CN112521936A - Yolk-shell structured rare earth doped polymer/inorganic nano particle composite material and preparation method thereof - Google Patents
Yolk-shell structured rare earth doped polymer/inorganic nano particle composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a rare earth doped polymer/inorganic nano particle composite material with a yolk-shell structure and a preparation method thereof. Firstly, synthesizing two types of multi-arm monomers containing catechol groups and boric acid groups, then sequentially adding catechol group monomers and boric acid group monomers into a dispersion solution of inorganic nanoparticles, and controllably coating the surfaces of the inorganic nanoparticles to form a polymer shell layer by virtue of the interaction of the catechol groups and the surfaces of the inorganic nanoparticles and the B-N coordination driving force with directional identification formed between molecular chain segments, thereby obtaining a core-shell structure nano material; and then, adding rare earth ions into the system, and triggering collapse of a polymer network in a shell layer through coordination between the rare earth ions and a catechol group to finally form the composite material with the yolk-shell structure in situ. The composite material with the structure is expected to realize the antenna effect of the rare earth ions through a special core-cavity-shell structure, thereby enhancing and expanding the original fluorescence characteristics.
Description
Technical Field
The invention belongs to the field of hybrid nano materials, and particularly relates to a preparation technology of a rare earth doped polymer/inorganic nano particle composite material with a yolk-shell structure.
Background
Rare earth is regarded as an important support for new material manufacturing and a key source for advanced national defense technology development as a non-renewable strategic resource and is widely applied to high and new technical fields such as energy, photoelectricity and information. In the development of rare earth functional materials, rare earth luminescent materials have attracted particular attention due to their unique properties. Rare earth has spectral properties incomparable with common elements due to its special electronic layer structure. The rare earth element atoms have an unfilled 4f 5d electron configuration shielded by the outside, so that the rare earth element has rich electron energy levels and long-life excited states, can generate various radiation absorption and emission, and form a wide range of light-emitting and laser materials. However, since the f → f transition of the rare earth ion in the free state is forbidden, the fluorescence intensity induced by directly exciting the rare earth ion is very low. The energy level transition can be smoothly performed by the indirect sensitization process of the rare earth ions by the matrix or the organic ligand, so that characteristic light is emitted, namely, the antenna effect.
The research and development of the material with the novel heterostructure as the matrix or the ligand of the rare earth ions is the key for developing the novel rare earth luminescent material. The core-shell structure is an effective means for endowing materials with different qualities, and is characterized in that cores and shells with different compositions, performances and structures are controllably integrated through a physical or chemical method, so that the cores and the shells can not only retain independent physical and chemical properties, but also can cooperate with each other to realize performance synergism. Compared with the core-shell structure nano material, the unique cavity layer structure of the yolk-eggshell (yolk-shell) structure can fully expose the inner core while ensuring the protection of the shell layer to the inner core, enhance the movement capability of the inner core and the exchange of substances and energy of the inner core and the environment, and further play the synergistic effect of the inner core, the cavity and the shell layer.
Disclosure of Invention
The invention aims to provide a rare earth doped polymer/inorganic nano particle composite material with a yolk-shell structure and a preparation method thereof.
One of the technical schemes adopted by the invention for solving the technical problems is as follows:
a method for preparing a rare earth doped polymer/inorganic nano particle composite material with a yolk-shell structure comprises the following steps:
1) preparation of borate polymer @ inorganic nanoparticle composite material: dispersing inorganic nanoparticles in a first solvent, adding a catechol group-containing monomer obtained by reacting a polyamino compound with 3, 4-dihydroxybenzaldehyde, and stabilizing for 0.5-2 h; then adding a boric acid group-containing monomer obtained by reacting a polyamino compound with 4-formylphenylboronic acid into a system, and carrying out condensation reaction for 1-3 h at 10-50 ℃ to obtain a borate polymer @ inorganic nanoparticle composite material; the inorganic nano particles comprise at least one of zinc oxide, silicon dioxide, titanium dioxide, ferric oxide, ferroferric oxide, cuprous oxide or gold nano particles;
2) the preparation of the rare earth doped polymer @ hollow @ inorganic nanoparticle composite material comprises the following steps: dispersing the borate polymer @ inorganic nanoparticle composite material in a second solvent, adding rare earth salt into the second solvent, and reacting at 10-50 ℃ for 1-12 h to obtain a rare earth doped polymer/inorganic nanoparticle composite material with a yolk-shell structure, wherein the rare earth doped polymer/inorganic nanoparticle composite material is marked as a rare earth doped polymer @ hollow @ inorganic nanoparticle composite material.
Further, the preparation method also comprises the preparation of the multi-arm monomer: performing Schiff base formation reaction on a polyamino compound and 3, 4-dihydroxy benzaldehyde at 10-50 ℃ in a dark place for 12-48 h to obtain a catechol group-containing monomer; and (3) carrying out Schiff base formation reaction on the polyamino compound and 4-formylphenylboronic acid at 10-50 ℃ in a dark place for 12-48 h to obtain the boric acid group-containing monomer.
Wherein the molar ratio of the polyamino-containing compound to 3, 4-dihydroxybenzaldehyde may be 1: (2-4); the molar ratio of the polyamino compound to 4-formylphenylboronic acid may be 1: (2-4).
Wherein the polyamino-containing compound comprises at least one of ethylenediamine, p-phenylenediamine, benzidine, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, tris (2-aminoethyl) amine, tris (4-aminophenyl) ammonia, 1,3, 5-tris (4-aminophenyl) benzene, 5 "- (4 '-amino [1,1' -biphenyl ] -4-yl) [1,1':4', 1": 3 ", 1": 4 "', 1" "-pentabiphenyl ] -4, 4"' -diamine, 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin, N, N ', N' -tetrakis (p-aminophenyl) p-phenylenediamine. The polyamino group-containing compound for preparing the catechol group-containing monomer and the polyamino group-containing compound for preparing the boronic acid group-containing monomer are each independently selected from the above-mentioned compounds, i.e., they may be the same or different.
Different polyamino compounds react with 3, 4-dihydroxy benzaldehyde and 4-formyl phenylboronic acid respectively to obtain different o-catechol group-containing monomers and boric acid group-containing monomers respectively. For example:
ethylene diamine and 3, 4-dihydroxybenzaldehyde can be prepared into DEC, and 4-formyl phenylboronic acid can be prepared into DEB;
preparing DC from p-phenylenediamine and 3, 4-dihydroxybenzaldehyde, and preparing DB from 4-formylphenylboronic acid;
the benzidine and 3, 4-dihydroxy benzaldehyde can be used for preparing BC, and the benzidine and 4-formyl phenylboronic acid can be used for preparing BB;
DFC can be prepared from 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane and 3, 4-dihydroxybenzaldehyde, and DFB can be prepared from 4-formylphenylboronic acid;
TEC can be prepared from tris (2-aminoethyl) amine and 3, 4-dihydroxybenzaldehyde, and TEB can be prepared from 4-formylphenylboronic acid;
TAC is prepared from tris (4-aminophenyl) amine and 3, 4-dihydroxybenzaldehyde, and TAB is prepared from 4-formylphenylboronic acid;
TBC is obtained by reacting 1,3, 5-tris (4-aminophenyl) benzene with 3, 4-dihydroxybenzaldehyde and TBB is obtained by reacting 4-formylphenylboronic acid;
5 ' - (4' -amino [1,1' -biphenyl ] -4-yl) [1,1':4', 1': 3 ', 1':4', 1' -pentabiphenyl ] -4, 4' -diamine with 3, 4-dihydroxybenzaldehyde to give TQC, and 4-formylphenylboronic acid to give TQB;
preparing PC from 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 3, 4-dihydroxybenzaldehyde, and preparing PB from 4-formylphenylboronic acid;
TPC is prepared from N, N, N ', N' -tetra (p-aminophenyl) p-phenylenediamine and 3, 4-dihydroxybenzaldehyde, and TPB is prepared from 4-formylphenylboronic acid.
Further, in the step 1), the molar ratio of the catechol-group-containing monomer to the boronic acid-group-containing monomer may be 1: (0.5 to 2);
further, in the step 1), after the catechol group-containing monomer is added into the first solvent in which the inorganic nanoparticles are dispersed, the concentration of the catechol group-containing monomer in the system is 0.1-1 mg/mL. Preferably, the concentration of the catechol group-containing monomer in the system is 0.7-0.9 mg/mL; under the condition, the obtained rare earth doped polymer/inorganic nano particle composite material can form an obvious yolk-shell structure.
Further, in the step 2), the rare earth salt includes at least one of a halide salt, a nitrate salt, a sulfate salt, an oxalate salt, a phosphate salt or a silicate salt of a rare earth metal element. The rare earth metal element includes lanthanoid elements and seventeen kinds of scandium, yttrium, and the like, and specifically includes at least one of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y), or scandium (Sc).
Further, the molar ratio of the rare earth salt to the catechol-group-containing monomer is 1-3: 2-4.
Further, in the step 1), the reaction of the polyamino group-containing compound with 3, 4-dihydroxybenzaldehyde is carried out in a third solvent; the reaction of the polyamino-containing compound with 4-formylphenylboronic acid is carried out in a fourth solvent.
The first solvent, the second solvent, the third solvent and the fourth solvent are respectively and independently selected from at least one of alcohols, DMF, DMSO and the like. The alcohol comprises at least one of methanol or ethanol.
The second technical scheme adopted by the invention for solving the technical problems is as follows:
a rare earth doped polymer/inorganic nano particle composite material has a yolk-shell structure, takes inorganic nano particles as a core and takes rare earth doped borate polymer as a shell; the inorganic nano particles comprise at least one of zinc oxide, silicon dioxide, titanium dioxide, ferric oxide, ferroferric oxide, cuprous oxide or gold nano particles.
The rare earth doped polymer/inorganic nano particle composite material can be prepared by the preparation method.
According to the invention, a catechol group-containing monomer and a boric acid group-containing monomer are sequentially added into a dispersion solution of inorganic nanoparticles, a borate polymer shell layer is formed on the surface of the inorganic nanoparticles by virtue of the interaction of catechol groups and the surface of the inorganic nanoparticles and the B-N coordination driving force with directional recognition formed between molecular chain segments, the inorganic nanoparticles are coated with the borate polymer shell layer in a controllable manner to prepare a core-shell structure nano material, and then the collapse of a polymer network in the shell layer is initiated by utilizing the coordination of rare earth ions and catechol to be doped into the core-shell material, so that the material exchange is further carried out, and a unique yolk-shell structure is formed in situ. The yolk-shell structure can simultaneously expose inorganic nano particles as the inner core and can play the roles of the cavity layer and the shell layer in a synergistic manner. The rare earth ions are expected to realize the antenna effect by virtue of the special core-cavity-shell structure, so that the fluorescence characteristics of the rare earth ions are enhanced.
The equipment, reagents, processes, parameters and the like related to the invention are conventional equipment, reagents, processes, parameters and the like except for special description, and no embodiment is needed.
All ranges recited herein include all point values within the range.
Due to the application of the technical scheme, the rare earth doped polymer/inorganic nano particle composite material with the yolk-shell structure, which is prepared by the invention, has the following characteristics:
(1) the rare earth doped polymer nano composite material with the yolk-shell structure and the excellent fluorescence property is synthesized, and the inorganic core or the organic shell is used as a matrix or a ligand to realize the indirect sensitization of rare earth ions, so that the fluorescence characteristic of the rare earth ions is induced and initiated under a specific condition.
(2) The invention is established on a borate polymer with B-N coordination characteristics, and has the characteristics of controllable coating, changeable inorganic core, suitability for various rare earth sources and the like.
(3) The invention can adjust the excitation spectrum and the fluorescence intensity of the rare earth ions by the change of the structure and the composition while initiating the characteristic light emission of the rare earth ions.
Drawings
FIGS. 1(a) to 1(c) are chemical structural formulas of a catechol group-containing monomer and a boronic acid group-containing monomer involved in the present invention, wherein FIG. 1(a) is a structural formula of DEC, DEB, DC, DB, BC, BB, DFC, DFB, wherein FIG. 1(b) is a structural formula of TEC, TEB, TAC, TAB, TBC, TBB, TQC, TQB, and wherein FIG. 1(c) is a structural formula of PC, PB, TPC, TPB.
FIG. 2 is a TEM image of pure zinc oxide (a), borate polymer @ zinc oxide (b) obtained at a BC concentration of 0.1mg/mL, borate polymer @ zinc oxide (c) obtained at a BC concentration of 0.25mg/mL, and borate polymer @ zinc oxide (d) obtained at a BC concentration of 0.5mg/mL in example 1. Scales in the figure are (a)100nm in sequence; (b)50 nm; (c)50 nm; (d)50 nm.
FIG. 3 is an XRD data for pure zinc oxide and borate polymer @ zinc oxide obtained at BC concentrations of 0.1mg/mL, 0.25mg/mL, 0.5mg/mL for example 1.
FIG. 4 is a TbCl doped borate polymer based on 0.5mg/mL and 0.75mg/mL BC concentration at @ zinc oxide in example 13: and (b) obtaining a TEM picture of the rare earth doped polymer/inorganic nano particle composite material with the yolk-shell structure, wherein BC is 2:3 (the proportion is a molar ratio, and the pictures are a picture and a picture b from left to right in sequence). Scales in the figure are (a)100nm in sequence; (b)200 nm.
Detailed Description
The invention is further illustrated by the following figures and examples.
Example 1
Firstly, preparing multi-arm monomers BC and BB:
(1) benzidine (0.092g, 0.5mmol) and 3, 4-dihydroxybenzaldehyde (0.138g, 1mmol) were dissolved in 20mL ethanol and the reaction was stirred at 400rpm in the dark at 25 ℃ for 24 hours. Kinetic studies samples were taken at set time intervals for GPC and NMR testing. And after the reaction is finished, centrifugally washing the reactant for three times by using ethanol, and drying the reactant in vacuum to obtain orange powder, namely the catechol group-containing two-arm monomer BC.
(2) Benzidine (0.092g, 0.5mmol) and 4-formylphenylboronic acid (0.15g, 1mmol) were dissolved in 20mL of methanol and the reaction was stirred at 400rpm in the dark at 25 ℃ for 24 h. Kinetic studies samples were taken at set time intervals for GPC and NMR testing. And after the reaction is finished, centrifugally washing the mixture for three times by using methanol, and drying the mixture in vacuum to obtain yellow powder, namely the boric acid group-containing two-arm monomer BB.
Preparation of a BC/BB borate polymer @ inorganic nanoparticle composite material:
(1) 4g of zinc oxide is dispersed in 20mL of ethanol, and then is centrifugally washed three times by the ethanol, and the pretreatment of the zinc oxide is finished after vacuum drying.
(2) Dividing the pretreated zinc oxide into four parts, wherein each part is 1g, respectively dispersing the four parts in 20mL of ethanol, sequentially adding a certain amount of BC according to final concentrations of 0.1mg/mL, 0.25mg/mL, 0.5mg/mL and 0.75mg/mL, and stirring at the speed of 400rpm at the temperature of 25 ℃ for reaction for 1 hour; then adding a certain amount of BB according to the same concentration and content of the added BC under the same conditions to ensure that the final concentration of the BB is 0.1mg/mL, 0.25mg/mL, 0.5mg/mL and 0.75mg/mL respectively; the reaction was stirred at 400rpm for 3 hours at 25 ℃. After the reaction is finished, centrifugally washing the mixture for three times by using ethanol, and drying the mixture in vacuum to obtain the BC/BB boric acid ester polymer @ zinc oxide composite material.
Thirdly, preparing the Tb doped polymer @ air @ zinc oxide composite material:
(1) the BC/BB borate polymer @ zinc oxide composite prepared under the conditions of final BC concentrations of 0.1mg/mL, 0.25mg/mL, 0.5mg/mL and 0.75mg/mL was taken and dissolved in 20mL of ethanol, each 0.3 g.
(2) Taking a certain amount of terbium chloride according to TbCl3: terbium chloride was added to the four solutions in (1) at a BC molar ratio of 2:3, and the reaction was stirred at 400rpm for 3 hours at 25 ℃. After the reaction is finished, centrifugally washing the mixture for three times by using ethanol, and drying the mixture in vacuum to obtain the Tb doped polymer @ air @ zinc oxide composite material.
Example 2
Preparation of multi-arm monomer TBC and TBB:
(1) 1,3, 5-tris (4-aminophenyl) benzene (0.117g, 0.334mmol) was dissolved in a mixed solution of 4mL of methylene chloride and 6mL of ethanol, 3, 4-dihydroxybenzaldehyde (0.138g, 1mmol) was dissolved in 10mL of ethanol, and then the two were mixed and the reaction was stirred at 400rpm for 24 hours at 25 ℃ under the exclusion of light. Kinetic studies samples were taken at set time intervals for GPC and NMR testing. And after the reaction is finished, removing the solvent by rotary evaporation, and drying in vacuum to obtain red powder, namely the three-arm monomer TBC containing the catechol group.
(2) 1,3, 5-tris (4-aminophenyl) benzene (0.117g, 0.334mmol) was dissolved in a mixed solution of 4mL of methylene chloride and 6mL of ethanol, 4-formylphenylboronic acid (0.15g, 1mmol) was dissolved in 10mL of ethanol, and then the two were mixed and the reaction was stirred at 400rpm for 24 hours at 25 ℃ under exclusion of light. Kinetic studies samples were taken at set time intervals for GPC and NMR testing. And after the reaction is finished, removing the solvent by rotary evaporation, and drying in vacuum to obtain orange powder, namely the boric acid group-containing three-arm monomer TBB.
Preparation of TBC/TBB borate polymer @ silica composite:
(1) 4g of silicon dioxide is dispersed in 20mL of ethanol, and then the silicon dioxide is centrifugally washed three times by the ethanol and is dried in vacuum, so that the pretreatment of the silicon dioxide is finished.
(2) Dividing the pretreated silicon dioxide into four parts, wherein each part is 1g, dispersing the silicon dioxide into 20mL of ethanol, sequentially adding a certain amount of TBC according to final concentrations of 0.1mg/mL, 0.2mg/mL, 0.3mg/mL and 0.4mg/mL, and stirring at the speed of 400rpm at 25 ℃ for reaction for 1 hour; then, under the same conditions, TBB was added in such amounts that the TBC was fed in the same concentration and content as the TBC to give final TBB concentrations of 0.1mg/mL, 0.2mg/mL, 0.3mg/mL and 0.4mg/mL, respectively, and the reaction was stirred at 400rpm at 25 ℃ for 3 hours. After the reaction is finished, centrifugally washing the reaction product for three times by using ethanol, and drying the reaction product in vacuum to obtain the TBC/TBB borate polymer @ silicon dioxide composite material.
Thirdly, preparing the Eu-doped polymer @ hollow @ silicon dioxide composite material:
(1) 0.3g each of the TBC/TBB borate polymer @ silica composites prepared at the above TBC final concentrations of 0.1mg/mL, 0.2mg/mL, 0.3mg/mL and 0.4mg/mL were taken and dissolved in 20mL of ethanol.
(2) Taking a certain amount of europium chloride according to EuCl3: the solution in (1) was charged with europium chloride at a molar ratio of TBC of 1:1, and the reaction was stirred at 400rpm at 25 ℃ for 3 hours. After the reaction is finished, centrifugally washing the Eu-doped polymer @ hollow @ silicon dioxide composite material for three times by using ethanol, and drying the Eu-doped polymer @ hollow @ silicon dioxide composite material in vacuum.
Examples 3 to 5: the process conditions of example 1 were the same, and the types of catechol group-containing monomers and boronic acid group-containing monomers were changed during the production of boronic acid esters, and the results are shown in table 1.
TABLE 1 formulations of examples 3-5
Examples 6 to 9: different kinds of composite materials were synthesized by changing the kind of rare earth salt during the rare earth ion doping process under the same process conditions as in example 1, and the results are shown in Table 2.
TABLE 2 formulations of examples 6-9
Examples 10 to 12: different kinds of composite materials were synthesized by changing the kind of the inorganic nanoparticles as the inner core under the same process conditions as in example 2, and the results are shown in Table 3.
TABLE 3 formulations of examples 10-12
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a chemical structural formula of a multi-arm monomer involved in the invention, and a series of monomers with end groups of catechol group and boric acid group are synthesized mainly by virtue of Schiff base formation reaction for subsequent synthesis of borate.
FIG. 2 is TEM images of BC/BB borate polymer @ zinc oxide composite materials prepared from pure zinc oxide in example 1 and three types of inorganic nanocore prepared from zinc oxide at different BC/BB concentrations. The picture (a) shows pure zinc oxide, the visible surface is smooth, and no shell layer is visible; based on pure zinc oxide, the graphs (b) - (d) were sequentially dosed with 0.1mg/mL, 0.25mg/mL, 0.5mg/mL final concentration BC and the corresponding amount of BB to form borate polymers. As can be seen, the shell thickness gradually increased with increasing concentration of BC/BB, which was 2.8nm, 5.5nm, and 20.9nm, respectively.
FIG. 3 is an XRD spectrum of pure zinc oxide from example 1 and a BC/BB borate polymer @ zinc oxide prepared under conditions of 0.1mg/mL, 0.25mg/mL, a final concentration of BC of 0.5mg/mL and the corresponding amount of BB. It can be seen that the XRD characteristic peak intensity of the composite material is gradually enhanced along with the gradual increase of the shell layer, which shows that the thickness of the polymer shell layer has certain influence on the crystal structure of the inorganic nanometer core, and the influence is gradually increased along with the increase of the shell layer thickness. This result also laterally demonstrates the feasibility of borate polymers for controlled encapsulation of inorganic nanomaterials.
FIG. 4 is a BC/BB borate polymer @ zinc oxide composite prepared in example 1 based on 0.5mg/mL and 0.75mg/mL final BC concentration and corresponding amounts of BB under the preparation conditions according to TbCl3: TEM image of yolk-shell structure composite material obtained under BC molar ratio of 2: 3. It can be seen that the cavities in panel a are small, with only a thin layer near the zinc oxide core; the cavity layer is very obvious in the graph b, and yolk-sh is formedell structure.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (10)
1. A method for preparing a rare earth doped polymer/inorganic nano particle composite material with a yolk-shell structure is characterized by comprising the following steps: the method comprises the following steps:
1) dispersing inorganic nanoparticles in a first solvent, adding a catechol group-containing monomer obtained by reacting a polyamino compound with 3, 4-dihydroxybenzaldehyde, adding a boric acid group-containing monomer obtained by reacting a polyamino compound with 4-formylphenylboronic acid after 0.5-2 h, and reacting at 10-50 ℃ for 1-3 h to obtain a borate polymer @ inorganic nanoparticle composite material; the inorganic nano particles comprise at least one of zinc oxide, silicon dioxide, titanium dioxide, ferric oxide, ferroferric oxide, cuprous oxide or gold nano particles;
2) and dispersing the borate polymer @ inorganic nanoparticle composite material in a second solvent, adding rare earth salt into the second solvent, and reacting for 1-12 h at 10-50 ℃ to obtain the rare earth doped polymer/inorganic nanoparticle composite material with the yolk-shell structure.
2. The method of claim 1, wherein: in the step 1), the polyamino compound and 3, 4-dihydroxy benzaldehyde react at 10-50 ℃ in a dark place for 12-48 h to obtain the catechol group-containing monomer, wherein the molar ratio of the polyamino compound to the 3, 4-dihydroxy benzaldehyde is 1: 2-4; the polyamino compound and 4-formyl phenylboronic acid react at 10-50 ℃ in a dark place for 12-48 hours to obtain the boric acid group-containing monomer, wherein the molar ratio of the polyamino compound to the 4-formyl phenylboronic acid is 1: 2 to 4.
3. The method of claim 1, wherein: in the step 1), the polyamino group-containing compound includes at least one of ethylenediamine, p-phenylenediamine, benzidine, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, tris (2-aminoethyl) amine, tris (4-aminophenyl) ammonia, 1,3, 5-tris (4-aminophenyl) benzene, 5 "- (4 '-amino [1,1' -biphenyl ] -4-yl) [1,1':4', 1": 3 ", 1" ':4 "', 1" "-pentabiphenyl ] -4, 4" '-diamine, 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin, or N, N' -tetrakis (p-aminophenyl) p-phenylenediamine.
4. The method of claim 1, wherein: in the step 1), the molar ratio of the catechol group-containing monomer to the boric acid group-containing monomer is 1: 0.5 to 2.
5. The method of claim 1, wherein: in the step 1), after the catechol group-containing monomer is added into the first solvent in which the inorganic nanoparticles are dispersed, the concentration of the catechol group-containing monomer in the system is 0.1-1 mg/mL.
6. The method of claim 1, wherein: the concentration of the catechol group-containing monomer in the system is 0.7-0.9 mg/mL.
7. The method of claim 1, wherein: the molar ratio of the rare earth salt to the catechol-group-containing monomer is 1-3: 2-4.
8. The method of claim 1, wherein: the rare earth salt includes at least one of a halide salt, a nitrate salt, a sulfate salt, an oxalate salt, a phosphate salt or a silicate salt of a rare earth metal element.
9. The method of claim 1, wherein: in the step 1), the reaction of the polyamino-containing compound with 3, 4-dihydroxybenzaldehyde is carried out in a third solvent; the reaction of the polyamino-containing compound and the 4-formylphenylboronic acid is carried out in a fourth solvent; the first solvent, the second solvent, the third solvent and the fourth solvent are respectively and independently selected from at least one of alcohols, DMF or DMSO.
10. A rare earth doped polymer/inorganic nanoparticle composite material is characterized in that: the composite material has a yolk-shell structure, takes inorganic nano particles as a core and takes a rare earth doped borate polymer as a shell; the inorganic nano particles comprise at least one of zinc oxide, silicon dioxide, titanium dioxide, ferric oxide, ferroferric oxide, cuprous oxide or gold nano particles.
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| CN115991935A (en) * | 2022-07-19 | 2023-04-21 | 厦门大学 | Core-shell structure supermolecule-based dielectric elastomer composite material and preparation method and application thereof |
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2020
- 2020-11-11 CN CN202011255621.6A patent/CN112521936A/en active Pending
Non-Patent Citations (3)
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| TAHA MOHAMED等: "Complexation and molecular modeling studies of europium(III)-gallic acid-amino acid complexes", 《JOURNAL OF INORGANIC BIOCHEMISTRY》 * |
| WU YUZHE等: "An etching approach to bimetal-doped hollow carbon nanospheres with boosted oxygen reduction reaction", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 李雅缨: "硼酸酯聚合物可控包覆无机纳米粒子及其金属离子刻蚀", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115991935A (en) * | 2022-07-19 | 2023-04-21 | 厦门大学 | Core-shell structure supermolecule-based dielectric elastomer composite material and preparation method and application thereof |
| CN115991935B (en) * | 2022-07-19 | 2024-01-26 | 厦门大学 | Core-shell structure supermolecule-based dielectric elastomer composite material and preparation method and application thereof |
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Application publication date: 20210319 |