0.1-1M;
B. prepare NaOH or KOH solution, the mole number of NaOH or KOH is M among the step a
2+And M
3+The mole summation 2-2.5 doubly;
C. with the nitrate mixed solution of step a preparation at N
2Slowly be added drop-wise under the condition of protection in the alkali lye of step b preparation, stir, the NaOH that utilizes 1-5mol/L with the pH value range regulation of slurries to 7-10,60 ℃-70 ℃ crystallization 12-24 hour, adopt except that CO
2De-ionized hot water centrifuge washing to neutral, 50-100 ℃ dry 12-24 hour, obtain the nitrate radical intercalated houghite;
2) with the nitrate radical intercalated houghite with 1: the mass volume ratio of 3000-1: 500g/ml is scattered in peels off 12-36 hour in the formamide solvent; Stirring velocity is 3000-5000 rev/min; Hydrotalcite solution centrifugal with after peeling off discards throw out, obtains clear colloidal solution B;
3) the blend solution C of preparation lucigenin and polymer anion P, wherein the concentration range of lucigenin is 100 μ mol/L-0.05mol/L, the total mole number of the monomeric unit of polymer anion is 5-20 a times of lucigenin mole number;
4) will use dense H
2SO
4Soaked 30-50 minute; And quartz plate, silicon chip, sheet mica or sheet glass after fully cleaning with deionized water soaked in solution B 10-20 minute; After fully cleaning with deionized water; Place in the solution C, soaked 10-20 minute and fully cleaning, obtain round-robin lucigenin positively charged ion and hydrotalcite composite light-emitting film;
5) repeating step 4), obtain lucigenin positively charged ion and hydrotalcite composite light-emitting film that multilayer is assembled;
Described M
2+Be Mg
2+, Co
2+, Ni
2+, Ca
2+, Cu
2+, Fe
2+Or Mn
2+, M
3+Be Al
3+, Cr
3+, Ga
3+, In
3+, Co
3+, Fe
3+Or V
3+Described polymer anion P is polyvinyl sulfonic acid root or polystyrolsulfon acid root negatively charged ion.
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|---|---|---|---|
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| CN102504802A (en) * | 2011-10-08 | 2012-06-20 | 北京化工大学 | Metallic organic luminescent molecule and hydrotalcite compounded electrochemiluminiscent ultrathin film and method of preparing same |
| CN102660256B (en) * | 2012-05-08 | 2014-04-16 | 北京化工大学 | Polymer-coated di(8-hydroxyquinoline) zinc composition micelle-hydrotalcite composite light-emitting film and preparation method thereof |
| CN102942927A (en) * | 2012-11-19 | 2013-02-27 | 北京化工大学 | Rare earth polyacid, organic light active molecule and layered double hydroxides composite luminous thin film and preparation method thereof |
| CN104531132B (en) * | 2014-12-01 | 2017-01-11 | 中国地质大学（北京） | Lucigenin intercalation organic/inorganic composite material, and preparation method and application thereof |
| CN104449692B (en) * | 2014-12-01 | 2016-06-29 | 中国地质大学（北京） | As lucigenin smectite composite material that scalable is luminous and its preparation method and application |
| CN105085985B (en) * | 2015-07-31 | 2018-04-27 | 浙江华丰新材料股份有限公司 | A kind of preparation method of anion intercalated modified hydrotalcite, product and the application in PVC boardy products |
| CN107224587A (en) * | 2017-06-28 | 2017-10-03 | 福州大学 | A kind of protoporphyrin zinc-aluminum hydrotalcite compound and its preparation method and application |
| CN107541718B (en) * | 2017-09-01 | 2020-01-21 | 苏州云舒新材料科技有限公司 | Preparation method of hydrotalcite-based magneto-optical film material |
| CN112871128A (en) * | 2021-01-19 | 2021-06-01 | 广西师范大学 | Anion intercalated double-metal hydroxide adsorbent, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195741A (en) * | 2007-12-14 | 2008-06-11 | 福建师范大学 | Zincium containing hydrotalcite with strong fluoresce and method for producing the same |
| CN101497786A (en) * | 2009-03-02 | 2009-08-05 | 北京化工大学 | Sulfonated poly-biphenyl and hydrotalcite composite light-emitting film, and preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195741A (en) * | 2007-12-14 | 2008-06-11 | 福建师范大学 | Zincium containing hydrotalcite with strong fluoresce and method for producing the same |
| CN101497786A (en) * | 2009-03-02 | 2009-08-05 | 北京化工大学 | Sulfonated poly-biphenyl and hydrotalcite composite light-emitting film, and preparation thereof |
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