CN102500297A - Method for preparing multifunctional nano microspheres (MPS) by utilizing drain nano particle self-assembly - Google Patents
Method for preparing multifunctional nano microspheres (MPS) by utilizing drain nano particle self-assembly Download PDFInfo
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Abstract
The invention relates to multifunctional nano microspheres (MPS) prepared by utilizing drain nano particle self-assembly, a preparation method thereof and dispersion thereof in water. The multifunctional nano MPS are prepared by (3-sulfydryl) propyltrimethoxyl silane, and the selected self-assembled drain particles are under 30nm. According to the invention, MPS are prepared, and the MPS and the drain particles produce self-assembly, so that the multifunctional nano MPS can be prepared, and further, the prepared multifunctional nano MPS are packaged by carbon dioxide so that the finally-obtained MPS can be uniformly dispersed in water solution. In the method disclosed by the invention, the drain nano particles are free from hydrophily modification before and during the self-assembly, and finally, the obtained nano material has better chemical/mechanical stability and water dispersibility so that the current requirements can be met.
Description
Technical field
The present invention relates to field of nanometer material technology, particularly relate to a kind of multifunctional nano microballoon that utilizes dewatering nano particle self assembly preparation and preparation method thereof and the dispersion in water.
Background technology
Be of a size of micron or sub-micron grade, the multi-functional particle with two or more character is the technical applications desirable material, can be used for collection of energy conversion, multimodal transport imaging, detection and diagnosis and treatment field.For example, the nano particle microballoon that embeds magnetic oxide and fluorescence quantum combines magnetic resonance imaging contrast can realize optical detection and biological targeting as multi-mode, and this technology has obtained broad research at present.Through the quantum dot that strictness control is written into, the compound particle that obtains possesses optics and the separable bi-functional of magnetic.Change quantum dot into inert metal and then can prepare novel new material with magnetic resonance and photo-thermal therapy function.Magnetic material can also be with nanocatalyst in conjunction with forming the separable nanocatalyst of magnetic, can realize the recovery of valuable catalyst after the catalytic reaction like this, reduces the expense gap of homogeneous catalysis and heterogeneous catalysis.
The nano particle self assembly is that a kind of preparation is difunctional, three functions and multifunctional material method effectively easily, and the composite for preparing has overcome the defective of single component material.Through inhomogeneous particle is combined, not only kept the function of single particle based on size and pattern, can also obtain the new property that interacts and produce owing between the particle.The preparation method of traditional multifunction structure for example layer-layer assemble method only is confined to the dewatering nano particle, because it depends on electrostatic interaction strongly.Nano particle was also once attempted through the direct-connected method of chemical bond layer by layer, but only limited to some special circumstances.Because not containing activity functional groups, the coordination particle that uses under most of situation do not make it that further reaction can take place.
CN 1746105 A disclose and have utilized multi-component nanometer tube with laminated assembling technology structure, as utilize between two kinds of materials between reactions and two kinds of materials of different electrically absorption and can act on the prepared in reaction multi-component nanometer tube between group.This material comprises: have electropositive and electronegative compound or biomolecule, with the positive and negative charge adelphotaxy, form the nanotube of polyelectrolyte.And have amino compound or biomolecule, with have the compound or the biomolecule of anhydride group (or carboxyl or acyl chlorides etc.); Adopt the method for chemical bonding; Make between the compound of amino and acid anhydrides (or carboxyl or acyl chlorides) and form amido link, the nanotube of formation even tube wall, stable in properties.This invention forms multi-component nanotube through the layer assembly method.Especially utilizing the nanotube that chemical action forms between two kinds of materials, is to do substrate by the good polymer substance of film forming, and functionalization material uniform spreading that can filming performance is bad makes it to have groups such as light functionalization, electric functionalization.
A lot of important high quality nano particles of technical field; Especially semiconductor (for example cadmium selenide, zinc selenide, cadmium antimonide) and metal oxide are (like γ-di-iron trioxide; Manganese oxide, titanium dioxide, zirconium dioxide) mainly obtain (general temperature is 150-320 ℃) through inorganic matter precursor Pintsch process in organic solvent.This preparation process makes the nano particle that finally prepares keep original hydrophobicity, and is water insoluble.Therefore be difficult to its self assembly as water-soluble molecules is formed functionalized particles.General, need hydrophobic grouping be become hydrophilic radical to increase its dispersiveness in water in nanoparticle surface.Announce a kind of preparation method of self-assembly nano-crystalline titanium dioxide film like CN 101830641 A, followed these steps to operation: (1) TiCl
4The preparation of the precursor aqueous solution of alcohol system; (2) cleaning of substrate base; (3) self assembly of nano-crystalline titanium dioxide film and post processing; (4) self assembly of double-layer nanometer crystal titanium dioxide film and post processing.The nano-crystalline titanium dioxide film form of self assembly preparation of the present invention is regular, well arranged, hole is many, one-tenth is network-like, do not have be full of cracks; And film performance is good; Be specially adapted to DSSC, the method for this self assembly can also obtain the nano-titanium dioxide powder byproduct.This preparation method's characteristics are that technology is simple, cheap, environmental friendliness, be suitable for large-scale production.Yet the process of ligand modification relates generally to several processes, and in most of the cases these all can produce adverse influence to the physical property of nano particle, because new hydrophilic part possibly effectively isolated inorganic core portion and water environment.For example, adopt the various hydrophilic surperficial hydrophobic TOPOs of ligand exchange CdSe/ZnS, all can cause the remarkable reduction of quantum efficiency.And, thereby the reunion and the deposition of new ligand can be gradually from the nano particle desorption causes nano particle.The more important thing is that need be used as self assembly if surpass a kind of nano particle, every kind of nano particle all will carry out surface modification separately before assembling.
Have strong coordination between alkanethiol and the metal surface, this content has obtained broad research and in the self assembly of metal surface monofilm forms, has used to some extent.There is research report alkanethiol can be adsorbed on metal oxide surface (like titanium dioxide, zinc oxide and tin ash) and semi-conducting material (indium phosphide, indium arsenide, indium gallium).Announced a kind of method of coating metal surfaces like CN 1664167 A, its be with the solution coat that contains alkanethiol compound and solvent to the metal surface, form the monolayer of self assembly, as firm anticorrosive barrier.The general formula of said alkanethiol compound is R (CH
2)
nSH, R is methyl, carboxyl, hydroxyl, formoxyl or amide groups in the formula, n is 7～21, is preferably 12～18.Recently, utilized the interaction of mercaptan-metal that nano particle is fixed on the solid matter of alkanethiol modification, and these effects have further been extended on the colloidal particle through golden nanometer particle is self-assembled to the silicon dioxide colloid of thiol functionization.But, also do not utilize the interaction preparation of mercaptan and metal to have the straightforward procedure of good water dispersible nano particle at present.
Therefore, be sought after developing a kind of simple and pervasive self-assembling method, can directly various hydrophobic nano particles be carried out self assembly and prepare the multifunctional nano structure.Because the main application of these particles is at biomedical sector, the composite construction nano particle that therefore final assembling is come out need have good dispersiveness in water.
The present invention relates to a pervasive and effective self-assembling method, available self-assembling method directly utilizes the dewatering nano particle preparation to go out the nano composite material of multifunction.This dewatering nano particle does not need hydrophilically modified before the self assembly and in the self assembling process, and the nano material that finally obtains has good chemical/mechanical stability and water dispersible.
Summary of the invention
To the deficiency of prior art, one of the object of the invention is to provide a kind of method of utilizing the self assembly of dewatering nano particle to prepare the multifunctional nano microballoon.
Said method comprising the steps of:
(1) preparation MPS microballoon: the MPS microballoon joins NH through the one-step method preparation with (3-sulfydryl) propyl trimethoxy silicane (MPS)
4Mix in the aqueous solution of OH, the solution that obtains is placed (comprised 3 hours) more than 3 hours and obtain the MPS microballoon, flushing MPS microballoon, and it is distributed to obtains MPS solution in the solvent;
(2) preparation MPS-self assembly hydrophobic particles hybrid microspheres: in the solution of self assembly hydrophobic particles, add the MPS solution that step (1) makes, mix back generation self assembly and can obtain MPS-self assembly hydrophobic particles hybrid microspheres.
Thereby one of the object of the invention also is to provide a kind of multifunctional nano microballoon with dewatering nano particle self assembly preparation to handle the method for disperseing in the realization aqueous solution.
Said method is characterized in that, carries out step afterwards in above-mentioned steps (2):
(3) coated with silica MPS-self assembly hydrophobic particles hybrid microspheres: use
Method is transferred to the ethanol/H that contains silica and surfactant with the microballoon for preparing in the step (2)
2O/NH
3In the solution, make its mixing can obtain the multifunctional nano microballoon.
Preferably, MPS adds with the solution form in the step (1), and solvent is an alcohols, further is preferably C
1-C
5Alcohols is preferably propyl alcohol or isopropyl alcohol or its mixture especially.
Preferably, MPS and NH described in the step (1)
4The ratio of the amount of substance of OH is 0.5: 1～4: 1, further is preferably 0.5: 1～3: 1, is preferably 0.5: 1～1.5: 1 especially.
Preferably, be mixed into the micro oscillation mode of using described in the step (1); Rotating speed is 500rpm～4000rpm, is preferably 1000rpm～3000rpm especially; Duration of oscillation is more than the 2min, is preferably 2min～8min especially.
Preferably, laying temperature is a normal temperature described in the step (1).
Preferably, be (to comprise 4 hours) more than 4 hours standing time described in the step (1), further is preferably 4～15 hours, is preferably 4～12 hours especially.
Preferably, MPS microballoon described in the step (1) adopts C
1-C
8Alcohols or the flushing of its mixture further are preferably C
1-C
3Alcohols or its mixture, for example methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or its mixture are preferably ethanol especially.
Preferably, solvent is a non-polar solven described in the step (1), further is preferably toluene, nonpolar alkane or its mixture, is preferably toluene, n-hexane, cyclohexane, normal heptane or its mixture especially.
Preferably, the self assembly hydrophobic particles is γ-Fe described in the step (2)
2O
3, Au, Ag, Pd, ZrO
2, TiO
2, MnO
2, SnO
2Or its combination, be preferably γ-Fe especially
2O
3, Au, ZrO
2, TiO
2Or its combination.
Preferably, self assembly hydrophobic particles particle diameter is below the 30nm described in the step (2), further is preferably below the 25nm, is preferably 1～20nm especially.
Preferably, described in the step (2) in the solution of self assembly hydrophobic particles solvent be non-polar solven, further be preferably toluene, nonpolar alkane or its mixture, be preferably toluene, n-hexane, cyclohexane, normal heptane or its mixture especially.
Preferably, described in the step (2) in the mixed solution ratio of self assembly hydrophobic particles and MPS microballoon amount of substance be 0.3: 1～3: 1, further be preferably 1: 1～3: 1, be preferably 2: 1～3: 1 especially.
Preferably; Surfactant described in the step (3) be anion surfactant or/and zwitterionic surfactant or/and non-ionic surface active agent; Further be preferably higher fatty acids or/and its esters, sulfonic acid or/and its esters, higher aliphatic sulfuric acid ester, lecithin, fatty acid glycerine lipid or its mixture, more preferably stearic acid, neopelex, lauryl sodium sulfate, lecithin, glycerin monostearate or its mixture.
Preferably, being mixed into vibration described in the step (3) mixes.
In the step (1), one of ordinary skill in the art can be according to the professional knowledge of grasping, and through the adjustment preparation condition, the microballoon that obtains can be controlled in 150nm～3.5 μ m, and has single dispersiveness.
In the step (2), the microballoon size that after the air drying, obtains microballoon size basic and step (1) is suitable, and difference is about (190 ± 28) nm～(3.5 ± 0.21) μ m.
In the step (3), said multifunctional nano microballoon can evenly disperse in the aqueous solution.
One of the object of the invention is the multifunctional nano microballoon that provides a kind of self assembly to obtain.
Said multifunctional nano microballoon is by the said method of preamble, and promptly step (1), (2), (3) make.
The main body microballoon of said multifunctional nano microballoon is prepared by (3-sulfydryl) propyl trimethoxy silicane; The self assembly hydrophobic particles of being selected for use is γ-Fe
2O
3, Au, Ag, Pd, ZrO
2, TiO
2, MnO
2, SnO
2Or its combination, its particle diameter is below the 30nm.
Preferred said self assembly hydrophobic particles is γ-Fe
2O
3, Au, ZrO
2, TiO
2Or its combination.
Preferred said self assembly hydrophobic particles particle diameter is below the 25nm, is preferably 1～20nm especially.
Said
Method is an affiliated field known technology, is
Deng the monodispersed SiO of preparation in alcoholic solution that proposes in nineteen sixty-eight
2The method of microballoon realizes the sol-gel process to the nano particle parcel.One of ordinary skill in the art can confirm the ratio of ethanol, water, ammoniacal liquor according to the professional knowledge of being grasped.
In the process of this invention preparation microballoon, need not carry out chemical modification, thereby the final functionalization complex microsphere that obtains has well kept the character of nanoparticle to hydrophobic nanoparticles.And the microballoon that finally prepares can well be distributed in the aqueous solution, reaches the fundamental property demand that biomedical sector is used.This invention is not only simple and easy to operate, and novelty is strong, and easy-regulating can be prepared the multi-functional microballoon of a series of narrow distributions in very wide size range flexibly.
The specific embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment 1
(1) preparation MPS microballoon: the MPS microballoon is through the one-step method preparation, is that the aqueous isopropanol of (3-sulfydryl) propyl trimethoxy silicane (MPS) of 12.5mM joins 12.5mL NH with 300 μ L concentration
4OH concentration be use in the aqueous solution of 0.075mM IKA MS3 microoscillator under the 2500rpm rotating speed with forced oscillation 2 minutes.The solution that obtains was placed 4 hours at normal temperatures.The product that obtains at last is distributed to product then and obtains MPS solution in the 100mL toluene with alcohol flushing 2 times.The MPS microballoon that obtains at last is of a size of 869nm.
(2) preparation MPS-Au hybrid microspheres: 2500 μ L diameters are that the concentration of the gold grain of 10nm is the toluene solution of 0.45mM, in above-mentioned solution, add the MPS microspheres solution for preparing in the step (1) then.Mix back generation self assembly and can obtain microballoon.The microballoon that after the air drying, obtains is 1059nm.This microballoon can not be distributed in the water again, can only be distributed in organic solvent such as the toluene.
(3) coated with silica MPS-Au hybrid microspheres: use
Method, with the particle transfer for preparing in (2) to the ethanol/H that contains silica and surfactant SDS lauryl sodium sulfate
2O/NH
3In the solution, slight vibration makes its mixing can obtain the multifunctional hydrophilic hybrid microspheres.This microballoon can evenly disperse in the aqueous solution.
Embodiment 2
(1) preparation MPS microballoon: the MPS microballoon is through the one-step method preparation, is that the aqueous isopropanol of (3-sulfydryl) propyl trimethoxy silicane (MPS) of 12.5mM joins the NH that 10mL concentration is 0.625mM with 250 μ L concentration
4Use in the OH aqueous solution IKA MS3 microoscillator under the 4000rpm rotating speed with forced oscillation 3 minutes.The solution that obtains was placed 3 hours at normal temperatures.The product that obtains at last is distributed to it then and obtains MPS solution in the 100mL n-hexane with propyl alcohol flushing 3 times.The MPS microballoon that obtains at last is of a size of 152nm.
(2) preparation MPS-ZrO
2Hybrid microspheres: 2500 μ L diameters are the ZrO of 30nm
2The concentration of particle is the hexane solution of 3.75mM, in above-mentioned solution, adds the MPS microspheres solution for preparing in the step (1) then.Mix back generation self assembly and can obtain microballoon.The microballoon that after the air drying, obtains is of a size of 563nm.This microballoon can not be distributed in the water again, can only be distributed in organic solvent such as the toluene.
(3) coated with silica MPS-ZrO
2Hybrid microspheres: use
Method, with the particle transfer for preparing in (2) to the ethanol/H that contains silica and surfactant neopelex
2O/NH
3In the solution, slight vibration makes its mixing can obtain the multifunctional hydrophilic hybrid microspheres.This microballoon can evenly disperse in the aqueous solution.
Embodiment 3
(1) preparation MPS microballoon: the MPS microballoon is through the one-step method preparation, is that the aqueous isopropanol of (3-sulfydryl) propyl trimethoxy silicane (MPS) of 20mM joins 10mL NH with 300 μ L concentration
4OH concentration be use in the aqueous solution of 0.2mM IKA MS3 microoscillator under the 500rpm rotating speed with forced oscillation 20 minutes.The solution that obtains was placed 12 hours at normal temperatures.The product that obtains at last is distributed to it then and obtains MPS solution in the 100mL normal heptane with isopropyl alcohol flushing 3 times.The MPS microballoon that obtains at last is of a size of 641nm.
(2) preparation MPS-TiO
2Hybrid microspheres: 2500 μ L diameters are the TiO of 1nm
2The concentration of particle is the n-heptane solution of 2.4mM, in above-mentioned solution, adds the MPS microspheres solution for preparing in the step (1) then.Mix back generation self assembly and can obtain microballoon.The microballoon that after the air drying, obtains is of a size of 855nm.This microballoon can not be distributed in the water again, can only be distributed in organic solvent such as the toluene.
(3) coated with silica MPS-TiO
2Hybrid microspheres: use
Method, with the particle transfer for preparing in (2) to the ethanol/H that contains silica and surfactant lecithin
2O/NH
3In the solution, slight vibration makes its mixing can obtain the multifunctional hydrophilic hybrid microspheres.This microballoon can evenly disperse in the aqueous solution.
Embodiment 4
(1) preparation MPS microballoon: the MPS microballoon is through the one-step method preparation, and the MPS microballoon is through the one-step method preparation, is that the aqueous isopropanol of (3-sulfydryl) propyl trimethoxy silicane (MPS) of 20mM joins 10mL NH with 200 μ L concentration
4OH concentration be use in the aqueous solution of 0.267mM the IKAMS3 microoscillator under the 3000rpm rotating speed with forced oscillation 6 minutes.The solution that obtains was placed 15 hours at normal temperatures.The product that obtains at last is distributed to it then and obtains MPS solution in the 100mL cyclohexane with isopropyl alcohol flushing 3 times.The MPS microballoon that obtains at last is of a size of 3.1 μ m.
(2) preparation MPS-γ-Fe
2O
3Hybrid microspheres: 2500 μ L diameters are γ-Fe of 20nm
2O
3The concentration of particle is the cyclohexane solution of 3.2mM, in above-mentioned solution, adds the MPS microspheres solution for preparing in the step (1) then.Mix back generation self assembly and can obtain microballoon.The microballoon that after the air drying, obtains is of a size of 3.3 μ m.This microballoon can not be distributed in the water again, can only be distributed in organic solvent such as the toluene.
(3) coated with silica MPS-γ-Fe
2O
3Hybrid microspheres: use
Method, with the particle transfer for preparing in (2) to containing the stearic ethanol/H of silica and surfactant
2O/NH
3In the solution, slight vibration makes its mixing can obtain the multifunctional hydrophilic hybrid microspheres.This microballoon can evenly disperse in the aqueous solution.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technological process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technological process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technological process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. method of utilizing the self assembly of dewatering nano particle to prepare the multifunctional nano microballoon may further comprise the steps:
(1) preparation MPS microballoon: the MPS microballoon joins NH through the one-step method preparation with (3-sulfydryl) propyl trimethoxy silicane (MPS)
4Mix in the aqueous solution of OH, the solution that obtains is placed (comprised 3 hours) more than 3 hours and obtain the MPS microballoon, flushing MPS microballoon, and it is distributed to obtains MPS solution in the solvent;
(2) preparation MPS-self assembly hydrophobic particles hybrid microspheres: in the solution of self assembly hydrophobic particles, add the MPS solution that step (1) makes, mix back generation self assembly and can obtain MPS-self assembly hydrophobic particles hybrid microspheres.
2. thereby the multifunctional nano microballoon with dewatering nano particle self assembly preparation is handled the method that realizes disperseing in the aqueous solution, it is characterized in that, carries out afterwards in the said step of claim 1 (2):
(3) coated with silica MPS-self assembly hydrophobic particles hybrid microspheres: use
Method is transferred to the ethanol/H that contains silica and surfactant with the microballoon for preparing in the step (2)
2O/NH
3In the solution, make its mixing can obtain the multifunctional nano microballoon.
3. according to claim 1 or claim 2 method is characterized in that MPS and NH described in the step (1)
4The ratio of the amount of substance of OH is preferably 0.5: 1～and 4: 1, further be preferably 0.5: 1～3: 1, be preferably 0.5: 1～1.5: 1 especially;
Preferably, MPS adds with the solution form in the step (1), and solvent is an alcohols, further is preferably the C1-C5 alcohols, is preferably propyl alcohol or isopropyl alcohol or its mixture especially;
Preferably, be mixed into the micro oscillation mode of using described in the step (1); Rotating speed is 500rpm～4000rpm, is preferably 1000rpm～3000rpm especially; Duration of oscillation is more than the 2min, is preferably 2min～8min especially;
Preferably, laying temperature is a normal temperature described in the step (1);
Preferably, be (to comprise 4 hours) more than 4 hours standing time described in the step (1), further is preferably 4～15 hours, is preferably 4～12 hours especially.
4. according to claim 1 or claim 2 method is characterized in that the MPS microballoon preferably adopts C described in the step (1)
1-C
8Alcohols or the flushing of its mixture further are preferably C
1-C
3Alcohols or its mixture, for example methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or its mixture are preferably ethanol especially;
Preferably, solvent is a non-polar solven described in the step (1), further is preferably toluene, nonpolar alkane or its mixture, is preferably toluene, n-hexane, cyclohexane, normal heptane or its mixture especially.
5. according to claim 1 or claim 2 method is characterized in that the self assembly hydrophobic particles is preferably γ-Fe described in the step (2)
2O
3, Au, Ag, Pd, ZrO
2, TiO
2, MnO
2, SnO
2Or its combination, be preferably γ-Fe especially
2O
3, Au, ZrO
2, TiO
2Or its combination.
6. according to claim 1 or claim 2 method is characterized in that self assembly hydrophobic particles particle diameter is preferably below the 30nm described in the step (2), further is preferably below the 25nm, is preferably 1～20nm especially;
Preferably, described in the step (2) in the solution of self assembly hydrophobic particles solvent be non-polar solven, further be preferably toluene, nonpolar alkane or its mixture, be preferably toluene, n-hexane, cyclohexane, normal heptane or its mixture especially.
7. according to claim 1 or claim 2 method; It is characterized in that; Described in the step (2) in the mixed solution ratio of self assembly hydrophobic particles and MPS microballoon amount of substance be preferably 0.3: 1～3: 1, further be preferably 1: 1～3: 1, be preferably 2: 1～3: 1 especially.
8. method as claimed in claim 2; It is characterized in that; Surfactant described in the step (3) be anion surfactant or/and zwitterionic surfactant or/and non-ionic surface active agent; Further be preferably higher fatty acids or/and its esters, sulfonic acid or/and its esters, higher aliphatic sulfuric acid ester, lecithin, fatty acid glycerine lipid or its mixture, more preferably stearic acid, neopelex, lauryl sodium sulfate, lecithin, glycerin monostearate or its mixture;
Preferably, being mixed into vibration described in the step (3) mixes.
9. the multifunctional nano microballoon by the described method preparation of claim 1-8 is characterized in that the main body microballoon of said multifunctional nano microballoon is prepared by (3-sulfydryl) propyl trimethoxy silicane; The self assembly hydrophobic particles of being selected for use is γ-Fe
2O
3, Au, Ag, Pd, ZrO
2, TiO
2, MnO
2, SnO
2Or its combination, its particle diameter is below the 30nm.
10. multifunctional nano microballoon as claimed in claim 9 is characterized in that, said self assembly hydrophobic particles is preferably γ-Fe
2O
3, Au, ZrO
2, TiO
2Or its combination;
Said self assembly hydrophobic particles particle diameter is preferably below the 25nm, is preferably 1～20nm especially.
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| CN105419778A (en) * | 2015-12-22 | 2016-03-23 | 莫婉玲 | Quantum dot composite material containing paraffin and preparation method thereof |
| CN108129671A (en) * | 2017-12-18 | 2018-06-08 | 常州大学 | A kind of method that the micro-nano bead with super-hydrophobicity is prepared based on silicon rubber microballoon |
| US10016745B2 (en) | 2016-06-15 | 2018-07-10 | Savannah River Nuclear Solutions, Llc | Multifunctional nanomaterials and methods of photothermal heating and catalysis using the same |
| US11307129B2 (en) | 2020-03-23 | 2022-04-19 | Savannah River Nuclear Solutions, Llc | Automatic gas sorption apparatus and method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103252199A (en) * | 2012-12-27 | 2013-08-21 | 苏州大学 | Preparation method of inorganic silicon dioxide/organic nano particle core-shell structure |
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| CN105419777A (en) * | 2015-12-22 | 2016-03-23 | 莫婉玲 | Quantum dot composite material containing fatty acid ester and preparation method thereof |
| CN105419778A (en) * | 2015-12-22 | 2016-03-23 | 莫婉玲 | Quantum dot composite material containing paraffin and preparation method thereof |
| CN105419778B (en) * | 2015-12-22 | 2017-11-14 | 重庆益新阳工贸有限公司 | A kind of quantum dot composite material containing paraffin and preparation method thereof |
| US10016745B2 (en) | 2016-06-15 | 2018-07-10 | Savannah River Nuclear Solutions, Llc | Multifunctional nanomaterials and methods of photothermal heating and catalysis using the same |
| CN108129671A (en) * | 2017-12-18 | 2018-06-08 | 常州大学 | A kind of method that the micro-nano bead with super-hydrophobicity is prepared based on silicon rubber microballoon |
| CN108129671B (en) * | 2017-12-18 | 2021-01-29 | 常州大学 | Method for preparing micro-nano small balls with super-hydrophobicity based on silicone rubber microspheres |
| US11307129B2 (en) | 2020-03-23 | 2022-04-19 | Savannah River Nuclear Solutions, Llc | Automatic gas sorption apparatus and method |
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