CN102127425B - 8-hydroxy-1,3,6-trisulfonyl pyrene anion/octanesulfonate anion co-intercalation hydrotalcite composite luminescent material - Google Patents
8-hydroxy-1,3,6-trisulfonyl pyrene anion/octanesulfonate anion co-intercalation hydrotalcite composite luminescent material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 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 title claims abstract description 21
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 21
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 21
- 238000009830 intercalation Methods 0.000 title abstract description 11
- -1 8-hydroxy-1,3,6-trisulfonyl pyrene anion Chemical class 0.000 title abstract 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 51
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 150000001768 cations Chemical class 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 75
- 150000002500 ions Chemical class 0.000 claims description 62
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 58
- 239000002253 acid Substances 0.000 claims description 37
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 29
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000012046 mixed solvent Substances 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- WGZOVUFEMSRDKB-UHFFFAOYSA-N [Na].[Na].[Na].C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C34 Chemical compound [Na].[Na].[Na].C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C34 WGZOVUFEMSRDKB-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000011229 interlayer Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 150000001457 metallic cations Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 3
- 238000010791 quenching Methods 0.000 abstract description 3
- 230000000171 quenching effect Effects 0.000 abstract description 3
- VHNQGGTVFCJSBF-UHFFFAOYSA-N 3,6,8-trisulfonylpyren-1-ol Chemical compound OC1=CC(C2=CC=C3C(CC(C4=CC=C1C2=C43)=S(=O)=O)=S(=O)=O)=S(=O)=O VHNQGGTVFCJSBF-UHFFFAOYSA-N 0.000 abstract 1
- 238000009825 accumulation Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- HRQDCDQDOPSGBR-UHFFFAOYSA-M sodium;octane-1-sulfonate Chemical compound [Na+].CCCCCCCCS([O-])(=O)=O HRQDCDQDOPSGBR-UHFFFAOYSA-M 0.000 abstract 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 abstract 1
- 230000002687 intercalation Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 230000005284 excitation Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses an 8-hydroxy-1,3,6-trisulfonyl pyrene anion/octanesulfonate anion co-intercalation hydrotalcite composite luminescent material and a preparation method thereof, belonging to the field of inorganic/organic composite luminescent materials. The method comprises the following steps: preparing a bivalent/trivalent metal cation solution A, and a solution B of trisodium salt of 8-hydroxy-1,3,6-trisulfonyl pyrene and sodium octanesulfonate; slowly and dropwisely adding a prepared NaOH solution into an A and B mixed solution; after finishing the dropwise adding, regulating the pH value to obtain slurry D; reacting the slurry D under hydrothermal conditions; and carrying out centrifugal washing on the obtained product, and carrying out vacuum drying. The method implements the immobilization of 8-hydroxy-1,3,6-trisulfonyl pyrene anions, effectively enhances the fluorescence efficiency of the luminescent dye molecules, and reduces the fluorescent quenching generated by the accumulation of the luminescent dye molecules.
Description
Technical field
The invention belongs to inorganic organic composite luminescent material preparing technical field, particularly a kind of 8-hydroxyl-1,3,6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion be intercalated hydrotalcite composite luminescent material and preparation method thereof altogether.
Background technology
Hydrotalcite intercalation material (LDHs) is the novel nano inorganic functional material that a class has laminate structure, and its similar is in brucite, and forming general formula can be expressed as: [M
2+ 1-xM
3+ x(OH)
2]
X+(A
N-)
X/nMH
2O, wherein M
2+And M
3+Be respectively the metallic cation of divalence and trivalent in the laminate, as: Mg
2+, Ni
2+, Co
2+, Zn
2+, Cu
2+And Al
3+, Cr
3+, Fe
3+, Sc
3+Deng; A
N-Interlayer anion, as: CO
3 2-, NO
3 -, Cl
-, OH
-, SO
4 2-, PO
4 3-, C
6H
4(COO)
2 2-Negatively charged ion etc.; X is M
3+/ (M
2++ M
3+) molar ratio, it is worth generally between 0.1～0.5; M is the number of middle water molecule.Metallic cation on the LDHs laminate evenly distributes on laminate in a certain way owing to be subjected to the impact of the minimum effect of lattice energy and lattice orientation effect thereof, so that on the laminate in each small structural unit, its chemical composition and structure is constant.Simultaneously, the divalent metal that is positioned on the laminate can be in the certain proportion scope by the close trivalent metal cation isomorphous substitution of ionic radius, the Modulatory character of this chemical constitution and the microscopic uniformity of structure, the good precursor material that makes it become composite structure and form uniform matrix material.
It is a kind of fluorescence molecule that is subject to extensive concern and research that 8-hydroxyl-1,3,6-trisulfonic acid base pyrene three are received salt, with 3 sulfonate radicals and a hydroxyl.It has been generally acknowledged that sulfonate radical ionization when the pH value is greater than 1, is 3 valency negatively charged ion; Hydroxyl ionization becomes the negatively charged ion of 4 valencys when the pH value is greater than 7.4.(ROH) its fluorescence emission peak was positioned at the 440nm place and belongs to blue emission when hydroxyl was unionized; And after hydroxyl ionization (RO
-) its fluorescence emission peak is positioned at the 510nm place and belongs to green emission.When ROH is excited rayed and (ROH*) its acid can greatly enhancing when transitting to excited state, very easily shift H this moment
+Give the acceptors such as water molecules in the solution, the excited state Proton-Transfer Reactions occurs, become RO
-* thereby the green glow that ground state is launched the 510nm place is returned in transition again.So 8-hydroxyl-1,3,6-trisulfonic acid base pyrene is an extremely special molecule, is not only to can be used as pH value sensor material because its luminous pH of being subjected to affects, its the luminous microenvironment impact that also is subject on every side can detect its microenvironment state on every side simultaneously.So it is in science, medical science, and the fields such as commerce have a wide range of applications.
But the dye class luminescent material easily forms aggregate under common solution state, is unfavorable for the High Efficiency Luminescence of dye molecule.If dye molecule is uniformly distributed in a kind of material of main part as object, then can improve to greatest extent the luminous efficiency of object.Therefore electronegative dye molecule is introduced the interlayer of stratified material hydrotalcite, formed organic-inorganic composition, can realize that dye molecule aligns and Uniform Dispersion at molecular scale, improves its fluorescence efficiency.
Summary of the invention
The purpose of this invention is to provide a kind of 8-hydroxyl-1,3,6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion are total to composite luminescent material of intercalated houghite and preparation method thereof.Perfluoroetane sulfonic acid root negatively charged ion inserts hydrotalcite layers and consists of the weak interlayer environment of a polarity, has played simultaneously dispersion 8-hydroxyl-1,3, and the gathering quenching phenomenon has been avoided in the effect of 6-trisulfonic acid base pyrene negatively charged ion, has improved fluorescence efficiency.
The 8-hydroxyl-1,3 of the present invention's preparation, 6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion altogether intercalated hydrotalcite composite luminescent material are a kind of anionic supramolecule stratiform composite luminescent materials, and its chemical formula is: [(M
2+)
1-x(M
3+)
x(OH)
2]
X+(A
1 A-)
y(A
2 B-)
zMH
2O, 0.2≤x≤0.33 wherein, 0.02x≤y≤0.1x, 0.7x≤z≤0.94x, and ya+zb=x, m=3～6 are interlayer crystal water molecule number, M
2+Represent divalent metal, M
3+Represent trivalent metal ion, A
1 A-Represent 8-hydroxyl-1,3,6-trisulfonic acid base pyrene negatively charged ion, a=3, A
2 B-Represent perfluoroetane sulfonic acid root negatively charged ion, b=1; The crystalline structure of this composite luminescent material is the crystalline structure of houghite material, and metallic cation and hydroxide ion consist of octahedra with covalent linkage, form sheet structure by common limit.
Preparation method's of the present invention concrete operation step is:
(1) preparation divalence, trivalent metal cation mol ratio M
2+/ M
3+Be 2: 1～4: 1 solution A, wherein divalent metal concentration is 0.01～1.6M; Solvent is the mixed solvent of water and ethanol, and the shared volume ratio of ethanol is 30%～50%;
(2) press 8-hydroxyl-1,3,6-trisulfonic acid base pyrene trisodium salt and perfluorooctane sulfonate mol ratio are 1: 32.6～1: 6.52 preparation mixing solutions B, and so that two kinds of electronegative sums of negatively charged ion equal M in the step (1)
3+The mole number of ion, it is 0.01～2.0M that two kinds of ions add up to volumetric molar concentration concentration; Solvent is selected the mixed solvent of water and ethanol, and the shared volume ratio of ethanol is 30%～50%;
(3) solution A and solution B are mixed to get solution C, then solution C are poured in the four-hole boiling flask;
(4) the preparation mole number is the M in the step (1)
2+, M
3+The NaOH solution that the metal ion total moles is 2～2.5 times, NaOH strength of solution are 0.01～3.0M, and solvent is selected the mixed solvent of water and ethanol, and the shared volume ratio of ethanol is 30%～50%; This NaOH solution by constant pressure funnel, is slowly dripped in the four-hole boiling flask that solution C is housed under the nitrogen protection condition;
(5) be added dropwise to complete and regulate pH value 4.0～9.0 with NaOH afterwards, obtain slurries D, place 50～80 ℃ of water-baths under the nitrogen protection condition, to react 12～24 hours four-hole boiling flask, or slurries D is transferred in the water heating kettle, 80～100 ℃ of lower reactions of temperature control 12～24 hours;
(6) reaction product in the step (5) is spent respectively CO
2Deionized water and alcohol mixed solution centrifuge washing 3～6 times, colourless to washings, the shared volume ratio of ethanol is 30%～50%; With the vacuum-drying 15～20 hours in 50～70 ℃ of temperature ranges of the centrifugal filter cake that obtains, namely obtain 8-hydroxyl-1,3,6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion be intercalated hydrotalcite composite luminescent material altogether.
Described M
2+Be Mg
2+, Ni
2+, Co
2+, Zn
2+Or Ca
2+, M
3+Be Al
3+Or Fe
3+
Beneficial effect of the present invention is: luminescent dye 8-hydroxyl-1,3,6-trisulfonic acid base pyrene negatively charged ion is introduced hydrotalcite layers, utilize the space confinement effect of hydrotalcite stratified material and the interaction between the Subjective and Objective, realize the immobilization of dye molecule, reduce simultaneously the fluorescent quenching that dye molecule produces because of gathering, provide the theoretical investigation basis for hydrotalcite being applied to solid dye luminescent device field.
Description of drawings
Fig. 1 is the 8-hydroxyl-1,3 that the embodiment of the invention 1 obtains, and 6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion be the XRD spectra of the composite luminescent material of intercalated houghite altogether.
Fig. 2 is the 8-hydroxyl-1,3 that the embodiment of the invention 2 obtains, and 6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion be the XRD spectra of the composite luminescent material of intercalated houghite altogether.
Fig. 3 is the 8-hydroxyl-1,3 that the embodiment of the invention 1 obtains, the fluorescence emission spectrogram that the composite luminescent material of the common intercalated houghite of 6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion is obtained by the 375nm ultraviolet excitation.
Fig. 4 is the 8-hydroxyl-1,3 that the embodiment of the invention 2 obtains, the fluorescence emission spectrogram that the composite luminescent material of the common intercalated houghite of 6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion is obtained by the 375nm ultraviolet excitation.
Embodiment
The present invention adopts coprecipitation method to obtain 8-hydroxyl-1,3, and 6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion be the composite luminescent material of intercalated houghite altogether.
Further explain the present invention below by specific embodiment.
Embodiment 1
1, takes by weighing 1.99g Zn (NO
3)
26H
2O and 0.94g Al (NO
3)
39H
2O is dissolved in 100ml and removes CO
2Deionized water and the mixed solvent of ethanol in, the shared volume ratio of ethanol is 30%, obtains solution A, Zn
2+/ Al
3+Mol ratio is 2: 1, Zn
2+Concentration be 0.05M;
2, with 0.529g perfluorooctane sulfonate and 0.0088g 8-hydroxyl-1,3,6-trisulfonic acid base pyrene trisodium salt is dissolved in 100ml and removes CO
2Deionized water and the mixed solvent of ethanol in, the shared volume ratio of ethanol is 30%, obtains solution B;
3, solution A and solution B are mixed to get solution C, solution C is poured in the four-hole boiling flask;
4, getting 0.8g NaOH is dissolved in 100ml and removes CO
2Deionized water and the mixed solvent of ethanol in, the shared volume ratio of ethanol is 30%; This NaOH solution by constant pressure funnel, under the nitrogen protection condition, is slowly dripped in the four-hole boiling flask that solution C is housed;
5, being added dropwise to complete rear is 4.5 with NaOH adjusting pH value, obtains slurries D, places 70 ℃ of water-baths to react 24 hours under the nitrogen protection condition four-hole boiling flask;
6, reaction product is spent respectively CO
2Deionized water and alcohol mixed solution centrifuge washing, colourless to washings, the shared volume ratio of ethanol is 30%; The centrifugal filter cake that obtains 70 ℃ of vacuum-dryings 20 hours, is namely obtained 8-hydroxyl-1,3, and 6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion be the composite luminescent material of intercalation ZnAl hydrotalcite altogether.
Product is characterized: as shown in Figure 1,8-hydroxyl-1,3, the serial diffraction peak that 00l is orientated has appearred in 6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root the negatively charged ion altogether XRD figure of intercalated hydrotalcite composite luminescent material, 003 diffraction peak appears near 4.5 °, and calculating interlamellar spacing is 1.98nm, and 8-hydroxyl-1 is described, the altogether intercalation success of 3,6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion.As shown in Figure 3,8-hydroxyl-1,3,6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion altogether intercalated houghite material go out the peak by the fluorescence emission spectrum that the 375nm ultraviolet excitation obtains at 452nm, with respect to pure 8-hydroxyl-1,3,6-trisulfonic acid base pyrene trisodium salt dilute solution, obvious bathochromic effect appears in the emmission spectrum of this composite luminescent material, again shows common intercalation success.
Embodiment 2
1, takes by weighing 1.28g Mg (NO
3)
26H
2O and 0.94g Al (NO
3)
39H
2O is dissolved in 100ml and removes CO
2Deionized water and the mixed solvent of ethanol in, the shared volume ratio of ethanol is 30%, obtains solution A, Mg
2+/ Al
3+Mol ratio is 2: 1, Zn
2+Concentration be 0.05M;
2, with 0.529g perfluorooctane sulfonate and 0.0088g 8-hydroxyl-1,3,6-trisulfonic acid base pyrene trisodium salt is dissolved in 100ml and removes CO
2Deionized water and the mixed solvent of ethanol in, the shared volume ratio of ethanol is 30%, obtains solution B;
3, solution A and solution B are mixed to get solution C, solution C is poured in the four-hole boiling flask;
4, getting 0.8g NaOH is dissolved in 100ml and removes CO
2Deionized water and the mixed solvent of ethanol in, the shared volume ratio of ethanol is 30%; This NaOH solution by constant pressure funnel, under the nitrogen protection condition, is slowly dripped in the four-hole boiling flask that solution C is housed;
5, being added dropwise to complete rear is 8.5 with NaOH adjusting pH value, obtains slurries D, places 70 ℃ of water-baths to react 24 hours under the nitrogen protection condition four-hole boiling flask;
6, reaction product is spent respectively CO
2Deionized water and alcohol mixed solution centrifuge washing, colourless to washings, the shared volume ratio of ethanol is 30%; The centrifugal filter cake that obtains 70 ℃ of vacuum-dryings 20 hours, is namely obtained 8-hydroxyl-1,3, and 6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion be the composite luminescent material of intercalation MgAl hydrotalcite altogether.
Product is characterized: as shown in Figure 2,8-hydroxyl-1,3, the serial diffraction peak that 00l is orientated has appearred in 6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root the negatively charged ion altogether XRD figure of intercalated hydrotalcite composite luminescent material, 003 diffraction peak appears near 4.29 °, and calculating interlamellar spacing is 2.06nm, and 8-hydroxyl-1 is described, the altogether intercalation success of 3,6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion.As shown in Figure 4,8-hydroxyl-1,3,6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion altogether intercalated houghite material go out the peak by the fluorescence emission spectrum that the 375nm ultraviolet excitation obtains at 527nm, with respect to pure 8-hydroxyl-1,3,6-trisulfonic acid base pyrene trisodium salt dilute solution, obvious bathochromic effect appears in the emmission spectrum of this composite luminescent material, again shows common intercalation success.
Embodiment 3
1, takes by weighing 1.99g Zn (NO
3)
26H
2O and 0.94g Al (NO
3)
39H
2O is dissolved in 40ml and removes CO
2Deionized water and the mixed solvent of ethanol in, the shared volume ratio of ethanol is 30%, obtains solution A, Zn
2+/ Al
3+Mol ratio is 2: 1, Zn
2+Concentration be 0.125M;
2, with 0.529g perfluorooctane sulfonate and 0.0088g 8-hydroxyl-1,3,6-trisulfonic acid base pyrene trisodium salt is dissolved in 40ml and removes CO
2Deionized water and the mixed solvent of ethanol in, the shared volume ratio of ethanol is 30%, obtains solution B;
3, solution A and solution B are mixed to get solution C, solution C is poured in the four-hole boiling flask;
4, getting 0.8g NaOH is dissolved in 100ml and removes CO
2Deionized water and the mixed solvent of ethanol in, the shared volume ratio of ethanol is 30%; This NaOH solution by constant pressure funnel, under the nitrogen protection condition, is slowly dripped in the four-hole boiling flask that solution C is housed;
5, being added dropwise to complete rear is 4.5 with NaOH adjusting pH value, obtains slurries D, and slurries D is transferred in the water heating kettle, and hydro-thermal reaction is 24 hours in 80 ℃ of baking ovens;
6, reaction product is spent respectively CO
2Deionized water and alcohol mixed solution centrifuge washing, colourless to washings, the shared volume ratio of ethanol is 30%; The centrifugal filter cake that obtains 70 ℃ of vacuum-dryings 20 hours, is namely obtained 8-hydroxyl-1,3, and 6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion be the composite luminescent material of intercalation ZnAl hydrotalcite altogether.
In sum, with the composite luminescent material of the present invention's preparation: 1, carry out XRD and characterize, calculating interlamellar spacing is 1.9～2.1nm, shows 8-hydroxyl-1,3, the altogether intercalation success of 6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion; 2, carry out fluorescence spectrum and characterize, show that the optimal luminescent peak of this composite luminescent material has obvious red shift characteristic with respect to its aqueous solution; Above-mentioned sign and test result show that this composite luminescent material takes full advantage of the space confinement effect of hydrotalcite layers and the interaction between the Subjective and Objective, has realized the dye molecule immobilization.
Claims (2)
1. 8-hydroxyl-1,3,6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion be intercalated hydrotalcite composite luminescent material altogether, it is characterized in that this composite luminescent material is a kind of anionic supramolecule stratiform composite luminescent material, and its chemical formula is: [(M
2+)
1-x(M
3+)
x(OH)
2]
X+(A
1 A-)
y(A
2 B-)
zMH
2O, 0.2≤x≤0.33 wherein, 0.02x≤y≤0.1x, 0.7x≤z≤0.94x, and ya+zb=x, m=3～6 are interlayer crystal water molecule number, M
2+Represent divalent metal, M
3+Represent trivalent metal ion, A
1 A-Represent 8-hydroxyl-1,3,6-trisulfonic acid base pyrene negatively charged ion, a=3, A
2 B-Represent perfluoroetane sulfonic acid root negatively charged ion, b=1; The crystalline structure of this composite luminescent material is the crystalline structure of houghite material, and metallic cation and hydroxide ion consist of octahedra with covalent linkage, form sheet structure by common limit;
Described M
2+Be Mg
2+, Ni
2+, Co
2+, Zn
2+Or Ca
2+, M
3+Be Al
3+Or Fe
3+
2. 8-hydroxyl-1,3,6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion be the preparation method of intercalated hydrotalcite composite luminescent material altogether, it is characterized in that concrete operation step is:
(1) preparation divalence, trivalent metal cation mol ratio M
2+/ M
3+Be the solution A of 2:1～4:1, wherein divalent metal concentration is 0.01～1.6M; Solvent is the mixed solvent of water and ethanol, and the shared volume ratio of ethanol is 30%～50%;
(2) press 8-hydroxyl-1,3,6-trisulfonic acid base pyrene trisodium salt and perfluorooctane sulfonate mol ratio are 1:32.6～1:6.52 preparation mixing solutions B, and so that two kinds of electronegative sums of negatively charged ion equal M in the step (1)
3+The mole number of ion, it is 0.01～2.0M that two kinds of ions add up to volumetric molar concentration; Solvent is selected the mixed solvent of water and ethanol, and the shared volume ratio of ethanol is 30%～50%;
(3) solution A and solution B are mixed to get solution C, then solution C are poured in the four-hole boiling flask;
(4) the preparation mole number is the M in the step (1)
2+, M
3+The NaOH solution that the metal ion total moles is 2～2.5 times, NaOH strength of solution are 0.01～3.0M, and solvent is selected the mixed solvent of water and ethanol, and the shared volume ratio of ethanol is 30%～50%; This NaOH solution by constant pressure funnel, is slowly dripped in the four-hole boiling flask that solution C is housed under the nitrogen protection condition;
(5) be added dropwise to complete and regulate pH value 4.0～9.0 with NaOH afterwards, obtain slurries D, place 50～80 ℃ of water-baths under the nitrogen protection condition, to react 12～24 hours four-hole boiling flask, or slurries D is transferred in the water heating kettle, 80～100 ℃ of lower reactions of temperature control 12～24 hours;
(6) reaction product in the step (5) is spent respectively CO
2Deionized water and alcohol mixed solution centrifuge washing 3～6 times, colourless to washings, the shared volume ratio of ethanol is 30%～50%; With the vacuum-drying 15～20 hours in 50～70 ℃ of temperature ranges of the centrifugal filter cake that obtains, namely obtain 8-hydroxyl-1,3,6-trisulfonic acid base pyrene negatively charged ion and perfluoroetane sulfonic acid root negatively charged ion be intercalated hydrotalcite composite luminescent material altogether;
Described M
2+Be Mg
2+, Ni
2+, Co
2+, Zn
2+Or Ca
2+, M
3+Be Al
3+Or Fe
3+
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