CN101250409A - Rear earth containing hydrotalcite having high fluorescence and preparation method thereof - Google Patents
Rear earth containing hydrotalcite having high fluorescence and preparation method thereof Download PDFInfo
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- CN101250409A CN101250409A CNA2007101440121A CN200710144012A CN101250409A CN 101250409 A CN101250409 A CN 101250409A CN A2007101440121 A CNA2007101440121 A CN A2007101440121A CN 200710144012 A CN200710144012 A CN 200710144012A CN 101250409 A CN101250409 A CN 101250409A
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- hydrotalcite
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- high fluorescence
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Abstract
The invention relates to a hydrotalcite with high fluorescence, which contains rare type hydrotalcite and the process for preparation. The process for preparation comprises replacing trivalent aluminium ion in hydroxide template layer in template layer or hydrotalcite-like compounds, and meanwhile, mixing a certain amount of ligand or the mixed ligand, and dispersing in hydrotalcite or oil wettability anion among hydrotalcite-like compound layers, and meanwhile coordinating with rare earth ions which is dispersed and scattered on hydroxide template layers, and preparing hydrotalcite-like compound which ha the chemical formula which is [M2+1-xAl3+x(1-y)Re3+yx(OH)-12]An-x/nDyx/mzB. The hydrotalcite-like compound effectively prevents rare earth ion which is utilized as luminescence center from causing fluorescence vanishing which is caused by aggregation, and ligand or mixed ligand which is mixed and dissolved in anion among layers is coordinated with rare earth ions which are embedded on template layers, and special assemblage structure which is formed improves unsymmetry of coordinated rare earth which is utilized as luminescence center, fluorescence intensity of hydrotalcite-like compounds which contain rare earth is greatly enhanced, thereby obtaining a novel hydrotalcite-like compounds with high fluorescence , which contain rare earth.
Description
Technical field
The present invention relates to a class and have rear earth containing hydrotalcite of high fluorescence and preparation method thereof.
Background technology
General formula is [M
2+ 1-xM
3+ x(OH)
2] A
N- X/n.yH
2O] hydrotalcite (layered double hydroxides, 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 is 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 " have rare earth compounding intercalated houghite of fluorescent characteristic and preparation method thereof ' ' patent application (number of patent application: 200510012245.7; 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 objective of the invention is will be with the trivalent aluminium ion in the oxyhydroxide flaggy in an amount of trivalent rare earth ions replacement hydrotalcite or the houghite, simultaneously with a certain amount of part, as thenoyltrifluoroacetone (HTTA), 2,2-dipyridyl (2,2-biby) grade or its mixed ligand are molten mixes, be scattered in the lipophilicity negatively charged ion of hydrotalcite or houghite interlayer, and with the rare-earth ion coordination that disperses to be embedded on the oxyhydroxide flaggy, prevented from effectively to go out because of the fluorescence essence that reunion causes as the rare earth ion of luminescence center, and moltenly mix part or the mixed ligand in interlayer anion and be embedded in rare-earth ion coordination on the flaggy, formed specific group assembling structure has improved the asymmetry as the coordination rare earth of luminescence center, all strengthen the fluorescence intensity of rear earth containing hydrotalcite greatly, obtain the rear earth containing hydrotalcite of the novel high fluorescence of a class.
The concrete technical scheme that adopts of the present invention is as follows:
1. the rear earth containing hydrotalcite (R of a class high fluorescence of the present invention
e-LLDHs) have a following chemical formula:
[M
2+ 1-xAl
3+ x(1-y)R
e 3+y
x(OH)
-1 2]A
n- x/n?Dy
x/mzB]
M wherein
2+Be the divalent metal of magnesium, zinc, copper or nickel; Al
3+Be trivalent aluminium ion; R
e 3+Be the trivalent rare earth positively charged ion, (OH)
-1Be monovalence hydroxide radical anion, A
N-Be n valency negatively charged ion, n=1,2 or 3; D is a part, its average coordination number m=2～3; B is the contained neutral molecule of houghite, and z is the neutral molecule number; X is Al
3+/ (M
2++ Al
3+) molar ratio, x=0.33～0.25; M
2+, Al
3+And R
e 3+The oxyhydroxide laminate of forming this houghite; A
N-Be interlayer anion; Part D is molten to be mixed in interlayer anion A
N-Among, and with laminate on R
e 3+Coordination.
2. the rear earth containing hydrotalcite [M of high fluorescence of the present invention
2+ 1-xAl
3+ X (1-y)R
e 3+y
x(OH)
-1 2] A
N- X/nDy
X/mZB], R wherein
e 3+Be europium (Eu
3+), terbium (Tb
3+), samarium (Sm
3+), thulium (Tm
3+), holmium (Ho
3+), erbium (Er
3+), neodymium (Nd
3+), ytterbium (Yb
3+), lanthanum (La
3+), cerium (Ce
3+), praseodymium (Pr
3+) gadolinium (Gd
3+) or dysprosium (Dy
3+) the trivalent rare earth positively charged ion;
3. the rear earth containing hydrotalcite [M of high fluorescence of the present invention
2+ 1-xAl
3+ X (1-y)R
e 3+y
x(OH)
-1 2] A
N- X/nDy
X/mZB], trivalent rare earth positively charged ion R wherein
e 3+Content be Al
3+The y of content (x) times, y=2.5 * 10
-2～5.0 * 10
-4, i.e. rare-earth cation R wherein
e 3+Content be 2.5 * 10 of x value
-2～5.0 * 10
-4
4. the rear earth containing hydrotalcite [M of high fluorescence of the present invention
2+ 1-xAl
3+ X (1-y)R
e 3+y
x(OH)
-1 2] A
N- X/nDy
X/mZB], wherein D is thenoyltrifluoroacetone (TTA), benzoyltrifluoroacetone (BTA), benzoyl acetone (BA), trifluoroacetylacetone (TFA), diphenylpropane-1,3-dione(DPPO) (DBM), methyl ethyl diketone beta-diketon classes such as (acac); Salicylate classes such as tetracyclines such as duomycin, terramycin, doxycycline, nitro salicyl fluorone, bromination salicylic acid ester, Methylrodin, and 2, the 2-dipyridyl (2,2-biby); 1, the adjacent luxuriant and rich with fragrance sound of vomiting quinoline (o-phen) of 10-; Oxine, phthalocyanine, azomethine (azomethine) or triphenylphosphine oxide (topo) or its binary or tertiary mixture.
5. the rear earth containing hydrotalcite [M of high fluorescence of the present invention
2+ 1-xAl
3+ X (1-y)R
e 3+y
x(OH)
-1 2] A
N- X/nDy
X/mZB], 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 or sodium salicylate or its mixture, thus the R for preparing by coprecipitation method
ePart D is molten among the-LLDHs mixes in interlayer anion A
N-Among, and with laminate on R
e 3+Coordination.
6. the rear earth containing hydrotalcite [M of high fluorescence of the present invention
2+ 1-xAl
3+ X (1-y)R
e 3+y
x(OH)
-1 2] A
N- X/nDy
X/mZB] in, molten mixing in C
12-20Sodium soap, C
12-20Part D content in fat sodium sulfonate, Sodium Benzoate, benzene sulfonic acid sodium salt or sodium salicylate or its mixture is trivalent rare earth positively charged ion R wherein
e 3+/ 2nd to 1/3rd of a molar content (yx).
7. as mentioned above, partly replace trivalent aluminium ion in the oxyhydroxide flaggy in hydrotalcite or the houghite with trivalent rare earth ions, simultaneously with part D, as thenoyltrifluoroacetone (HTTA), 2,2-dipyridyl (2,2-biby) grade or its mixed ligand are scattered in the lipophilicity negatively charged ion of hydrotalcite or houghite interlayer, make and be embedded in the rare-earth ion coordination on the oxyhydroxide flaggy, obtain to have [M
2+ 1-xAl
3+ X (1-y)R
e 3+y
x(OH)
-1 2] A
N- X/nDy
X/mZB] houghite of chemical formula.Because rare earth ion is scattered in the oxyhydroxide flaggy that is embedded in houghite, not only prevented from effectively to go out because of the fluorescence essence that reunion causes as the rare earth ion of luminescence center, and moltenly mix part or the mixed ligand in interlayer anion and be embedded in rare-earth ion coordination on the flaggy, its formed specific group assembling structure has improved the asymmetry as the coordination rare earth of luminescence center, both all strengthen the fluorescence intensity of rear earth containing hydrotalcite greatly, and make R
e-LLDHs has hyperfluorescence.
8. have [M2+1-xAl3+x (1-y) Re3+y x (OH)-12] An-x/n Dyx/mzB] the rear earth containing hydrotalcite (R of the high fluorescence of chemical formula
e-LLDHs), be to implement preparation by coprecipitation method.Coprecipitation method preparation method generally? does take following concrete steps: preparation contain the aluminum soluble salt of x (1-y) mol with an amount of? the water solution A of NaOH; Preparation contains the aqueous solution B of 1-x mol solubility magnesium salts; Take by weighing the europium sesquioxide of (yx) mol, or europium carbonate, or Europium trichloride, or nitrate (control makes y 2.5 * 10
-2～5.0 * 10
-4Interval), after dissolving fully, pours among the B in the dilute hydrochloric acid with 2.5%, be solution C; Preparation contains the lipophilicity organic acid sodium of x/n mol, the part of yx/m mol or the aqueous solution D of mixed ligand.In violent stirring, or ultrasonic wave, or under the microwave action, simultaneously solution A and C dropwise are added solution D, with suitable? the aqueous sodium hydroxide solution conditioned reaction mixed serum of concentration 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, post precipitation carries out suction filtration, and filter Pie was dried 2 hours down in 100～110 ℃, obtained the rear earth containing hydrotalcite (R of high fluorescence
e-LLDHs).
Utilize the rear earth containing hydrotalcite of the high fluorescence that method of the present invention prepares, can prevent from effectively to go out because of the fluorescence essence that reunion causes as the rare earth ion of luminescence center, and moltenly mix part or the mixed ligand in interlayer anion and be embedded in rare-earth ion coordination on the flaggy, formed specific group assembling structure has improved the asymmetry as the coordination rare earth of luminescence center, all strengthen the fluorescence intensity of rear earth containing hydrotalcite greatly, thereby obtain the rear earth containing hydrotalcite of the novel high fluorescence of a class.
Embodiment
Below rear earth containing hydrotalcite of high fluorescence of the present invention and preparation method thereof is described further, will helps the understanding of the present invention with indefiniteness embodiment, and not as a limitation of the invention,
Embodiment 1.
Preparation contains 0.04 gram (5.0 * 10
-4Mol) NaAlO
2With 0.02 gram (5.0 * 10
-4Mol) the NaOH aqueous solution (A); Preparation contains 0.1428 gram (1.5mol * 10
-3) MgCl
2The aqueous solution (B); Take by weighing 0.2019 gram (6.0 * 10
-4Mol) europium sesquioxide (is equivalent to y=2.4 * 10
-3), the dilute hydrochloric acid with 2.5% is poured into after dissolving fully in (B), is solution (C); Preparation contains 3.76 grams (6.15 * 10
-4Mol) sodium stearate, 0.8 gram (3.7 * 10
-3Mol) thenoyltrifluoroacetone (HTTA) and 0.2 gram (1.25 * 10
-3Mol) 2, and the 2-dipyridyl (2,2-biby) (be equivalent to y/m=2.475 * 10
-3) the aqueous solution (D).Under violent stirring, simultaneously with solution (A) with (C) dropwise add (D) solution, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to PH=11, 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 containing europium houghite sample (Eu-LLDHS).With λ ex=394nm ultraviolet excitation, send the feature red fluorescence (613nm) of intensive europium ion (III), fluorescence intensity is up to 4.1 * 10
4(a.u.).
Embodiment 2.
Preparation contains 0.04 gram (5.0 * 10
-4Mol) NaAlO
2With 0.02 gram (5.0 * 10
-4Mol) the NaOH aqueous solution (A); Preparation contains 0.1428 gram (1.5mol * 10
-3) MgCl
2The aqueous solution (B); Take by weighing 2.019 grams (6.0 * 10
-3Mol) europium sesquioxide (is equivalent to y=2.4 * 10
-2), the dilute hydrochloric acid with 2.5% is poured into after dissolving fully in (B), is solution (C); Preparation contains 3.44 grams (6.15 * 10
-4Mol) 16 yellow soda ash, 8.0 grams (3.7 * 10
-2Mol) thenoyltrifluoroacetone (HTTA) and 2.0 grams (1.25 * 10
-2Mol) 2, and the 2-dipyridyl (2,2-biby) (be equivalent to y/m=2.475 * 10
-2) the aqueous solution (D).Under the ultrasonic wave effect, simultaneously with solution (A) with (C) dropwise add (D) solution, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to PH=11, 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 containing the europium houghite.With λ ex=394nm ultraviolet excitation, send the feature red fluorescence (613nm) of intensive europium ion (III), fluorescence intensity is up to 3.0 * 10
3(a.u.).
Embodiment 3.
Preparation contains 0.04 gram (5.0 * 10
-4Mol) NaAlO
2With 0.02 gram (5.0 * 10
-4Mol) the NaOH aqueous solution (A); Preparation contains 0.1428 gram (1.5mol * 10
-3) MgCl
2The aqueous solution (B); Take by weighing 0.02019 gram (6.0 * 10
-5Mol) europium sesquioxide (is equivalent to y=2.4 * 10
-4), the dilute hydrochloric acid with 2.5% is poured into after dissolving fully in (B), is solution (C); Preparation contains 2.76 grams (6.15 * 10
-4Mol) Sodium dodecylbenzene sulfonate, 0.08 gram (3.7 * 10
-4Mol) thenoyltrifluoroacetone (HTTA) and 0.02 gram (1.25 * 10
-4Mol) 2, and the 2-dipyridyl (2,2-biby) (be equivalent to yx/m=2.475 * 10
-4) the aqueous solution (D).Under the violent stirring of not stopping, simultaneously with solution (A) with (C) dropwise add (D) solution, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to PH=11, 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 containing the europium houghite.With λ ex=394nm ultraviolet excitation, send the feature red fluorescence (613nm) of intensive europium ion (III), fluorescence intensity is up to 1.1 * 10
5(a.u.).
Embodiment 4.
Preparation contains 0.04 gram (5.0 * 10
-4Mol) NaAlO
2With 0.02 gram (5.0 * 10
-4Mol) the NaOH aqueous solution (A); Preparation contains 0.1428 gram (1.5mol * 10
-3) MgCl
2The aqueous solution (B); Take by weighing 0.2195 gram (6.0 * 10
-4Mol) terbium sesquioxide (is equivalent to y=2.4 * 10
-3), the dilute hydrochloric acid with 2.5% is poured into after dissolving fully in (B), is solution (C); Preparation contains 3.76 grams (6.15 * 10
-4Mol) sodium stearate, 0.3777 gram (3.7 * 10
-3Mol) methyl ethyl diketone (Hacac) and 0.2344 gram (1.25 * 10
-3Mol) 1, the adjacent luxuriant and rich with fragrance sound of vomiting quinoline of 10-(o-phen) (is equivalent to y/m=2.475 * 10
-3) the aqueous solution (D).Under violent stirring, simultaneously with solution (A) with (C) dropwise add (D) solution, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to PH=11, 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 containing terbium houghite sample (Tb-LLDH
S).With λ ex=394nm ultraviolet excitation, send the feature green fluorescence (545nm) of intensive terbium ion (III), fluorescence intensity is up to 4.5 * 10
4(a.u.).
Embodiment 5.
Preparation contains 0.04 gram (5.0 * 10
-4Mol) NaAlO
2With 0.02 gram (5.0 * 10
-4Mol) the NaOH aqueous solution (A); Preparation contains 0.1428 gram (1.5mol * 10
-3) MgCl
2The aqueous solution (B); Take by weighing 2.195 grams (6.0 * 10
-3Mol) terbium sesquioxide (is equivalent to y=2.4 * 10
-2), the dilute hydrochloric acid with 2.5% is poured into after dissolving fully in (B), is solution (C); Preparation contains 3.75 grams (6.15 * 10
-4Mol) sodium oleate, 3.777 grams (3.7 * 10
-2Mol) methyl ethyl diketone (Hacac) and 2.344 grams 1, the adjacent luxuriant and rich with fragrance sound of vomiting quinoline of 10-(o-phen) (1.25 * 10
-2Mol) (be equivalent to y/m=2.475 * 10
-2) the aqueous solution (D).Under the ultrasonic wave violent stirring, simultaneously with solution (A) with (C) dropwise add (D) solution, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to PH=11, 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 containing terbium houghite (Tb-LLDH
S).With λ ex=394nm ultraviolet excitation, send the feature green fluorescence (545nm) of intensive terbium ion (III), fluorescence intensity is up to 1.6 * 10
3(a.u.).
Embodiment 6.
Preparation contains 0.04 gram (5.0 * 10
-4Mol) NaAlO
2With 0.02 gram (5.0 * 10
-4Mol) the NaOH aqueous solution (A); Preparation contains 0.1428 gram (1.5mol * 10
-3) MgCl
2The aqueous solution (B); Take by weighing 0.02195 gram (6.0 * 10
-5Mol) terbium sesquioxide (is equivalent to y=2.4 * 10
-4), the dilute hydrochloric acid with 2.5% is poured into after dissolving fully in (B), is solution (C); Preparation contains 3.76 grams (6.15 * 10
-4Mol) sodium stearate, 0.03777 gram (3.7 * 10
-4Mol) methyl ethyl diketone (Hacac) and 0.02344 gram 1, the adjacent luxuriant and rich with fragrance sound of vomiting quinoline of 10-(o-phen) (1.25 * 10
-4Mol) (be equivalent to yx/m=2.475 * 10
-4) the aqueous solution (D).Under violent stirring, simultaneously with solution (A) with (C) dropwise add (D) solution, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to PH=11, 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 containing terbium houghite (Tb-LLDH
S).With λ ex=394nm ultraviolet excitation, send the feature green fluorescence (545nm) of intensive terbium ion (III), fluorescence intensity is up to 6.2 * 10
5(a.u.).
Embodiment 7.
Preparation contains 0.04 gram (5.0 * 10
-4Mol) NaAlO
2With 0.02 gram (5.0 * 10
-4Mol) the NaOH aqueous solution (A); Preparation contains 0.1428 gram (1.5mol * 10
-3) MgCl
2The aqueous solution (B); Take by weighing 0.2315 gram (6.0 * 10
-4Mol) trioxide (is equivalent to y=2.4 * 10
-3), the dilute hydrochloric acid with 2.5% is poured into after dissolving fully in (B), is solution (C); Preparation contains 3.76 grams (6.15 * 10
-4Mol) sodium stearate, 0.5 gram (3.7 * 10
-3Mol) diphenylpropane-1,3-dione(DPPO) (DBM) and 0.2 gram (1.25 * 10
-3Mol) 2, the 2-dipyridyl (is equivalent to y/m=2.475 * 10
-3) the aqueous solution (D).Under the ultrasonic wave effect, simultaneously with solution (A) with (C) dropwise add (D) solution, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to PH=11, 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 containing thulium houghite sample ((Tm-LLDH
S).With λ ex=394nm ultraviolet excitation, send the feature blue-fluorescence (460nm) of intensive thulium ion (III), fluorescence intensity is up to 7.3 * 10
3(a.u.).
Embodiment 8.
Preparation contains 0.04 gram (5.0 * 10
-4Mol) NaAlO
2With 0.02 gram (5.0 * 10
-4Mol) the NaOH aqueous solution (A); Preparation contains 0.1428 gram (1.5mol * 10
-3) MgCl
2The aqueous solution (B); Take by weighing 0.06375 gram (6.0 * 10
-3Mol) Holmium trioxide (is equivalent to y=2.4 * 10
-2), the dilute hydrochloric acid with 2.5% is poured into after dissolving fully in (B), is solution (C); Preparation contains 3.75 grams (6.15 * 10
-4Mol) ten tetra-carbonic sodium, 4.218 grams (3.7 * 10
-2Mol) methyl ethyl diketone (Hacac) and 2.0 grams (1.25 * 10
-2Mol) 2,2-dipyridyl (2,2-biby) (1.25 * 10
-2Mol) (be equivalent to y/m=2.475 * 10
-2) the aqueous solution (D).Under the violent stirring of not stopping, simultaneously with solution (A) with (C) dropwise add (D) solution, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to PH=11, 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 containing holmium houghite ((Ho-LLDH
S).With λ ex=394nm ultraviolet excitation, the feature bluish voilet fluorescence (408-429nm) of the holmium ion that sends (III), fluorescence intensity 0.7 * 10
2(a.u.).
Embodiment 9
Preparation contains 0.04 gram (5.0 * 10
-4Mol) NaAlO
2With 0.02 gram (5.0 * 10
-4Mol) the NaOH aqueous solution (A); Preparation contains 0.1428 gram (1.5mol * 10
-3) MgCl
2The aqueous solution (B); Take by weighing 0.02093 gram (6.0 * 10
-5Mol) Samarium trioxide (is equivalent to y=2.4 * 10
-4), the dilute hydrochloric acid with 2.5% is poured into after dissolving fully in (B), is solution (C); Preparation contains 3.76 grams (6.15 * 10
-4Mol) sodium stearate, 0.0607 gram (3.7 * 10
-4Mol) benzoyl acetone (BA) and 2.0 grams (1.25 * 10
-2Mol) 2,2-dipyridyl (2,2-biby) (1.25 * 10
-4Mol) (be equivalent to yx/m=2.475 * 10
-4) the aqueous solution (D).Under microwave action, simultaneously with solution (A) with (C) dropwise add (D) solution, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to PH=11, 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 containing samarium houghite (Sm-LLDH
S).With λ ex=394nm ultraviolet excitation, the characteristic fluorescence of the samarium ion that sends (III) (390,565,600,646nm), fluorescence intensity 0.87 * 10
3(a.u.).
Claims (8)
1. a class has rear earth containing hydrotalcite of high fluorescence and preparation method thereof, it is characterized in that the rear earth containing hydrotalcite of high fluorescence of the present invention has following chemical formula:
[M
2+ 1-xAl
3+ x(1-y)R
e 3+y
x(OH)
-1 2]A
n- x/nDy
x/mzB]
M wherein
2+Be the divalent metal of magnesium, zinc, copper or nickel, R
e 3+Be trivalent rare earth positively charged ion, A
N-Be n valency negatively charged ion, n=1,2 or 3; D is a part, molten mixing in interlayer anion A
N-Among, and with laminate on R
e 3+Coordination, its average coordination number m=2～3; B is the contained neutral molecule of houghite, and z is the neutral molecule number; X is Al
3+/ (M
2++ Al
3+) molar ratio, x=0.33～0.25; M
2+, Al
3+And R
e 3+Form the oxyhydroxide laminate.
2. by described rear earth containing hydrotalcite of claim 1 and preparation method thereof, it is characterized in that described trivalent rare earth positively charged ion R with high fluorescence
e 3+Be meant Eu
3+, Tb
3+, Sm
3+, Tm
3+, Ho
3+, Er
3+, Nd
3+, Yb
3+, La
3+, Ce
3+, Pr
3+, Gd
3+Or Dy
3+
3. by described rear earth containing hydrotalcite of claim 1 and preparation method thereof, it is characterized in that described trivalent rare earth positively charged ion R with high fluorescence
e 3+Content be Al
3+The y of content times, y=2.5 * 10
-2～5.0 * 10
-4, i.e. rare-earth cation R wherein
e 3+Content be 2.5 * 10 of x value
-2～5.0 * 10
-4
4. by described rear earth containing hydrotalcite of claim 1 and preparation method thereof, it is characterized in that described D is with high fluorescence;
The beta-diketon class of thenoyltrifluoroacetone, benzoyltrifluoroacetone, benzoyl acetone, trifluoroacetylacetone, diphenylpropane-1,3-dione(DPPO) or methyl ethyl diketone;
The salicylate class of the tetracyclines of duomycin, terramycin or doxycycline, nitro salicyl fluorone, bromination salicylic acid ester or Methylrodin, and 2, the 2-dipyridyl;
1, the adjacent luxuriant and rich with fragrance sound of vomiting quinoline of 10-; Phthalocyanine, azomethine or triphenylphosphine oxide or its binary or tertiary mixture.
5. a class has rear earth containing hydrotalcite of high fluorescence and preparation method thereof, and part D is the molten in advance C of being mixed in when it is characterized in that preparing
12-20Sodium soap, C
12-20Fat sodium sulfonate, C
0-12Alkylbenzoic acid sodium, C
0-12In sodium alkyl benzene sulfonate or sodium salicylate or its mixture, thus the R that obtains
ePart D is molten among the-LLDHs mixes in interlayer anion A
N-Among, and with laminate on R
e 3+Coordination.
6. by described rear earth containing hydrotalcite and the preparation side thereof of claim 5, it is characterized in that molten mixing in C with high fluorescence
12-20Sodium soap, C
12-20Part D content in fat sodium sulfonate, Sodium Benzoate, benzene sulfonic acid sodium salt or sodium salicylate or its mixture is trivalent rare earth positively charged ion R wherein
e 3+/ 2nd to 1/3rd of a molar content.
7. by described rear earth containing hydrotalcite of claim 5 and preparation method thereof, it is characterized in that because part replaces R with high fluorescence
eAluminum ions rare earth ion R in the-LLDHs flaggy
e 3+With the molten part coordination that mixes in Re-LLDHs interlayer lipophilicity negatively charged ion.
8. by described rear earth containing hydrotalcite of claim 5 and preparation method thereof, it is characterized in that being to prepare by coprecipitation method with high fluorescence.
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| CN101823003A (en) * | 2010-05-10 | 2010-09-08 | 大连理工大学 | Catalyst, method for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid and salt thereof by using same |
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| CN115109588A (en) * | 2022-07-19 | 2022-09-27 | 中国农业科学院农业环境与可持续发展研究所 | Rare earth doped hydrotalcite nanometer optical fertilizer and preparation method and application thereof |
| CN115109588B (en) * | 2022-07-19 | 2024-05-28 | 中国农业科学院农业环境与可持续发展研究所 | Rare earth doped hydrotalcite nano-optical fertilizer and preparation method and application thereof |
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