CN101966978A - Method for preparing multi-metal-oxygen cluster-doped silicon dioxide nanoparticles - Google Patents
Method for preparing multi-metal-oxygen cluster-doped silicon dioxide nanoparticles Download PDFInfo
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- CN101966978A CN101966978A CN 201010500149 CN201010500149A CN101966978A CN 101966978 A CN101966978 A CN 101966978A CN 201010500149 CN201010500149 CN 201010500149 CN 201010500149 A CN201010500149 A CN 201010500149A CN 101966978 A CN101966978 A CN 101966978A
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Abstract
The invention relates to the field of chemistry and materials, in particular to a new method for preparing multi-metal-oxygen cluster-doped silicon dioxide nanoparticles, which is developed by performing the hydroxylation modification of the surface of a multi-metal-oxygen cluster by using electrostatic interaction and introducing the hydroxylated multi-metal-oxygen cluster into silicon dioxide by a sol-gel process. The multi-metal-oxygen cluster-doped silicon dioxide nanoparticles prepared by the method have the characteristics of controllable size, high monodispersity and the like, and the reaction yield is 100 percent. The method ensures the complete structure of the multi-metal-oxygen cluster and the physical and chemical properties of the multi-metal-oxygen cluster. The obtained nano material, when used, can effectively prevent the leakage of the multi-metal-oxygen cluster and therefore is widely applicable to a majority of multi-metal-oxygen clusters.
Description
Technical field
This invention relates to chemistry and material field, be specifically related to a kind of new method for preparing multi-metal oxygen cluster doped silica particle, it is by electrostatic interaction hydroxylating to be carried out on the surface of multi-metal oxygen cluster to modify, and the process sol-gel process is incorporated into hydroxylated multi-metal oxygen cluster in the silica and then develops a kind of new method for preparing the multi-metal oxygen cluster doped Nano particles of silicon dioxide then.
Background technology
Multi-metal oxygen cluster claims polyoxometallate again, is the inorganic material of a class nanoscale.Multi-metal oxygen cluster normally is made up of the early transition metal oxide, and it has abundant chemical composition and various topological structure, and this makes multi-metal oxygen cluster all show huge application potential in fields such as catalysis, medicine, magnetic, proton conductor, optics.Yet multi-metal oxygen cluster is all soluble in water usually, pH poor stability, mechanical strength are low, be a kind of material processed that is difficult to.This has hindered greatly with the exploitation of multi-metal oxygen cluster as the function element of material of main part.With multi-metal oxygen cluster be incorporated into be easy to process and matrix system that structure is determined in, the functional character that realizes multi-metal oxygen cluster is to realize the key of multi-metal oxygen cluster functional material.Nano particles of silicon dioxide is the very important host material of a class, and it has easily advantages such as modification property, size adjustable, hole adjustability of chemical inertness, porous, surface.Some functional motifs are mixed the character that the characteristics that can utilize Nano particles of silicon dioxide in the Nano particles of silicon dioxide can embody functional motif again, are the very important nano materials of a class.Up to the present, people have successfully prepared the silica nano material of various functionalization, as, with the Fe of magnetic
3O
4Be incorporated into the magnetic Nano material that obtains in the silica nanometer and have significant application value in fields such as target transmission, magnetic imagings; With CdSe, CaTe fluorescence quantum, organic chromophores or last conversion NaYF4:Yb, the nanocrystalline fluorescent nano material that obtains in the Nano particles of silicon dioxide that is incorporated into of Er can be used for cell marking and bio-imaging; Drug molecule is incorporated into the nano material that obtains in the porous silicon dioxide nano particle can be used for medicament slow release and controlled release; Multiple functional motif is doped in the Nano particles of silicon dioxide simultaneously then can obtains multi-functional nano material, as having fluorescence and magnetic-doped complex function silica nano material concurrently, to can be used for biomagnetism luminous.In a word, the silica nano material of functionalization has important use in fields such as catalysis, medicine, photonic crystal, biomarker, magnetic, fluorescence.
Consider the advantage of multi-metal oxygen cluster rich functions character and silica matrix, the method that development prepares the multi-metal oxygen cluster doped Nano particles of silicon dioxide is to realize the effective way of multi-metal oxygen cluster functional material.The method of the multi-metal oxygen cluster doped Nano particles of silicon dioxide of report mainly contains two kinds at present: infusion process and original position collosol and gel method.Infusion process is to obtain Nano particles of silicon dioxide by sol gel reaction earlier under alkali condition, then Nano particles of silicon dioxide is soaked in containing the polar solvent of multi-metal oxygen cluster (as ethanol, methyl alcohol, ethanol/water, methanol/acetone etc.) and stir, after physical absorption a few hours, rotary evaporation removes to desolvate and must arrive the silicon dioxide colloid particulate material of multi-metal oxygen cluster absorption.Yet, the gathering of multi-metal oxygen cluster, inhomogeneous doping can take place in multi-metal oxygen cluster doped silica nano particle that the method for this physical absorption obtains usually, and the most in use (especially in the polar solvent) multi-metal oxygen cluster is very easy to leak; IN-SITU SOL-GEL is that silica precursor (as siloxanes, sodium metasilicate) is joined (as water, ethanol) in the polar solvent that contains multi-metal oxygen cluster, multi-metal oxygen cluster can be wrapping in the reaction of silica presoma generation sol-gel under alkali condition and obtain multi-metal oxygen cluster doped silica material in the Nano particles of silicon dioxide.Yet this method can not generally be applicable to most of multi-metal oxygen clusters.This is because most of multi-metal oxygen clusters have the pH unstability, particularly very easily decomposes under alkali condition, and the original position sol gel reaction then need could take place under alkali condition, and this contradiction has limited the universality of this method greatly.In order to solve the deficiency of current method, the present invention has developed a kind of simple and blanket method and has prepared multi-metal oxygen cluster doped silica nano particle.
Summary of the invention
The purpose of this invention is to provide a kind of new method for preparing the multi-metal oxygen cluster doped Nano particles of silicon dioxide, this method is simple, can generally be applicable to most of multi-metal oxygen clusters.The character of multi-metal oxygen cluster remains unchanged in the nano particle that forms, and is difficult for during use leaking.
The present invention is achieved by the following technical solutions: utilize the organic cation surfactant of hydrophobic terminal hydroxyl by electrostatic interaction multi-metal oxygen cluster to be coated earlier, form surfactant embedding multi-metal oxygen cluster organic/inorganic composite.The organic surface active agent on multi-metal oxygen cluster surface can effectively be protected multi-metal oxygen cluster in order to avoid environment damage in the compound; Again this compound is mixed with silicone agent, under alkali condition, prepare multi-metal oxygen cluster doped silica colloidal nanoparticles by IN-SITU SOL-GEL.The hydroxyl of compound periphery can connect and form multi-metal oxygen cluster doped silica nano particle with silicone agent generation covalent bond.Because the protection of organic surface active agent, the sol gel reaction under alkali condition can't be destroyed the structure and the character of multi-metal oxygen cluster.This method has successfully solved current preparation method's deficiency, can generally be applicable to most of multi-metal oxygen clusters.
The present invention includes following steps:
1) hydroxyl cationic surfactant static coating multi-metal oxygen cluster prepares electrostatic complexes
The cationic surfactant basic structure of the hydroxyl that the present invention relates to is made of quaternary ammonium salt cationic head, hydrophobic alkyl chain and terminal hydroxyl.General molecular formula: (CH
3)
3N
+(CH
2)
nOH, (CH
3)
2N
+[(CH
2)
nOH]
2, (CH
3)
2N
+[(CH
2)
mCH
3] [(CH
2)
nOH], (C
6NH
5)
+[(CH
2)
nOH] cationic surfactant of (5≤n≤18,5≤m≤18) all be fit to the present invention (but concrete synthetic method list of references Adv.Mater.2005,17,2688-2692; Chem.Commun.2005,3785-3787).
The multi-metal oxygen cluster synthetic method is simple, and bibliographical information is arranged more, even the part multi-metal oxygen cluster realized commercially producing, and therefore will directly use as raw material in the present invention.Multi-metal oxygen cluster is formed various, and character is abundant.As, have the multi-metal oxygen cluster Na of photoluminescent property
9[EuW
10O
36], K
11[Eu (PW
11O
39)
2], K
13[Eu (SiW
11O
39)
2], K
15[Eu (BW
11O
39)
2], have photochromic K
12[EuP
5W
30O
110], H
3PMo
12O
40, have the H of excellent catalytic property
4SiW
12O
40, K
12[NaP
5W
30O
110], the H with magnetic
3Na
9[Fe
4(H
2O)
2(P
2W
15O
56)
2], have visible absorption character K
6CoSiW
11O
39(showing red), K
8Co
2W
12O
42(showing green), and the multi-metal oxygen cluster with nonlinear optical property are as Na
8[HPW
9O
34], Na
12[P
2W
15O
56], these multi-metal oxygen clusters all can be suitable for method of the present invention.
In practical operation, can select the hydroxyl surface activating agent of multi-metal oxygen cluster and suitable hydrophobic property to carry out static as required and coat and prepare organic/inorganic composite.According to the dissolubility difference of surfactant, can select in the aqueous solution homogeneous phase to coat or the organic and inorganic two-phase coats two kinds of methods and obtains organic/inorganic composite.The method that homogeneous phase coats is suitable for surfactant and multi-metal oxygen cluster soluble in water.The method that the organic and inorganic two-phase coats is applicable to the surfactant that is soluble in organic solvent and water-soluble multi-metal oxygen cluster.
The method that homogeneous phase coats is: at first that multi-metal oxygen cluster to be coated is soluble in water, in addition that the cationic surfactant of hydrophobic side hydroxyl is soluble in water.Control both consumptions, make the ratio of total electrical charge number of the total electrical charge number of surfactant and multi-metal oxygen cluster be 0.8～1: 1 (wherein total electrical charge number equal the individual molecule charge number multiply by mole).Then, under stirring, the multi-metal oxygen cluster aqueous solution is added drop-wise in the aqueous surfactant solution.Be added dropwise to complete the back and continue to stir 4～10 hours (according to the kind of surfactant and multi-metal oxygen cluster, mixing time is variant), collect the precipitation that reaction generates, be drying to obtain the multi-metal oxygen cluster electrostatic complexes that the hydroxyl cationic surfactant coats, electrostatic complexes outer surface hydroxyl, can be dissolved in well in the alcohols solvent, as methyl alcohol, ethanol, propyl alcohol etc.
The method that the organic and inorganic two-phase coats is: at first that multi-metal oxygen cluster to be coated is soluble in water, the cationic surfactant with the hydrophobic side hydroxyl is dissolved in the organic solvent (as carrene, dichloroethanes, chloroform, benzene and toluene) in addition.Same the two consumption of control, making the ratio of the total electrical charge number of the total electrical charge number of surfactant and multi-metal oxygen cluster is 0.8～1: 1, (wherein total electrical charge number equal the individual molecule charge number multiply by mole).Then, under stirring, the organic solution of surfactant is added drop-wise in the multi-metal oxygen cluster aqueous solution.Be added dropwise to complete 4～10 hours (according to surfactant and multi-metal oxygen cluster and kind, mixing time is variant) backs of back continuation stirring and tell organic facies, and wash organic facies with water 3～5 times with separatory funnel.At last, organic facies is filtered and solvent evaporated, promptly obtain the multi-metal oxygen cluster electrostatic complexes that the hydroxyl cationic surfactant coats.The outer surface hydroxyl of electrostatic complexes can be good at being dissolved in the alcohols solvent, as methyl alcohol, ethanol, propyl alcohol etc.
2) sol-gel process prepares the multi-metal oxygen cluster doped Nano particles of silicon dioxide
Be fit to silicone agent of the present invention tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane and four butoxy silanes are arranged.The amine reagent that is fit to this patent comprises ammoniacal liquor, methylamine, ethamine etc.
The electrostatic complexes that the outer surface that above-mentioned steps is obtained has hydroxyl is dissolved in the alcohols solvent, as ethanol, propyl alcohol etc., the concentration of compound in alcohols solvent is 0.01～20 mg/ml, the concentration of compound has determined the final doping of multi-metal oxygen cluster, in the alcoholic solution that is dissolved with the multi-metal oxygen cluster electrostatic complexes, add entry and amine reagent then, the volume of water and amine reagent and be not higher than 15% of the total liquor capacity of system, add silicone agent more at twice, making the mass percent (being compound/[compound+silicone agent]) of (outside desolventizing) compound in the end reaction system is 0.01～25%; The gained mixture stirs 3～8 hours to guarantee abundant hydrolysis of siloxanes and condensation after adding for the first time silicone agent; In reaction system, add for the second time silicone agent then, the quality of silicone agent is advisable not to be higher than for the first time addition, stir 3～8 hours once more to guarantee abundant hydrolysis of siloxanes and condensation, promptly obtain multi-metal oxygen cluster doped silica nano particle.According to the content of solvent for use molecule, water in the experimentation, the doping of compound, the size of gained nano particle (being diameter) is adjustable in 8～600 nanometer range.Solvent molecule is more little, and the size of nano particle is more little; Ammonia concn is more little, and the size of particle is more little; Complex concentration is big more, and the size of nano particle is more little; For example make solvent with 50 milliliter of 98% (mass fraction) methyl alcohol, when the multi-metal oxygen cluster complex concentration was 10 mg/ml, under the catalysis of 1 milliliter of ammoniacal liquor, we can obtain the SiO 2 hybrid particle of size about 8 nanometers; With 50 milliliter of 90% ethanol serves as to hold agent, and when the multi-metal oxygen cluster complex concentration was 0.3 mg/ml, under the catalysis of 5 milliliters of ammoniacal liquor, the size of particle was about 600 nanometers.
Innovation part of the present invention is to coat in the formed electrostatic complexes of multi-metal oxygen cluster with the terminal cationic surfactant that has hydroxyl; multi-metal oxygen cluster as centronucleus and cationic surfactant for casing is arranged; the hydrophobic chain of surfactant provides hydrophobic microenvironment; this has protective effect to multi-metal oxygen cluster nuclear, makes it also can keep the complete of multi-metal oxygen clustering architecture and character under alkali condition.Because the outer surface of compound is a hydroxyl, so can under alkali condition, utilize sol gel reaction easily with the hydroxyl and the covalently bound multi-metal oxygen cluster doped silica nano particle for preparing of silicone agent of compound outer surface.Characteristics such as the nano particle that obtains has controllable size, and monodispersity is good; Reaction yield 100%.This method had both guaranteed the structural integrity of multi-metal oxygen cluster, had protected physics, the chemical property of multi-metal oxygen cluster again.Resulting nano material can effectively suppress the leakage of multi-metal oxygen cluster in use, therefore can generally be applicable to most multi-metal oxygen cluster.
Description of drawings
Fig. 1: a) the multi-metal oxygen cluster Na of two hydroxyl surface activating agent embedding
9[EuW
10O
36] (PM-1) compound illustraton of model; B) the Electronic Speculum figure of PM-1 doped Nano particles of silicon dioxide;
Fig. 2: the x-ray photoelectron energy spectrogram of PM-1 doped Nano particles of silicon dioxide;
Fig. 3: the infrared spectrogram of PM-1 doped Nano particles of silicon dioxide, ultraviolet spectrogram;
Fig. 4: the fluorescence excitation spectrum of different PM-1 doping Nano particles of silicon dioxide and emission spectrogram;
Fig. 5: the fluorescence spectrum after PM-1 doping Nano particles of silicon dioxide soaks in acid, aqueous alkali;
Fig. 6: the multi-metal oxygen cluster K of monohydroxy surfactant embedding
12[EuP
5W
30O
110] (PM-2) compound illustraton of model; The Electronic Speculum figure of PM-2 doped Nano particles of silicon dioxide;
Fig. 7: the X-ray photoelectron spectroscopic analysis of PM-2 doped Nano particles of silicon dioxide;
Fig. 8: the infrared spectrogram of PM-2 doped Nano particles of silicon dioxide, and illumination before and after ultraviolet spectrogram.
As shown in Figure 1, Fig. 1 a has described two hydroxyl cationic surfactants (N, the N-dimethyl is two-(11-hydroxyl-undecyl) ammonium bromide, is called for short DOHDA) and has coated multi-metal oxygen cluster Na9[EuW
10O
36] (PM-1) illustraton of model of formed compound (SEP-1) (synthetic referring to embodiment 1-1). Compound forms nucleocapsid shape structure as we can see from the figure, and PM-1 is nuclear, and DOHDA is shell. And the periphery of compound SEP-1 comprises a plurality of hydroxyls. SEP-1 further forms the Nano particles of silicon dioxide (being called for short S5, synthetic referring to embodiment 2-1) that PM-1 mixes with silicone agent by sol gel reaction. Fig. 1 b has described the transmission electron microscope photo that the PM-1 doping is 5.3% Nano particles of silicon dioxide. We can find out the formation of nano spherical particle from figure, and the size of particle is homogeneous relatively, and full-size distributes and is about 22 nanometers. The edge color that can see nano particle from the enlarged drawing of illustration is more shallow, and the point of a plurality of dark colors that are scattered here and there in the inside of nano particle, we think that dark zone is that this is hinting the existence of multi-metal oxygen cluster because the bigger heavy metal atom of electron density causes. Fig. 1 c has described the transmission electron microscope photo of the pure silicon dioxide nano particle of the PM-1 that undopes, does not see obvious dark point from the particle that illustration amplifies, and this has further supported above supposition, and namely the dark color point among Fig. 1 b is multi-metal oxygen cluster. That is to say that in the silica nanometer that synthetic PM-1 mixes, the more shallow zone of edge color is pure silicon dioxide, and the PM-1 Uniform Doped is in the inside of Nano particles of silicon dioxide.
The x-ray photoelectron of having described the PM-1 doped Nano particles of silicon dioxide such as Fig. 2 can spectrogram. Fig. 2 a is nanoparticle surface and inner X ray X ray photoelectron spectroscopy figure. The surface can spectrogram in exist four obvious peaks, be respectively 104eV, 155eV, 285eV, the peak at 533eV place, these peaks respectively correspondence Si2p，Si
2s，C
1s，O
1sDeng element in conjunction with can, illustrate that nanoparticle surface only exists Si, C, elements such as O, and do not observe the existence of characteristic element tungsten (W) element among the multi-metal oxygen cluster PM-1. Coming to the same thing of this result and above transmission electron microscope, namely the surface of nano particle does not have multi-metal oxygen cluster, only has network of silica. The x-ray photoelectron spectroscopic technique is a kind of surface analysis technique, can only detect apart from the component information of the not enough several nanometers of sample surfaces, in order to detect the internal composition of nano particle, we are earlier with the synthetic nano particle of hydrofluoric acid treatment, hydrofluoric acid can etch away the silicon dioxide layer of nanoparticle surface, and we can observe directly the component information of inside nanoparticles like this. Shown in energy spectrogram inner among Fig. 2 a, there are a plurality of obvious peaks among the figure. With can spectrogram comparing of surface, what we can significantly find inside nanoparticles can five new peaks occur in the spectrogram, respectively at 37eV, 248eV, 261eV, 402eV and 428eV place, these peaks respectively correspondences W4f、W
4d5/2、W
4d3/2、N
1sAnd W4p3/2The combination energy of element, there is multi-metal oxygen cluster in the existence explanation inside of W elements. Fig. 2 b is the enlarged drawing of carbon in the nanoparticle surface energy spectrogram, and the unimodal of corresponding C-C only appears in carbon at the 284.66eV place as we can see from the figure, illustrates that only there is a kind of chemical environment in the carbon of nanoparticle surface. Fig. 2 c is the enlarged drawing of carbon in the inside nanoparticles energy spectrogram, can find that inner carbon has four power spectrum peaks and is respectively 288.97,287.68,286.16, and 284.55eV, these peaks are corresponding C-O-Si respectively, C-O-H, C-N, carbon in conjunction with energy under four kinds of varying environments of C-C. The existence of W elements, and the different chemical environment of carbon is hinting that inside nanoparticles exists multi-metal oxygen cluster and surfactant. The peak area ratio that we can also calculate C-O (comprising C-O-Si and C-O-H) and C-N and C-C from Fig. 2 c is 1: 2.8, and the ratio 1: 2.9 of the molal quantity of three kinds of different carbons is similar in this ratio and the DODHA molecular formula. In addition, the peak area ratio of C-O-Si and C-O-H is 1: 0.8, and this is hinting that the part of hydroxyl of compound SEP-1 and the condensation of silicone agent covalency have formed the C-O-Si key, and namely compound is inner covalently bound with silica matrix at hybrid particle. The data analysis of comprehensive front as can be known, the multi-metal oxygen cluster compound evenly distributes and covalently bound with silica matrix in that Nano particles of silicon dioxide is inner.
As shown in Figure 3 be multi-metal oxygen cluster PM-1, the SiO that SEP-1 and PM-1 mix2Infrared spectrum and the ultraviolet spectrogram of nano particle (S5). Fig. 3 a is infrared spectrogram, 943cm in the infrared spectrum of SEP-1-1Be W-OdAntisymmetric stretching vibration, 845cm-1Be W-Oc-W antisymmetric stretching vibration, 773cm-1Be W-Oc-W antisymmetric stretching vibration, this shows that the structure of multi-metal oxygen cluster POM-1 keeps complete in compound SEP-1; 3425cm in the SEP-1 infrared spectrum-1Be O-H antisymmetric stretching vibration, 2921,2849cm-1Be CH2Antisymmetry and symmetrical stretching vibration, 1468cm-1Be CH2Scissoring vibration, this shows the existence of surfactant in compound SEP-1; The strong absorption band of 1000-1200 wave-number range is the vibration of Si-O-Si network in the S5 infrared spectrum, and the formation of network of silica structure is described. The peak at 2932,2858 wave number places is CH2Antisymmetry and symmetrical stretching vibration, this shows the existence of compound SEP-1 in S5; But the intensity at peak a little less than, SEP-1 is described in the inside of nano particle S5, but not the surface. Fig. 3 b is ultraviolet spectrogram, and S5 the part oxygen of corresponding multi-metal oxygen cluster PM-1 occurred to electric charge transfer (O → W LMCT) band of tungsten among the figure in 260 nanometers, and this shows that also PM-1 is successfully introduced in the Nano particles of silicon dioxide.
As shown in Figure 4 be PM-1, the SiO that SEP-1 and PM-1 mix2Fluorescence excitation spectrum and the emission spectra of nano particle (S5) when solid-state. Fig. 4 a is exciting of multi-metal oxygen cluster PM-1 and emission spectra, and the absorption band of 276 nanometers shifts to the electric charge between tungsten corresponding to part oxygen among the PM-1 in the PLE, and the peak of 594 and 619 nanometers then corresponds respectively among the PM-1 in the fluorescence emission spectrum5D
0→
7F
1With5D
0→
7F
2Emission, be Eu3+Characteristic emission. Fig. 4 b and 4c are respectively exciting of SEP-1 and exciting and emission spectra of emission spectra and S5. Can find out to exist exciting and launching of PM-1 feature among SEP-1 and the S5, these presentation of results static coat and sol-gel process in structure and the character of multi-metal oxygen cluster be not damaged. The SiO that PM-1 mixes2The character of multi-metal oxygen cluster has obtained maintenance in the nano particle (S5).
As shown in Figure 5 be the SiO that PM-1 mixes2The fluorescence spectrum of nano particle after the pH value is to soak 24 hours in 6 and 11 the aqueous solution. We know that exposed PM-1 can almost disappear at the fluorescence of this condition. Yet can see that herein although S5 soaked 24 hours in the solution of pH=6 and pH=11, the photoluminescent property of PM-1 still keeps among the S5. And soak in the rear centrifugal supernatant and do not find Eu3+Characteristic fluorescence. The method of mentioning among these experimental data explanations the present invention not only makes the fluorescence of PM-1 be maintained in nano particle S5, and the PM-1 that mixes also is difficult for leaking in solution.
As shown in Figure 6 be monohydroxy cationic surfactant 11-hydroxyl-undecyl-dimethyl hydrogen bromide tertiary amine (be called for short HUDAH) embedding multi-metal oxygen cluster K12[EuP
5W
30O
110] illustraton of model (synthetic referring to embodiment 1-2) of the compound SEP-2 that forms after (PM-2). Compound forms nucleocapsid shape structure as we can see from the figure, and PM-2 is nuclear, and HUDAH is shell. And the periphery of compound SEP-2 comprises a plurality of hydroxyls can further form the PM-2 doping by sol gel reaction with silicone agent Nano particles of silicon dioxide (being called for short S5, synthetic referring to embodiment 2-2). It is that 13.6% Nano particles of silicon dioxide (is called for short PM-2/SiO that Fig. 6 b has described the PM-2 doping2-2, synthetic referring to embodiment 2-2) stereoscan photograph. The as we can see from the figure existence of nano spherical particle, the size of particle is comparatively even, and maximum distribution is about 150 nanometer range. Fig. 6 c has described the transmission electron microscope photo of nano particle, can see the formation of nano spherical particle, and the size of particle is homogeneous relatively, and maximum distribution is about 150 nanometer range. Edge (about 7 nanometers of the thickness) color that can see nano particle from the enlarged drawing of Fig. 6 d is more shallow, and the point of a plurality of dark colors that are scattered here and there in the inside of nano particle, we think that dark zone is because the bigger heavy metal atom of electron density causes, that is to say, in the silica nanometer that synthetic PM-2 mixes, the more shallow zone of edge color is pure silicon dioxide, and the PM-2 Uniform Doped is in the inside of Nano particles of silicon dioxide.
Such as Fig. 7 PM-2/SiO has been described2The x-ray photoelectron of-2 nano particles can spectrogram. Fig. 7 a is nanoparticle surface and inner X ray X ray photoelectron spectroscopy figure. Exist three obvious peaks in the energy spectrogram on surface, be respectively 103.4eV, 284.6eV, the peak at 532.6eV place, these peaks correspond respectively to Si2p，C
1s，O
1sDeng element in conjunction with can, illustrate that nanoparticle surface only exists O, C, elements such as Si, and do not observe the existence of characteristic element tungsten (W) element among the multi-metal oxygen cluster PM-2. Coming to the same thing of this result and above transmission electron microscope, namely the surface of nano particle does not have multi-metal oxygen cluster, only has network of silica. The x-ray photoelectron spectroscopic technique is a kind of surface analysis technique, can only detect apart from the not enough several nanometers of sample surfaces component information, in order to detect the internal composition of nano particle, we are earlier with the synthetic nano particle of hydrofluoric acid treatment, hydrofluoric acid can etch away the silicon dioxide layer of nanoparticle surface, and we can observe directly the component information of inside nanoparticles like this. Shown in energy spectrogram inner among Fig. 7 a, there are a plurality of obvious peaks among the figure. With can spectrogram comparing of surface, what we can significantly find inside nanoparticles can four new peaks occur in the spectrogram, exist respectively, and 35.58eV, 37.66eV, 133.85eV, the 402.05eV place, these peaks are respectively W4f7/2，W
4f5/2，P
2pAnd N1sDeng the combination energy of element, there is multi-metal oxygen cluster in the existence of W elements explanation inside. Fig. 7 b is the enlarged drawing of carbon in the nanoparticle surface energy spectrogram, and the unimodal of corresponding C-C only appears in carbon at the 284.63eV place as we can see from the figure, illustrates that only there is a kind of chemical environment in the carbon of nanoparticle surface. Fig. 7 c is the enlarged drawing of carbon in the inside nanoparticles energy spectrogram, can find that inner carbon has four power spectrum peaks and is respectively 288.95,287.76,286.12, and 284.55eV, these peaks are corresponding C-O-Si respectively, C-O-H, C-N, carbon in conjunction with energy under four kinds of varying environments of C-C. Above x-ray photoelectron power spectrum presentation of results multi-metal oxygen cluster and surfactant are present in inside nanoparticles. In addition, the peak area ratio that we can also calculate C-O (comprising C-O-Si and C-O-H) and C-N and C-C from Fig. 7 c is 1: 3.1, and the ratio 1: 3 of the molal quantity of three kinds of different carbons is similar in this ratio and the HUDAH molecular formula. In addition, the area at C-O-Si peak is 55.3% of C-O peak area, and this shows that the part of hydroxyl of compound SEP-2 and the condensation of silicone agent covalency have formed the C-O-Si key, and namely compound is inner covalently bound with silica matrix at hybrid particle. The data analysis of comprehensive front as can be known, the multi-metal oxygen cluster compound evenly distributes and covalently bound with silica matrix in that Nano particles of silicon dioxide is inner.
As shown in Figure 8 be multi-metal oxygen cluster PM-2, SEP-2, SiO2SiO with the PM-2 doping2Nano particle (PM-2/SiO2) infrared spectrum and ultraviolet spectrogram. Fig. 8 a is PM-2, SEP-2 and PM-2/SiO2Infrared spectrogram, among Fig. 8 a in the infrared spectrum of SEP-2 the peak at 1158,1062 wave number places be P-OaVibration, the peak at 982 wave number places is W-OdAntisymmetric stretching vibration, the peak at 916 wave number places are W-Ob-W antisymmetric stretching vibration, the peak at 785 wave number places are W-OcThis shows that the structure of multi-metal oxygen cluster POM-2 keeps complete in compound SEP-2-W antisymmetric stretching vibration; The peak at 3403 wave number places is the antisymmetric stretching vibration of O-H in the hydroxyl in the SEP-2 infrared spectrum, and the peak at 2924,2851 wave number places is CH in the alkyl chain2Antisymmetry and symmetrical stretching vibration, the peak quaternary ammonium head NH at 2746 wave number places2Stretching vibration, the peak at 1468 wave number places is CH in the alkyl chain2Scissoring vibration, the peak at 1054 wave number places then is the stretching vibration of the terminal C-O of surfactant, this shows the existence of surfactant HUDAH in compound SEP-2; The nano particle PM-2/SiO that is mixing2Infrared spectrum in the strong absorption band of 1000-1200 wave-number range be the absorption vibration of Si-O-Si network, the formation of network of silica structure is described. Because the strong vibration of silica absorbs the shielding action to the multi-metal cluster absorption of vibrations, we can't be from Fig. 8 a PM-2/SiO2The absorption spectrogram in clearly tell the vibration that comes from PM-2. Fig. 8 b is SEP-2, SiO2And PM/SiO2Absorption spectrum at 1005-750 wave number place is different from SiO2The level and smooth absorption band in 943 wave number places, hybrid material PM-2/SiO2Infrared vibration at 918,936 and 955 wave number places three absorption of vibrations bands have appearred respectively, this is because 939,916 W-O of wave number placebThe stack of-W vibration and 943 Si-O-H of wave number place vibration causes, and this shows that multi-metal oxygen cluster is successfully introduced in the composite hybridization material. Fig. 8 c is ultraviolet spectrogram, the nano particle (PM-2/SiO of SEP-2 and doping among the figure2) in 275 nanometers the part oxygen of corresponding multi-metal oxygen cluster PM-2 has all appearred to electric charge transfer (O → W LMCT) band of tungsten, and this shows that also compound SEP-2 is successfully introduced in the Nano particles of silicon dioxide. Fig. 8 d is PM-2/SiO2Ultraviolet spectrogram before and after the illumination. As we can see from the figure, new absorption band occurs at the 730nm place after the 365 nanometer illumination, this is corresponding to W among the PM-2V→W
VIValence band in electric charge shift (IVCT) band, this photochromic property that shows multi-metal oxygen cluster PM-2 still keeps in hybrid material.
The specific embodiment
Following specific embodiment is that the present invention is further elaborated, does not limit the invention and do not represent according to this.
1, the quaternary cationics of terminal hydroxyl is to the coating of multi-metal oxygen cluster
Principle: dissociating of surperficial counter ion counterionsl gegenions takes place in multi-metal oxygen cluster easily in polar solvent, form the cluster ion that has negative electrical charge; The cationic surfactant of terminal hydroxyl is because dissociating of counter ion counterionsl gegenions forms the ion that has positive charge; Both form stable organic/inorganic composite by electrostatic interaction, the compound that obtains can well be dissolved in the alcohols solvent of suitable polarity as, ethanol, propyl alcohol.Can adopt homogeneous phase coating and organic and inorganic two-phase coating dual mode in the aqueous solution according to surfactant and the deliquescent difference of multi-metal oxygen cluster.
Multi-metal oxygen cluster K
12[EuP
5W
30O
110] and K
12.5Na
1.5[NaP
5W
30O
110] reference literature Inorg.Chem.1993,32,1573 is synthetic; K
8[Co
2W
12O
42] with reference to J.Am.Chem.Soc.1956,78,4503 is synthetic; Na
9[EuW
10O
36] with reference to Bull.Chem.Soc.Jpn.1993,66,444 is synthetic.Other common multi-metal oxygen cluster also all is fit to the present invention.
Hydroxyl cationic surfactant N, the N-dimethyl is two-and (be called for short DOHDA, chemical formula is C to (11-hydroxyl-undecyl) ammonium bromide
24H
52NO) and 11-hydroxyl-undecyl-dimethyl hydrogen bromide tertiary amine (be called for short HUDAH, chemical formula is C
13H
30NO) concrete synthetic method is referring to document Adv.Mater.2005,17,2688-2692.
Embodiment 1-1:N, the N-dimethyl is two-and (11-hydroxyl-undecyl) ammonium bromide (being called for short DOHDA) coats Na
9[EuW
10O
36] (PM-1)
0.2 gram DOHDA is dissolved in 20 ml deionized water 0.14 gram Na
9EuW
10O
36Be dissolved in 20 ml deionized water DOHDA and Na
9EuW
10O
36Mol ratio be 9: 1 (charge ratio is 9: 9).Under stirring, will contain Na
9EuW
10O
36The aqueous solution be added drop-wise in the aqueous solution of DOHDA.After being added dropwise to complete, continue to stir 5 hours, the precipitation that generates is filtered with molten hourglass bucket, the white solid that obtains can obtain the Na of DOHDA embedding in the room temperature vacuum drying
9[EuW
10O
36] compound (being called for short SEP-1), productive rate is 60%.SEP-1 elementary analysis: C% 35.45, H% 6.81, and N% 1.52, and the chemical formula of SEP-1 is (DOHDA)
6EuW
10O
364H
2O.
Embodiment 1-2:11-hydroxyl-undecyl-dimethyl hydrogen bromide tertiary amine (being called for short HUDAH) coats K
12[EuP
5W
30O
110] (PM-2)
0.2 gram HUDAH is dissolved in 20 ml deionized water 0.24 gram K
12[EuP
5W
30O
110] be dissolved in 20 ml deionized water HUDAH and K
12[EuP
5W
30O
110] mol ratio be 12: 1 (charge ratio is 12: 12).Under stirring, will contain K
12[EuP
5W
30O
110] the aqueous solution be added drop-wise in the aqueous solution of HUDAH.After being added dropwise to complete, continue to stir 5 hours, the precipitation that generates is filtered with molten hourglass bucket, obtain white solid, can obtain the K of HUDAH embedding in the room temperature vacuum drying
12[EuP
5W
30O
110] compound (being called for short SEP-2), productive rate is 55%.SEP-2 elementary analysis: C% 18.00, H% 3.26, and N% 1.60, and the chemical formula of SEP-2 is (HUDAH)
11HEuP
5W
30O
1103H
2O.
Embodiment 1-3:DOHDA coats K
8[Co
2W
12O
42] (PM-3)
0.2 gram DOHDA is dissolved in 20 ml deionized water 0.19 gram K
8Co
2W
12O
42Be dissolved in 20 ml deionized water DOHDA and K
8Co
2W
12O
42Mol ratio be 8: 1 (charge ratio is 8: 8).Under stirring, will contain K
8Co
2W
12O
42The aqueous solution be added drop-wise in the aqueous solution of DOHDA.After being added dropwise to complete, continue to stir 5 hours, the precipitation that generates is filtered with molten hourglass bucket, obtain green solid, can obtain the K of DOHDA embedding in the room temperature vacuum drying
8[Co
2W
12O
42] compound (being called for short SEP-3), productive rate is 55%.SEP-3 elementary analysis: C% 34.65, H% 6.66, and N% 1.70, and the chemical formula of SEP-3 is (DOHDA)
7Co
2W
12O
424H
2O.
Embodiment 1-4:HUDAH coats K
12.5Na
1.5[NaP
5W
30O
110] (PM-4)
0.2 gram HUDAH is dissolved in 20 ml deionized water 0.41 gram K
12.5Na
1.5[NaP
5W
30O
110] be dissolved in 20 ml deionized water HUDAH and K
12.5Na
1.5[NaP
5W
30O
110] mol ratio be 14: 1 (charge ratio is 14: 14).Under stirring, will contain K
12.5Na
1.5[NaP
5W
30O
110] the aqueous solution be added drop-wise in the aqueous solution of HUDAH.After being added dropwise to complete, continue to stir after 1 hour, the precipitation that generates is filtered with molten hourglass bucket, obtain white solid, can obtain HUDAH embedding K in the room temperature vacuum drying
12.5Na
1.5[NaP
5W
30O
110] compound (be called for short SEP-4), productive rate 60%.SEP-4 elementary analysis: C% 18.58, H% 3.60, and N% 1.56, and the chemical formula of SEP-4 is (HUDAH)
12HNaP
5W
30O
1103H
2O.
2, the preparation of multi-metal oxygen cluster doped Nano particles of silicon dioxide
Reaction principle: its structure of multi-metal oxygen cluster compound that the hydroxyl cationic surfactant coats is the nucleocapsid shape, multi-metal oxygen cluster is a centronucleus, the hydrophobic chain of surfactant is a shell, and hydrophobic shell can guarantee that alkali in the sol-gel process reaction system etc. can not destroy the structure of multi-metal oxygen cluster.In addition, the hydroxyl of compound periphery can impel compound to be dissolved in the alcohols solvent, and with silicone agent pure exchange reaction takes place under alkali condition, and becomes network with the silicone agent condensation is covalently bound, forms stable Nano particles of silicon dioxide.
To be top grade pure for used alcohol solvent in the experiment, and water is deionized water.
Embodiment 2-1:Na
9[EuW
10O
36] preparation of doped Nano particles of silicon dioxide
The SEP-1 of difference amount being dissolved in the mixed solvent of 50 milliliters of second alcohol and waters (volume ratio of second alcohol and water is 49: 1, and the mass fraction of ethanol is 97.4%) respectively is mixed with SEP-1 concentration and is respectively 0.04,0.08,0.2,0.32, the solution of 0.84,1.20 mg/ml.In the SEP-1 solution that 1.58 gram tetraethoxysilanes are prepared more than adding respectively, stir the back to wherein adding 2 milliliters of concentrated ammonia liquors (mass fraction of ammonia is 28% in the concentrated ammonia liquor) respectively with 350 rev/mins speed mechanical, reaction system stirred 5 hours with 100 rev/mins rotating speed at ambient temperature, add 1.02 gram tetraethoxysilanes again in solution respectively, the rotating speed stirring that at room temperature continues then with 100 rev/mins finishes reaction after 5 hours.Reacted mixed liquor is centrifugal respectively, and the precipitation after centrifugal water is respectively cleaned and can be obtained the PM-1 doping for 4 times and be respectively 0.3%, 0.5%, 1.3%, 2.1%, 5.3% and 7.4% Nano particles of silicon dioxide S1, S2, S3, S4, S5, S6.The size of gained nano particle reduces successively by the increase of compound doping, is about 60 nanometers as S1, and S2 is about 52 nanometers, and S3 is about 45 nanometers, and S4 is about 30 nanometers, and S5 is about 22 nanometers, and S6 is about 13 nanometers).
The sign of PM-1 doped Nano particles of silicon dioxide is referring to description of drawings (Fig. 1～Fig. 5)
Table 1 is Na
9EuW
10O
36, compound SEP-1, PM-1/SiO
2Hybrid material fluorescence data conclusive table, wherein PM-1 represents multi-metal oxygen cluster Na in sample column
9EuW
10O
36, SEP-1 represents Na
9EuW
10O
36It is 0.3%, 0.5%, 1.3%, 7.4% hybrid material that/DOHDA compound, S1, S2, S5, S6 are represented compound doping quality percentage composition respectively; k
TotRepresent the rate of decay constant, k
rRepresent the fluorescent emission speed constant; T represents fluorescence lifetime; η represents fluorescence quantum efficiency; 5d
0-7f
2/ 5d
0-7f
1Represent Eu
3+Ion 5d
0-7f
2Transition emissive porwer and 5d
0-7f
1The ratio of transition emissive porwer.Because centre of luminescence Eu in the multi-metal oxygen cluster molecule
3+The variation of residing chemical environment, to compound SEP-1, fluorescence lifetime shortens from multi-metal oxygen cluster PM-1, and luminous efficiency reduces; In the doped silica particle, the fluorescence lifetime of PM-1 further shortens, but along with the increase of load capacity, the luminescent lifetime of nano particle increases, luminous efficiency and multi-metal oxygen cluster are at the same order of magnitude, so we have obtained the silica nano material PM-1/SiO of higher fluorescence quantum efficiency
2
Table 1: multi-metal oxygen cluster, the fluorescence data conclusive table of compound and doped Nano particles of silicon dioxide
Excitation band k
Tot 5d
0-
7f
2
Sample (Gu) T (ms) k
r(ms
-1) η
(nm) (ms
-1) /
5d
0-
7f
1
PM-1 278 2.80 0.38 0.27 75.61 0.16
SEP-1 271 1.82 0.55 0.31 56.36 0.97
S1(0.3wt％) 285 0.83 1.20 0.86 71.67 3.66
S2(0.5wt％) 285 0.87 1.15 0.77 66.96 3.02
S3(1.3wt％) 285 0.93 1.08 0.48 44.44 2.39
S6(7.4wt％) 290 1.23 0.81 0.52 64.20 2.56
Embodiment 2-2:K
12[EuP
5W
30O
110] preparation of doped Nano particles of silicon dioxide
Respectively 16 milligrams and 63 milligrams of SEP-2 are dissolved in respectively in the mixed solvent of 50 milliliters of second alcohol and waters (volume ratio of second alcohol and water is 49: 1), 0.93 gram tetraethoxysilane is added respectively in the ethanol/water mixed solution of above SEP-2, and respectively to wherein adding 5 ml waters, after stirring with 350 rev/mins speed mechanical respectively to wherein adding 1 milliliter of concentrated ammonia liquor (mass fraction of ammonia is 28% in the concentrated ammonia liquor), reactant liquor at room temperature continues mechanical agitation after 5 hours with 100 rev/mins rotating speed, in reaction solution, add 0.46 gram tetraethoxysilane more respectively, at room temperature finishes after 5 hours to react with 100 rev/mins rotating speed mechanical agitation.Respectively that reaction mixture is centrifugal, the precipitation after centrifugal water respectively cleans that can to obtain the PM-2 doping for 4 times be 3.9% and 13.6% Nano particles of silicon dioxide, is designated as PM-2/SiO respectively
2-1 and PM-2/SiO
2-2.The size of relevant nanometer particle is about 100 nanometers and 150 nanometers respectively.
Gained K
12[EuP
5W
30O
110] sign of doped Nano particles of silicon dioxide sees description of drawings (Fig. 6～Fig. 8).
Embodiment 2-3:K
12.5Na
1.5[NaP
5W
30O
110] preparation of doped Nano particles of silicon dioxide
16 milligrams of SEP-4 are dissolved in the mixed solvent of 50 milliliters of second alcohol and waters (volume ratio of second alcohol and water is 49: 1).0.93 gram tetraethoxysilane is joined in the solution of the above SEP-4 of containing.In above mixed liquor, add 5 ml waters and stir with 350 rev/mins speed mechanical.Then to wherein adding 1 milliliter of concentrated ammonia liquor (mass fraction of ammonia is 28% in the concentrated ammonia liquor), at room temperature with 100 rev/mins rotating speed mechanical agitation 5 hours.In reaction solution, add 0.46 gram tetraethoxysilane again, at room temperature continue to stir and finish reaction after 5 hours with 100 rev/mins rotating speed.Reaction mixture is centrifugal, and the precipitation after centrifugal water respectively cleans that can to obtain the PM-4 doping for 4 times be 3.9% Nano particles of silicon dioxide (about 180 nanometers of size).
Gained K
12.5Na
1.5[NaP
5W
30O
110] characterizing method, step and the experimental result of doped Nano particles of silicon dioxide and the result of embodiment 2-2 be similar.
Claims (6)
1. method for preparing the multi-metal oxygen cluster doped Nano particles of silicon dioxide, its step is as follows:
1) the multi-metal oxygen cluster electrostatic complexes of preparation hydroxyl cationic surfactant coating
Obtain the multi-metal oxygen cluster electrostatic complexes that the hydroxyl cationic surfactant coats by the method that homogeneous phase coats or the organic and inorganic two-phase coats, the method that homogeneous phase coats is suitable for surfactant and multi-metal oxygen cluster soluble in water, and the method that the organic and inorganic two-phase coats is applicable to the surfactant that is soluble in organic solvent and water-soluble multi-metal oxygen cluster;
2) sol-gel process prepares the multi-metal oxygen cluster doped Nano particles of silicon dioxide
The multi-metal oxygen cluster electrostatic complexes that the hydroxyl cationic surfactant that above-mentioned steps is obtained coats is dissolved in the alcohols solvent, the concentration of compound in alcohols solvent is 0.01～20 mg/ml, in the alcoholic solution that is dissolved with electrostatic complexes, add entry and amine reagent then, the volume of water and amine reagent and be not higher than 15% of the total liquor capacity of system, add silicone agent more at twice, the mass percent that makes electrostatic complexes/(electrostatic complexes+silicone agent) is 0.01～25%; The gained mixture stirs 3～8 hours to guarantee abundant hydrolysis of siloxanes and condensation after adding for the first time silicone agent, in reaction system, add for the second time silicone agent then, the silicone agent that adds is of low quality in the quality of the silicone agent that adds for the first time for the second time, stir 3～8 hours once more to guarantee abundant hydrolysis of siloxanes and condensation, the diameter that promptly obtains the multi-metal oxygen cluster doping is the Nano particles of silicon dioxide of 8～600 nanometers.
2. a kind of method for preparing the multi-metal oxygen cluster doped Nano particles of silicon dioxide as claimed in claim 1 is characterized in that: the cationic surfactant of hydroxyl is made of quaternary ammonium salt cationic head, hydrophobic alkyl chain and terminal hydroxyl, and its general formula is (CH
3)
3N
+(CH
2)
nOH, (CH
3)
2N
+[(CH
2)
nOH]
2, (CH
3)
2N
+[(CH
2)
mCH
3] [(CH
2)
nOH] or (C
6NH
5)
+[(CH
2)
nOH], wherein m, n are integer, and 5≤n≤18,5≤m≤18.
3. a kind of method for preparing the multi-metal oxygen cluster doped Nano particles of silicon dioxide as claimed in claim 1 is characterized in that: multi-metal oxygen cluster is Na
9[EuW
10O
36], K
11[Eu (PW
11O
39)
2], K
13[Eu (SiW
11O
39)
2], K
15[Eu (BW
11O
39)
2], K
12[EuP
5W
30O
110], H
3PMo
12O
40, H
4SiW
12O
40, K
12[NaP
5W
30O
110], H
3Na
9[Fe
4(H
2O)
2(P
2W
15O
56)
2], K
6CoSiW
11O
39, K
8Co
2W
12O
42, Na
8[HPW
9O
34] or Na
12[P
2W
15O
56].
4. a kind of method for preparing the multi-metal oxygen cluster doped Nano particles of silicon dioxide as claimed in claim 1, it is characterized in that: the homogeneous phase method for coating at first is that multi-metal oxygen cluster to be coated is soluble in water, in addition that the cationic surfactant of hydrophobic side hydroxyl is soluble in water, control both consumptions, make that the ratio of total electrical charge number of the total electrical charge number of surfactant and multi-metal oxygen cluster is 0.8～1: 1; Then, under stirring, the multi-metal oxygen cluster aqueous solution is added drop-wise in the aqueous surfactant solution, be added dropwise to complete the back and continue to stir 4～10 hours, collect the precipitation that reaction generates, be drying to obtain the multi-metal oxygen cluster electrostatic complexes that the hydroxyl cationic surfactant coats.
5. a kind of method for preparing the multi-metal oxygen cluster doped Nano particles of silicon dioxide as claimed in claim 1, it is characterized in that: organic and inorganic two-phase method for coating at first is that multi-metal oxygen cluster to be coated is soluble in water, cationic surfactant with the hydrophobic side hydroxyl is dissolved in the organic solvent in addition, control the two consumption, making the ratio of the total electrical charge number of the total electrical charge number of surfactant and multi-metal oxygen cluster is 0.8～1: 1; Then, under stirring, the organic solution of surfactant is added drop-wise in the multi-metal oxygen cluster aqueous solution, is added dropwise to complete the back and continues to stir after 4～10 hours and tell organic facies, and wash organic facies with water 3～5 times with separatory funnel; At last, organic facies is filtered and solvent evaporated, promptly obtain the multi-metal oxygen cluster electrostatic complexes that the hydroxyl cationic surfactant coats.
6. a kind of method for preparing the multi-metal oxygen cluster doped Nano particles of silicon dioxide as claimed in claim 5 is characterized in that: organic solvent is carrene, dichloroethanes, chloroform, benzene or toluene.
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