CN112934196A - Hollow carbon sphere HCS porous liquid with flowing behavior at room temperature and preparation method thereof - Google Patents
Hollow carbon sphere HCS porous liquid with flowing behavior at room temperature and preparation method thereof Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000002608 ionic liquid Substances 0.000 claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000005349 anion exchange Methods 0.000 claims abstract description 7
- XPQCSBZXDJSXAI-UHFFFAOYSA-N 4-nonylphenol;potassium Chemical compound [K].CCCCCCCCCC1=CC=C(O)C=C1 XPQCSBZXDJSXAI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000015047 pilsener Nutrition 0.000 claims abstract 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 239000006228 supernatant Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 16
- 229910052681 coesite Inorganic materials 0.000 claims description 15
- 229910052906 cristobalite Inorganic materials 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 229910052682 stishovite Inorganic materials 0.000 claims description 15
- 229910052905 tridymite Inorganic materials 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 150000003254 radicals Chemical class 0.000 claims description 11
- -1 poly 1- (4-vinyl phenyl) methyl-3-butyl imidazole chloride salt Chemical compound 0.000 claims description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 239000005011 phenolic resin Substances 0.000 claims description 9
- 229920001568 phenolic resin Polymers 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- 239000005416 organic matter Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 claims description 5
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 4
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000008098 formaldehyde solution Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229920001289 polyvinyl ether Polymers 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- GLYLHMCJISWWLL-UHFFFAOYSA-N 3-ethenyl-1-heptyl-1,2-dihydroimidazol-1-ium bromide Chemical compound CCCCCCC[NH+]1CN(C=C1)C=C.[Br-] GLYLHMCJISWWLL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000012643 polycondensation polymerization Methods 0.000 claims description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims 4
- 239000011148 porous material Substances 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000012621 metal-organic framework Substances 0.000 abstract description 3
- 239000010457 zeolite Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 abstract description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 244000282866 Euchlaena mexicana Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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- B01J20/28016—Particle form
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Abstract
The invention relates to a hollow carbon sphere HCS porous liquid with flowing behavior at room temperature and a preparation method thereof, which integrates the characteristics of porous solid (such as zeolite and metal organic framework, and has permanent property, rigidity and well-defined pores) and liquid (having fluidity, rapid heating and mass transfer). A hollow carbon sphere HCS is adopted as a core, polymer ionic liquid PILs are modified on the surface of the hollow carbon sphere HCS through electrostatic assistance, and then organic oligomers (such as 4-nonylphenol-potassium polyoxyethylene ether PEGS) with electric polarity opposite to that of the PILs are grafted on the surface of the HCS through anion exchange to prepare porous liquid, wherein the porous liquid is in a liquid state at room temperature, and the HCS is monodisperse. The preparation method of the HCS porous liquid is simple and easy to implement, and the hollow carbon sphere nanoparticles are in a monodisperse state in the porous liquid at room temperature, so that the hollow carbon sphere nanoparticles have potential application prospects in the aspects of gas adsorption, photo-thermal conversion, catalytic conversion and the like.
Description
Technical Field
The invention belongs to porous liquid and a preparation method thereof, relates to hollow carbon sphere HCS porous liquid with a flowing behavior at room temperature and a preparation method thereof, is a high-performance adsorption material, and can be applied to the fields of efficient solvents, gas selective adsorption, separation, photothermal conversion and the like.
Background
The porous material has the advantages of stable internal pore structure, high porosity, controllable pore structure and the like, and has wide application in many fields of gas adsorption/separation, sound insulation and shock absorption, catalysis, host-guest molecule identification and the like. But it imposes a certain limitation on its application because it does not have fluidity by itself. The liquid material has fluidity, but each molecule moves nearby, changes positions, is unstable in pore space and disappears along with thermal movement, namely a transient extrinsic cavity structure existing in the traditional liquid. In order to compensate for this disadvantage and to broaden its application range, a cavity structure is introduced into the dense liquid so that the cavity structure can be permanently and stably present in the liquid, and a liquid having permanent pores, i.e., a porous liquid, is prepared. The difference from the traditional liquid is that the porous solid and the liquid are combined, and the porous solid and the liquid have great potential application values in the aspects of gas adsorption, gas selective separation, catalysis, photothermal conversion and the like.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a hollow carbon sphere HCS porous liquid with a flowing behavior at room temperature and a preparation method thereof, and the porous liquid contains a stable HCS hollow structure and imidazole-type PILs, wherein the adjustable range of the average outer diameter of HCS is 100nm-500nm, the average wall thickness is 5-10nm, the mass percentage content is more than 5%, and the porosity is more than 30%, and for CO2The gas has high adsorption performance to CO2/N2Also has high selectivity. Improving dispersibility and adsorption/separation properties.
Technical scheme
A hollow carbon sphere HCS porous liquid having a flow behavior at room temperature, characterized in that: HCS is taken as a core, and a long-chain organic matter is coated outside the core; the mass fraction of the two is as follows: 5-15% of HCS and 85-95% of long-chain organic matter; the long-chain organic matter is an organic long chain obtained after the exchange of polymer ionic liquid PILs and 4-nonylphenol-potassium polyvinylether sulfonate PEGS anions, and the molar ratio of the PILs to the PEGS is 1:1.
The HCS is a hollow nanoparticle.
The average diameter range of the hollow nano-particle HCS is 100nm-500 nm.
The average wall thickness of the hollow nano-particle HCS is 5nm-10 nm.
The polymer ionic liquid PILs comprise poly 1- (4-vinyl phenyl) methyl-3-butyl imidazole chloride salt P [ VBBI ] Cl or poly 1- (4-vinyl phenyl) methyl-3-butyl imidazole bromide salt P [ VHIm ] Br.
A method for preparing the hollow carbon sphere HCS porous liquid with flowing behavior at room temperature is characterized by comprising the following steps:
step 1, preparing HCS by a hard template method: to be provided withThe silicon dioxide nano particles prepared by the method are used as a template, the phenolic resin prepared by condensation polymerization of resorcinol and formaldehyde solution with the molar ratio of 1:1.2-2 is used as a carbon source, and the phenolic resin is deposited on SiO2On a template, centrifuging, repeatedly washing and precipitating by absolute ethyl alcohol and deionized water, drying the precipitate to prepare SiO2@ RF nanoparticles;
carbonizing the mixture at 350-800 ℃ for 4-8 h in a tube furnace under the nitrogen atmosphere to remove organic matters to prepare SiO2@ C nanoparticles;
then, the SiO template is removed by etching the template with hydrofluoric acid2And centrifugal drying to obtain mesoporous porous hollow carbon sphere HCS;
Step 2: dispersing HCS in deionized water at a mass ratio of 1:100-120, and performing ultrasonic uniform dispersion; dissolving polymer ion PILs in deionized water according to the mass ratio of 1:10-12, and performing ultrasonic treatment to completely dissolve the polymer ion PILs; mixing the two solutions, and stirring for 20-30h at 30-50 ℃ to obtain PILs-coated HCS, which is named as PILs @ HCS; weighing PEGS with a molar ratio of 1:1 to PILs, dissolving the PEGS into deionized water, adding the dissolved PEGS into the previous mixed solution after complete dissolution, magnetically stirring, reacting for 20-30h at 60-100 ℃, and carrying out anion exchange; and after the reaction is finished, adding acetone for ultrasonic treatment after drying, standing, pouring out the supernatant, continuously putting the supernatant into an oven for drying to remove the acetone, and obtaining the porous liquid based on the hollow carbon spheres, which is named as HCS-PILs-PEGS.
And the drying in the step 1 is carried out in an oven at 50-100 ℃.
The hydrofluoric acid accounts for 5 wt%.
When the adopted polymer ionic liquid PILs is poly 1-vinyl-3-heptyl imidazole bromide salt P [ VHIm]Br, P [ VHim]Preparing Br, weighing vinyl imidazole and bromoheptane with the molar ratio of 1-1:1.2, adding 0.1g of 2, 6-di-tert-butylphenol into a three-neck flask, and adding 60mL of ethanol; n is a radical of2Carrying out reflux reaction for 20-30h at 50-80 ℃ under protection; after the reaction is finished, removing ethanol by a rotary evaporator, then precipitating and washing by using diethyl ether, removing excessive reactants and polymerization inhibitor, and finally obtaining light brown viscous liquid [ VHIm]Br; with double bonds [ VHIm]Br is polymerized by free radical solution initiated by initiator AIBN to obtain P [ VHIm]Br, the specific process is as follows: weighing 5-6g of VHIm]Br, 2-3mg initiator AIBN, 60mL DMF as solvent into a dry round bottom flask, N2Carrying out reflux reaction for 20-30h at 50-80 ℃ under protection; and after the reaction is finished, pouring the obtained solution into ethyl acetate for precipitation, then pouring out supernatant, and drying at 50-100 ℃ for 20-30h to obtain white powdery solid.
When the polymer ionic liquid PILs is poly 1- (4-vinyl phenyl) methyl-3-butyl imidazole chloride salt P [ VBBI]Cl, P [ VBBI ]]Preparation of Cl p-chloromethyl styrene and N-butylimidazole in a molar ratio of 1:1 to 1.2 were weighed0.1g of 2, 6-di-tert-butylphenol was put in a three-necked flask, and 60mL of ethanol, N, was added2And carrying out reflux reaction for 20-30h at 50-80 ℃ under protection. Removing ethanol by rotary evaporator after reaction, precipitating with diethyl ether, washing for three times, removing excessive reactant and polymerization inhibitor, and drying to obtain yellowish viscous liquid [ VBBI ]]And (4) Cl. With double bonds [ VBBI ]]Cl is polymerized by free radical solution initiated by initiator AIBN to obtain P [ VBBI]And Cl, wherein the specific process is as follows: weighing 5-6g of ionic liquid monomer, 2-3mg of initiator AIBN and 60mL of DMF as solvents, adding the mixture into a dry round-bottom flask, and adding N2Carrying out reflux reaction for 20-30h at 50-80 ℃ under protection; and after the reaction is finished, pouring the obtained solution into ethyl acetate for precipitation, then pouring out the supernatant, and drying at 50-100 ℃ for 20-30h to obtain yellow viscous liquid.
Advantageous effects
The invention provides a Hollow Carbon Sphere (HCS) porous liquid with a flowing behavior at room temperature and a preparation method thereof, and the Hollow Carbon Sphere (HCS) porous liquid is a porous liquid containing a stably existing cavity structure based on Hollow Carbon Spheres (HCS) and Polymer Ionic Liquids (PILs). It combines the properties of a porous solid (such as zeolite and metal-organic framework, with permanent, rigid, well-defined pores) with a liquid (with fluidity, rapid heating and mass transfer). A hollow carbon sphere HCS is adopted as a core, polymer ionic liquid PILs are modified on the surface of the hollow carbon sphere HCS through electrostatic assistance, and then organic oligomers (such as 4-nonylphenol-potassium polyoxyethylene ether PEGS) with electric polarity opposite to that of the PILs are grafted on the surface of the HCS through anion exchange to prepare porous liquid, wherein the porous liquid is in a liquid state at room temperature, and the HCS is monodisperse. The preparation method of the HCS porous liquid is simple and easy to implement, and the hollow carbon sphere nanoparticles are in a monodisperse state in the porous liquid at room temperature, so that the hollow carbon sphere nanoparticles have potential application prospects in the aspects of gas adsorption, photo-thermal conversion, catalytic conversion and the like.
Compared with the prior art, the invention has the advantages that:
the prepared porous liquid has the advantages of inherent pore structure, high specific surface area, low density, rigidity, liquid fluidity, rapid heating and mass transfer and the like of solid porous materials (such as zeolite and metal organic frameworks). The porous liquid prepared by using HCS as a core and PILs (containing imidazole groups or quaternary ammonium salts) and PEGS (containing ether bonds) as outer layers has the characteristics of a solid porous material HCS, has larger pore content than conventional liquid, and can adopt a sustainable and continuous liquid process under the combined action of physical adsorption and chemical adsorption so as to ensure that the porous liquid has better solubility, gas adsorption/selectivity. Meanwhile, the carbon material can have strong absorption in a near infrared region due to the structural particularity, and can realize photothermal conversion. Compared with the traditional heat transfer enhancement research, the porous liquid based on the HCS has better light absorption performance, well solves the problems of stable suspension and uniform dispersion of the nano material in the fluid, and has wide application prospect in the fields of disease treatment, seawater desalination and new energy.
Drawings
FIG. 1: schematic preparation of HCS
FIG. 2: synthesis of poly (1- (4-vinylphenyl) methyl-3-butylimidazolium bromide) (P [ VHIm ] Br)
FIG. 3: schematic preparation of porous liquid
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the technical idea of the invention is as follows:
according to the invention, HCS is taken as a core, and a long-chain organic matter obtained by exchanging imidazole type PILs with PEGS anion is taken as an outer layer to be modified on the surface of HCS through electrostatic interaction, so as to prepare the porous liquid containing 5-15% of HCS by mass and 85-95% of long-chain organic matter (PILs-PEGS) by mass.
The hollow nano-particle HCS used in the invention is prepared by adopting a hard template method.
The adjustable preparation range of the average diameter of the hollow nano-particle HCS used in the invention is 100nm-500nm, and the average wall thickness is 5-10 nm.
The polymeric ionic liquids PILs used in the present invention are of the imidazole type, called neck-layers.
The long chain organic used in the present invention is an organic oligomer (e.g., potassium 4-nonylphenol-polyvinylether sulfonate) of opposite electrical polarity to the PILs, referred to as a corona layer.
The preparation method of the HCS porous liquid with flowing behavior at room temperature comprises the following steps.
The invention adopts a hard template method to prepare hollow carbon spheres HCS, and adoptsThe prepared silicon dioxide is used as a hard template, formaldehyde and resorcinol are added, the prepared phenolic resin is used as a carbon source, and SiO is prepared by depositing on the silicon dioxide template2@ RF. Performing high-temperature carbonization under the vacuum condition of a tube furnace to remove organic matters to obtain SiO2@ C, then removing SiO by hydrofluoric acid etching2After this time, HCS was obtained. Preparation of 1- (4-vinylphenyl) methyl-3-butylimidazolium bromide ([ VHIm) using vinylimidazole and bromoheptane]Br) ionic liquid monomer, and preparing the polymer ionic liquid, namely P [ VHIm ] through free radical polymerization]Br is added. Modifying PILs on the surface of HCS through electrostatic interaction, and grafting PEGS on the surface of the PILs through anion exchange to prepare the porous liquid.
The preparation scheme of the invention takes P [ VHIm ] Br as an example, and is shown in the attached drawing.
Example 1:
preparation of HCS: to be provided withThe silicon dioxide prepared by the method is used as a hard template, and the phenolic resin is used as a carbon source to prepare HCS. The specific experimental procedure is as follows: 200mL of absolute ethyl alcohol, 75mL of deionized water and 32.5mL of NH are measured3·H2O (25 wt%), pouring the mixture into a three-neck flask after being uniformly mixed, magnetically stirring the mixture for 15min at room temperature, slowly adding 40mL of TEOS into the three-neck flask, stirring the mixture for reaction for 15min, and changing the solution from transparent to white emulsion to prepare SiO2(ii) a The phenolic resin prepared by adding 2.31g of resorcinol and 3.24mL of formaldehyde solution (37 wt%) as a carbon source was stirred at room temperature for 24h, and after the reaction was completed, the solution changed from a white emulsion to a dark brown emulsion. After centrifugation, the precipitate was washed repeatedly with absolute ethanol and deionized water, and washedDrying the mixture in an oven at 70 ℃ to prepare SiO2@ RF nanoparticles. Carbonizing at 800 deg.C in nitrogen atmosphere for 4h to remove organic substances to obtain SiO2@ C nanoparticles. Then, etching the template SiO by hydrofluoric acid (HF, 5 wt%) to remove the template SiO2And centrifugally drying to obtain hollow carbon spheres HCS with the particle size of 440nm-460 nm.
Synthesis of poly (1- (4-vinylphenyl) methyl-3-butylimidazolium bromide) (P [ VHIm)]Br) preparation: accurately weighed 4.7g (0.05mol) of vinylimidazole, 8.95g (0.05mol) of bromoheptane, 0.1g of 2, 6-di-tert-butylphenol (DBMP), 60mL of ethanol, and charged into a 150mL three-necked flask, N2The reaction is refluxed for 24h at 70 ℃ under protection. After the reaction is finished, removing ethanol by rotary evaporation, then precipitating and washing with diethyl ether, removing excessive reactants and polymerization inhibitor, removing diethyl ether by rotary evaporation, and drying at room temperature to obtain light brown viscous liquid. The ionic liquid monomer with double bonds is polymerized by free radical solution initiated by initiator AIBN to obtain polymer ionic liquid, and the specific process is as follows: 3g of ionic liquid monomer, 1mg of initiator Azobisisobutyronitrile (AIBN), 50mL of N, N-Dimethylformamide (DMF) were weighed as a solvent and added to a dry 100mL round bottom flask, N2And (4) protecting, and carrying out reflux reaction at 80 ℃ for 24 hours. After the reaction was completed, the resulting solution was poured into ethyl acetate to precipitate, and then the supernatant was poured out and dried at 70 ℃ for 24 hours to obtain white powdery PILs.
Preparation of porous liquid: dispersing 0.5g of HCS in deionized water, performing ultrasonic treatment to uniformly disperse the HCS, dissolving 0.5g P [ VHIm ] Br in the deionized water, performing ultrasonic treatment to completely dissolve the HCS, adding the dissolved HCS into a solution in which the HCS is dispersed, and stirring the solution at 35 ℃ for 24 hours to obtain HCS coated with PILs, wherein the HCS is named as HCS @ PILs. Weighing PEGS with corresponding mass, dissolving the PEGS into deionized water in the same way, adding the PEGS into the mixed solution after complete dissolution, magnetically stirring, reacting at 70 ℃ for 24 hours, and carrying out anion exchange. And after the reaction is finished, pouring the mixture into a beaker, drying the mixture in a 75 ℃ oven, adding acetone, performing ultrasonic treatment for 10min, standing the mixture for 30min, pouring out the supernatant, continuously putting the supernatant into the oven, drying the supernatant to remove the acetone, and preparing the porous liquid based on the hollow carbon spheres, wherein the porous liquid is named as HCS-P [ VHIm ] Br-PEGS.
Example 2: substitution of P [ VHIm ] Br with P [ VBBI ] Cl
P[VBBI]Preparation of Cl p-chloromethyl styrene and N-butylimidazole in a molar ratio of 1:1-1.2, 0.1g of 2, 6-di-tert-butylphenol were weighed into a three-necked flask, and 60mL of ethanol, N2And carrying out reflux reaction for 20-30h at 50-80 ℃ under protection. Removing ethanol by rotary evaporator after reaction, precipitating with diethyl ether, washing for three times, removing excessive reactant and polymerization inhibitor, and drying to obtain yellowish viscous liquid [ VBBI ]]And (4) Cl. With double bonds [ VBBI ]]Cl is polymerized by free radical solution initiated by initiator AIBN to obtain P [ VBBI]And Cl, wherein the specific process is as follows: weighing 5-6g of ionic liquid monomer, 2-3mg of initiator AIBN and 60mL of DMF as solvents, adding the mixture into a dry round-bottom flask, and adding N2Carrying out reflux reaction for 20-30h at 50-80 ℃ under protection; and after the reaction is finished, pouring the obtained solution into ethyl acetate for precipitation, then pouring out the supernatant, and drying at 50-100 ℃ for 20-30h to obtain yellow viscous liquid.
Example 4:
preparation of HCS with different particle sizes: to be provided withThe silicon dioxide prepared by the method is used as a hard template, and the phenolic resin is used as a carbon source to prepare HCS. The specific experimental procedure is as follows: weighing 150mL of absolute ethyl alcohol, 56mL of deionized water and 30.8mL of NH3·H2O (25 wt%), pouring the mixture into a three-neck flask after being uniformly mixed, magnetically stirring the mixture for 15min at room temperature, slowly adding 14mL of TEOS into the three-neck flask, stirring the mixture for reaction for 15min, and changing the solution from transparent to white emulsion to prepare SiO2(ii) a 2.4g of resorcinol and 3.2mL of formaldehyde solution (37 wt%) were added to prepare a phenolic resin as a carbon source, and stirring was continued at room temperature for 24h, after the reaction was completed, the solution changed from a white emulsion to a dark brown emulsion. After centrifugation, the precipitate is repeatedly washed by absolute ethyl alcohol and deionized water, and is dried in a 70 ℃ oven to prepare SiO2@ RF nanoparticles. Carbonizing at 800 deg.C in a tubular furnace under nitrogen atmosphere4h to remove organic matters to prepare SiO2@ C nanoparticles. Then, etching the template SiO by hydrofluoric acid (HF, 5 wt%) to remove the template SiO2And centrifugally drying to obtain the hollow carbon sphere HCS with the particle size of 240nm-260 nm. By adjusting TEOS, NH3·H2The proportion of O and deionized water can prepare SiO with different grain diameters2And preparing a template to obtain the HCS with the adjustable hollow structure size range of 100nm-500 nm.
Poly 1- (4-vinylphenyl) methyl-3-butylimidazolium chloride salt (P [ VBBI ]]Cl) preparation: and P [ VHIm]The Br preparation process is similar. First, 7.63g (0.05mol) of p-chloromethylstyrene, 5.67g (0.05mol) of N-butylimidazole, 0.1g of 2, 6-di-tert-butylphenol (DBMP), and 60mL of ethanol were accurately weighed and charged in a 150mL three-necked flask, and N was added2The reaction is refluxed for 24h at 70 ℃ under protection. And after the reaction is finished, removing the solvent by rotary evaporation, washing with diethyl ether for three times, removing excessive reactants and a polymerization inhibitor, removing the diethyl ether by rotary evaporation, and drying at room temperature to finally obtain light yellow viscous liquid which is an ionic liquid monomer. The ionic liquid monomer with double bonds is polymerized by free radical solution initiated by initiator AIBN to obtain the polymerized ionic liquid, and the specific process is as follows: 6g of ionic liquid monomer, 2mg of initiator Azobisisobutyronitrile (AIBN), 50mL of N, N-Dimethylformamide (DMF) were weighed as a solvent and added to a dry 100mL round bottom flask, and N was bubbled2The reaction is carried out for 20min and the reflux is carried out for 24h at the temperature of 80 ℃. After the reaction was completed, the resulting solution was poured into ethyl acetate to precipitate, and then the supernatant was poured out and dried at 70 ℃ for 24 hours to obtain a yellow viscous liquid.
Preparation of porous liquid: similar to the preparation process of HCS-P [ VHIm ] Br-PEGS. Dispersing 0.5g of HCS in deionized water, performing ultrasonic treatment to uniformly disperse the HCS, dissolving 0.5g P [ VBBI ] Cl in the deionized water, performing ultrasonic treatment to completely dissolve the solution, adding the solution into the solution in which the HCS is dispersed, and stirring the solution at the temperature of 35 ℃ for 24 hours to obtain the HCS coated with the PILs, wherein the HCS is named as HCS @ PILs. Weighing PEGS with corresponding mass, dissolving the PEGS into deionized water in the same way, adding the PEGS into the mixed solution after complete dissolution, magnetically stirring, reacting at 70 ℃ for 24 hours, and carrying out anion exchange. And after the reaction is finished, pouring the mixture into a beaker, drying the mixture in a 75 ℃ oven, adding acetone, performing ultrasonic treatment for 10min, standing the mixture for 30min, pouring out the supernatant, continuously putting the supernatant into the oven, drying the supernatant to remove the acetone, and preparing the porous liquid based on the hollow carbon spheres, wherein the porous liquid is named as HCS-P [ VBBI ] Cl-PEGS.
Example 4: replacement of P [ VBBI ] Cl with P [ VHIm ] Br:
P[VHIm]preparing Br, weighing vinyl imidazole and bromoheptane with the molar ratio of 1-1:1.2, adding 0.1g of 2, 6-di-tert-butylphenol into a three-neck flask, and adding 60mL of ethanol; n is a radical of2Carrying out reflux reaction for 20-30h at 50-80 ℃ under protection; after the reaction is finished, removing ethanol by a rotary evaporator, then precipitating and washing by using diethyl ether, removing excessive reactants and polymerization inhibitor, and finally obtaining light brown viscous liquid [ VHIm]Br; with double bonds [ VHIm]Br is polymerized by free radical solution initiated by initiator AIBN to obtain P [ VHIm]Br, the specific process is as follows: weighing 5-6g of VHIm]Br, 2-3mg initiator AIBN, 60mL DMF as solvent into a dry round bottom flask, N2Carrying out reflux reaction for 20-30h at 50-80 ℃ under protection; and after the reaction is finished, pouring the obtained solution into ethyl acetate for precipitation, then pouring out supernatant, and drying at 50-100 ℃ for 20-30h to obtain white powdery solid.
Claims (10)
1. A hollow carbon sphere HCS porous liquid having a flow behavior at room temperature, characterized in that: HCS is taken as a core, and a long-chain organic matter is coated outside the core; the mass fraction of the two is as follows: 5-15% of HCS and 85-95% of long-chain organic matter; the long-chain organic matter is an organic long chain obtained after the exchange of polymer ionic liquid PILs and 4-nonylphenol-potassium polyvinylether sulfonate PEGS anions, and the molar ratio of the PILs to the PEGS is 1:1.
2. The hollow carbon sphere HCS porous liquid having a flow behavior at room temperature according to claim 1, characterized in that: the HCS is a hollow nanoparticle.
3. The hollow carbon sphere HCS porous liquid having a flow behavior at room temperature according to claim 2, characterized in that: the average diameter range of the hollow nano-particle HCS is 100nm-500 nm.
4. The hollow carbon sphere HCS porous liquid having a flow behavior at room temperature according to claim 2, characterized in that: the average wall thickness of the hollow nano-particle HCS is 5nm-10 nm.
5. The hollow carbon sphere HCS porous liquid having a flow behavior at room temperature according to claim 2, characterized in that: the polymer ionic liquid PILs comprise poly 1- (4-vinyl phenyl) methyl-3-butyl imidazole chloride salt P [ VBBI ] Cl or poly 1- (4-vinyl phenyl) methyl-3-butyl imidazole bromide salt P [ VHIm ] Br.
6. A method for preparing the hollow carbon sphere HCS porous liquid with flowing behavior at room temperature according to any one of claims 1 to 5, which is characterized by comprising the following steps:
step 1, preparing HCS by a hard template method: to be provided withThe silicon dioxide nano particles prepared by the method are used as a template, the phenolic resin prepared by condensation polymerization of resorcinol and formaldehyde solution with the molar ratio of 1:1.2-2 is used as a carbon source, and the phenolic resin is deposited on SiO2On a template, centrifuging, repeatedly washing and precipitating by absolute ethyl alcohol and deionized water, drying the precipitate to prepare SiO2@ RF nanoparticles;
carbonizing the mixture at 350-800 ℃ for 4-8 h in a tube furnace under the nitrogen atmosphere to remove organic matters to prepare SiO2@ C nanoparticles;
then, the SiO template is removed by etching the template with hydrofluoric acid2Centrifugal drying to obtain mesoporous porous hollow carbon spheres HCS;
step 2: dispersing HCS in deionized water at a mass ratio of 1:100-120, and performing ultrasonic uniform dispersion; dissolving polymer ion PILs in deionized water according to the mass ratio of 1:10-12, and performing ultrasonic treatment to completely dissolve the polymer ion PILs; mixing the two solutions, and stirring for 20-30h at 30-50 ℃ to obtain PILs-coated HCS, which is named as PILs @ HCS; weighing PEGS with a molar ratio of 1:1 to PILs, dissolving the PEGS into deionized water, adding the dissolved PEGS into the previous mixed solution after complete dissolution, magnetically stirring, reacting for 20-30h at 60-100 ℃, and carrying out anion exchange; and after the reaction is finished, adding acetone for ultrasonic treatment after drying, standing, pouring out the supernatant, continuously putting the supernatant into an oven for drying to remove the acetone, and obtaining the porous liquid based on the hollow carbon spheres, which is named as HCS-PILs-PEGS.
7. The method of claim 6, wherein: and the drying in the step 1 is carried out in an oven at 50-100 ℃.
8. The method of claim 6, wherein: the hydrofluoric acid accounts for 5 wt%.
9. The method of claim 6, wherein: when the adopted polymer ionic liquid PILs is poly 1-vinyl-3-heptyl imidazole bromide salt P [ VHIm]Br, P [ VHim]Preparing Br, weighing vinyl imidazole and bromoheptane with the molar ratio of 1-1:1.2, adding 0.1g of 2, 6-di-tert-butylphenol into a three-neck flask, and adding 60mL of ethanol; n is a radical of2Carrying out reflux reaction for 20-30h at 50-80 ℃ under protection; after the reaction is finished, removing ethanol by a rotary evaporator, then precipitating and washing by using diethyl ether, removing excessive reactants and polymerization inhibitor, and finally obtaining light brown viscous liquid [ VHIm]Br; with double bonds [ VHIm]Br is polymerized by free radical solution initiated by initiator AIBN to obtain P [ VHIm]Br, the specific process is as follows: weighing 5-6g of VHIm]Br, 2-3mg initiator AIBN, 60mL DMF as solvent into a dry round bottom flask, N2Carrying out reflux reaction for 20-30h at 50-80 ℃ under protection; and after the reaction is finished, pouring the obtained solution into ethyl acetate for precipitation, then pouring out supernatant, and drying at 50-100 ℃ for 20-30h to obtain white powdery solid.
10. The method of claim 6, wherein: when the adopted polymer ionic liquid PILs is poly 1- (4-vinyl phenyl) methyl-3-butyl imidazole chlorideSalt P [ VBBI ]]Cl, P [ VBBI ]]Preparation of Cl, weighing p-chloromethyl styrene and N-butyl imidazole in a molar ratio of 1:1-1.2, 0.1g of 2, 6-di-tert-butylphenol, adding 60mL of ethanol, N2And carrying out reflux reaction for 20-30h at 50-80 ℃ under protection. Removing ethanol by rotary evaporator after reaction, precipitating with diethyl ether, washing for three times, removing excessive reactant and polymerization inhibitor, and drying to obtain yellowish viscous liquid [ VBBI ]]And (4) Cl. With double bonds [ VBBI ]]Cl is polymerized by free radical solution initiated by initiator AIBN to obtain P [ VBBI]And Cl, wherein the specific process is as follows: weighing 5-6g of ionic liquid monomer, 2-3mg of initiator AIBN and 60mL of DMF as solvents, adding the mixture into a dry round-bottom flask, and adding N2Carrying out reflux reaction for 20-30h at 50-80 ℃ under protection; and after the reaction is finished, pouring the obtained solution into ethyl acetate for precipitation, then pouring out the supernatant, and drying at 50-100 ℃ for 20-30h to obtain yellow viscous liquid.
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