CN115725100A - Perovskite quantum dot/4-aminophenylporphyrin/graphene oxide high-thermal-conductivity composite membrane and preparation method thereof - Google Patents
Perovskite quantum dot/4-aminophenylporphyrin/graphene oxide high-thermal-conductivity composite membrane and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 33
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 21
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 20
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 18
- 239000012286 potassium permanganate Substances 0.000 claims description 16
- 238000004090 dissolution Methods 0.000 claims description 15
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 13
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 13
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 13
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 13
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000005642 Oleic acid Substances 0.000 claims description 13
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 13
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 13
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- 235000010344 sodium nitrate Nutrition 0.000 claims description 9
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
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- 229910021382 natural graphite Inorganic materials 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
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- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 4
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- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
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- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 4
- 239000013310 covalent-organic framework Substances 0.000 description 4
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
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- 150000004032 porphyrins Chemical class 0.000 description 2
- DLIOHRNRAIDJAW-UHFFFAOYSA-N N1C2=CC([N]3)=CC=C3C=C(N3)C=CC3=CC([N]3)=CC=C3C=C1C(N)=C2C1=CC=CC=C1 Chemical compound N1C2=CC([N]3)=CC=C3C=C(N3)C=CC3=CC([N]3)=CC=C3C=C1C(N)=C2C1=CC=CC=C1 DLIOHRNRAIDJAW-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of a perovskite quantum dot/4-aminophenylporphyrin/graphene oxide high-thermal-conductivity composite membrane, which comprises the following steps: the preparation method comprises the following steps of synthesis of 4-aminophenylporphyrin, preparation of graphene oxide, compounding of 4-aminophenylporphyrin and graphene oxide, preparation of perovskite quantum dots, and compounding of perovskite quantum dots/4-aminophenylporphyrin/graphene oxide. The perovskite quantum dot/4-aminophenylporphyrin/graphene oxide high-thermal-conductivity composite film prepared by the invention has excellent electric conductivity and thermal conductivity, good film forming effect, stable service life and thermal conductivity under strong ultraviolet illumination, and is suitable for the conditions of heat dissipation, refrigeration and the like of electronic components under the strong ultraviolet illumination.
Description
Technical Field
The invention belongs to the technical field of conforming materials, and particularly relates to a perovskite quantum dot/4-aminophenylporphyrin/graphene oxide high-thermal-conductivity composite membrane and a preparation method thereof.
Background
Graphene is known to be the most thermally conductive coefficient so farHigh carbon material, when it is used as carrier, the heat conductivity coefficient can reach 600W/m -1 k -1 The material can be applied to heat dissipation materials of high-power and high-integration electronic equipment. In addition, the graphene has the characteristics of high conductivity, high strength, ultralightness, thinness and the like, so that the graphene has a wide application prospect when being used as a heat conduction material.
The lead-halide perovskite material has excellent photoelectric properties such as high quantum yield, a tunable optical band gap and the ability of easily and rapidly generating charge carriers, is mainly quantum dots, has strong ultraviolet light absorption capacity, needs to be prepared in a liquid environment and dispersed in a solvent for storage, but has strong ionic characteristics so that the selection of the solvent is very limited.
Covalent organic framework materials (COFs) constructed by amino functional porphyrin have the characteristics of higher specific surface area, good crystallinity, designable pore channel size, easy functional modification and the like, and are widely applied to the aspect of heat-conducting composite materials due to higher specific surface area and excellent thermal stability. As a main body, the pore structure can load perovskite quantum dots, so that the perovskite quantum dots have a more uniform distribution state. Meanwhile, the COF material loaded with the perovskite quantum dots can have longer service life under the condition of strong ultraviolet light.
Disclosure of Invention
According to the application, aiming at the characteristics of graphene, lead halide salt perovskite materials and covalent organic framework materials, the film is formed by graphene and 4-aminophenylporphyrin, and perovskite quantum dots are compounded on the surface of the film, so that a novel heat-conducting film composite material is obtained.
In order to achieve the purpose, the invention adopts the technical scheme that: the preparation method of the perovskite quantum dot/4-aminophenylporphyrin/graphene oxide high-thermal-conductivity composite membrane comprises the following steps:
step one, synthesizing 4-aminophenylporphyrin, namely adding stirring magnetons into a three-neck round-bottom flask, installing a reflux device, and adding a certain amount of trinonylphenyl phosphite and SnCl 2 Adding a certain amount of concentrate by a conduitHydrochloric acid, oil bath reacting at a certain temperature for a period of time, sucking the half-tube liquid with a rubber head dropper, filtering with a conical suction filter funnel, putting filter paper into a small beaker, adding a certain amount of triethylamine, adding a small amount of dichloromethane for dissolving, adding MgSO (MgSO) into the small beaker 4 Drying, washing the filter cake with distilled water, dissolving the filter cake with 5% NaOH solution, adjusting pH to show alkalinity, filtering with Buchner funnel, washing with distilled water, drying the filter cake on a watch glass, wrapping the filter cake after drying with filter paper, and using CH 2 Cl 2 Soxhlet extraction is carried out on the solvent until the solvent is colorless, and vacuum drying is carried out to obtain 4-aminophenylporphyrin solid;
step two, preparing graphene oxide, namely putting a certain amount of natural graphite and sodium nitrate into a big beaker, slowly adding a certain amount of concentrated sulfuric acid to obtain a black solution, continuously stirring for a period of time in an ice bath, then slowly adding a certain amount of potassium permanganate to obtain a dark green solution, continuously stirring for a period of time in the ice bath, then slowly adding a certain amount of distilled water to obtain a tan solution, then diluting the tan solution with a certain amount of warm water, removing residual potassium permanganate with a certain amount of hydrogen peroxide to obtain a bright yellow solution, finally filtering the solution, washing the obtained solution with dilute hydrochloric acid and distilled water respectively until the solution is neutral, drying and grinding to obtain graphite oxide, centrifugally washing the product with hydrochloric acid and distilled water to near neutrality, then dialyzing the product to be neutral, and standing the solution for later use;
step three, compounding 4-aminophenylporphyrin and graphene oxide, adding a certain amount of 4-aminophenylporphyrin into a certain amount of graphene oxide suspension, magnetically stirring until the dissolution is completed, then placing the mixed solution into an ultrasonic dispersion machine for dispersion to obtain a uniform dispersion liquid of the 4-aminophenylporphyrin and the graphene oxide, measuring a certain volume of the dispersion liquid by using a liquid transfer gun, obtaining a composite heat conducting membrane on a PVDF membrane by using a vacuum filtration method, placing the composite heat conducting membrane into an oven, drying the composite heat conducting membrane for a period of time at a constant temperature, and removing the obtained 4-aminophenylporphyrin/graphene oxide membrane from the filter membrane;
step four, preparation of perovskite quantum dots, perovskite quantumPoint is CsPbBr 3 Quantum dot, csPbI 3 Quantum dots and CsPbCl 3 Dispersing the prepared perovskite quantum dots in a certain amount of toluene to obtain toluene dispersion liquid of the perovskite quantum dots for later use;
and step five, compounding the perovskite quantum dots/4-aminophenylporphyrin/graphene oxide, uniformly coating a toluene dispersion liquid of the perovskite quantum dots on the surface of the 4-aminophenylporphyrin/graphene oxide composite heat-conducting membrane in a sample bottle, and naturally drying to obtain the perovskite quantum dots/4-aminophenylporphyrin/graphene oxide high-heat-conducting composite membrane.
Preferably, the perovskite quantum adopts CsPbBr 3 The quantum dot is prepared by the following steps: preparing precursor solution, adding certain amount of CsBr and PbBr 2 Dissolving the powder in a certain amount of dimethyl sulfoxide solvent, then quickly injecting a certain amount of HBr into the solution to promote the dissolution of CsBr, continuously stirring for a period of time until the precursor powder is completely dissolved, adding a certain amount of oleic acid and oleylamine into the solution, fully stirring and uniformly mixing to obtain a precursor solution; measuring a certain amount of toluene as a solvent, quickly adding a certain amount of the precursor solution into the toluene solvent which is vigorously stirred, continuously stirring the solution for a period of time, centrifuging, pouring out the supernatant, adding a certain amount of toluene again, fully mixing, centrifuging again, removing the supernatant, and finally adding CsPbBr at the bottom of the solution 3 And dispersing the perovskite precipitate in a certain amount of toluene to obtain a toluene dispersion liquid of perovskite quantum dots for later use.
As the preferable technical proposal, in the step one, the trisnonylphenyl phosphite and SnCl 2 The mass ratio of (2) is 4: sodium nitrate: concentrated sulfuric acid: the weight ratio of potassium permanganate is 1; the weight ratio of the 4-aminophenylporphyrin to the graphene oxide suspension in the third step is 1; csBr and PbBr in the fourth step 2 And the weight ratio of dimethyl sulfoxide to HBr is 1:1.27:30:5.3; in the fifth step, the toluene dispersion liquid of the perovskite quantum dots is dispersed in 4-aminobenzeneThe coating thickness of the surface of the porphyrin-based/graphene oxide composite heat-conducting film is 30-60 mu m.
Preferably, the pH of the filter cake in the first step is adjusted to 7.5 by using potassium carbonate.
As the optimization of the technical scheme, in the first step, a stirring magneton is added into a three-neck round-bottom flask, a reflux device is arranged, and 0.4g of trisnonylphenyl phosphite and 1.5g of SnCl are added 2 Adding 20ml of concentrated hydrochloric acid into a conduit, carrying out oil bath reaction at the temperature of 80 ℃ for 2h, sucking a half-tube liquid by using a rubber head dropper, filtering by using a conical suction filter funnel, putting filter paper with a filter material into a small beaker, adding 2ml of triethylamine, adjusting the pH value of a filter cake by using a potassium carbonate solution, adding the filter cake with the adjusted pH value into a small amount of dichloromethane for dissolving, and then adding MgSO (MgSO) into the filter cake 4 Drying, washing the filter cake with distilled water, dissolving the filter cake with 5% NaOH solution, adjusting pH to show alkalinity with potassium carbonate, filtering with Buchner funnel, washing with distilled water, naturally drying the filter cake on a watch glass, wrapping the primarily filtered filter cake with filter paper, and adopting CH 2 Cl 2 Soxhlet extraction is carried out on the solvent until the solvent is colorless, and vacuum drying is carried out to obtain 4-aminophenylporphyrin solid; putting 1g of natural graphite and 1g of sodium nitrate into a big beaker, slowly adding 46ml of 98% concentrated sulfuric acid to obtain a black solution, continuously stirring for 4 hours in an ice bath, then slowly adding 6g of potassium permanganate to obtain a dark green solution, continuously stirring for 2 hours in the ice bath, then slowly adding 92ml of distilled water to obtain a tan solution, then diluting the tan solution with 350ml of warm water at 40-60 ℃, removing residual potassium permanganate with 20ml of 30% hydrogen peroxide to obtain a bright yellow solution, finally filtering the solution, washing the obtained solution with dilute hydrochloric acid and distilled water respectively until the solution is neutral, drying and grinding to obtain graphite oxide, centrifugally washing the product with hydrochloric acid and distilled water to near neutrality, then dialyzing the product to neutrality, and standing the solution for later use; in the third step, 5mg of 4-aminophenylporphyrin is added into 10ml of graphene oxide turbid liquid, the mixture is magnetically stirred for 2 hours until the dissolution is finished, and then the mixed solution is placed into an ultrasonic dispersion machine for dispersion for 1 hour to obtain 4Uniformly dispersing aminophenylporphyrin and graphene oxide, measuring a certain volume of dispersion by using a liquid transfer gun, obtaining a composite heat-conducting membrane on a PVDF membrane with the thickness of 0.48 mu m by using a vacuum filtration method, putting the composite heat-conducting membrane into a drying oven with the temperature of 50 ℃ for drying for 12 hours at constant temperature, and removing the obtained 4-aminophenylporphyrin/graphene oxide membrane from the filter membrane; when preparing the precursor solution in the fourth step, 0.5mmol CsBr and 0.4mmol PbBr are added 2 Dissolving the powder in 10ml of dimethyl sulfoxide solvent, then quickly injecting 0.5ml of HBr into the solution to promote the dissolution of CsBr, continuously stirring for 1h until the powder is completely dissolved, adding 1.0ml of oleic acid and 0.4ml of oleylamine into the solution, and fully stirring and uniformly mixing to obtain a precursor solution; measuring 10ml of toluene as solvent, quickly adding 1ml of the precursor solution into the toluene solvent which is vigorously stirred, continuously stirring the solution for 10min, centrifuging, pouring out the supernatant, adding a certain amount of toluene again, fully mixing, centrifuging again, removing the supernatant, and finally adding CsPbBr at the bottom of the solution 3 And dispersing the perovskite precipitate in 5ml of toluene to obtain a toluene dispersion liquid of perovskite quantum dots for later use.
The perovskite quantum dot/4-aminophenylporphyrin/graphene oxide high-thermal-conductivity composite membrane is prepared by the preparation method.
The invention has the beneficial effects that: the perovskite quantum dot/4-aminophenylporphyrin/graphene oxide high-thermal-conductivity composite film prepared by the invention has excellent electric conductivity and thermal conductivity, good film forming effect, stable service life and thermal conductivity under strong ultraviolet illumination, and is suitable for the conditions of heat dissipation, refrigeration and the like of electronic components under the strong ultraviolet illumination.
Drawings
Fig. 1 is an SEM scanning electron microscope image of the perovskite quantum dot/4-aminophenylporphyrin/graphene oxide composite heat conductive film prepared in example 1.
Fig. 2 is an SEM scanning electron microscope image of the perovskite quantum dot/4-aminophenylporphyrin/graphene oxide composite heat conductive film prepared in example 2.
Fig. 3 is an SEM scanning electron microscope image of the perovskite quantum dot/4-aminophenylporphyrin/graphene oxide composite heat conductive film prepared in example 3.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in a specific case to those of ordinary skill in the art.
Example 1
Synthesis of 4-aminophenylporphyrins
Adding stirring magneton into a 250mL three-neck round-bottom flask, installing a reflux device, performing three-pumping and three-charging, adding TNPP (0.4 g, 0.503mmol) and SnCl 2 (1.5g, 7.93mmol), triple pumping and triple charging, adding 20mL concentrated hydrochloric acid by a conduit, carrying out oil bath reaction at 80 ℃ for 2h, sucking the half-tube liquid by a rubber head dropper, filtering by a conical suction funnel, putting filter paper into a small beaker, adding 2mL triethylamine, adding a small amount of dichloromethane into the filter cake with the adjusted pH value for dissolving, adding MgSO 2 4 Drying, washing the filter cake with distilled water for removing excessive stannous chloride, dissolving the filter cake with 5% NaOH, adjusting pH to show alkalinity with pH test paper for further removing unreacted concentrated hydrochloric acid, filtering with Buchner funnel, washing with distilled water, drying the filter cake on a watch glass, wrapping the dried filter cake with filter paper, and using CH 2 Cl 2 Soxhlet extraction was carried out as a solvent until colorless, and vacuum-dried to obtain 0.23g of a solid.
Preparation of graphene oxide
Graphite oxide was first obtained by a modified Hummers method. 1g of natural graphite and 1g of sodium nitrate (NaNO) 3 ) Put into a 500ml big beaker, and 46ml of 98% concentrated sulfuric acid (concentrated HSO) is slowly added 4 ) A black solution is obtained, the stirring is continuously carried out in an ice bath for 4 hours, then 6g of potassium permanganate is slowly added in an ice bath environment (the process is an exothermic process and needs to be slow) to obtain a dark green solution, the ice bath stirring is continuously carried out for 2 hours, and then 92ml of distilled water is slowly added (the process is also an exothermic process and needs to be slow) to obtain a dark brown solution. Subsequently, the mixed solution was diluted with 350ml of warm water (40 to 60 ℃) at about 50 ℃ and 20ml of 30% hydrogen peroxide (H) 2 0 2 ) Removing residual potassium permanganate (KMnO) 4 ) A bright yellow solution was obtained. And finally, filtering the solution, washing the obtained product with dilute hydrochloric acid and distilled water respectively until the solution is neutral, and standing the solution for later use.
Preparation of composite heat conduction film of 4-aminophenylporphyrin and graphene oxide
5mg of 4-aminophenylporphyrin was added to 10mL of a suspension of 2mg/mLGO and magnetically stirred for 2h until dissolution was complete. And then, dispersing the mixed solution in an ultrasonic dispersion machine for 1 hour to obtain a uniform dispersion liquid of 4-aminophenylporphyrin and graphene oxide. Accurately measuring a certain volume of dispersion liquid by using a liquid transfer gun, obtaining a composite heat-conducting film on a PVDF film (0.48 mu m) by using a vacuum filtration method, placing the composite heat-conducting film in a 50 ℃ drying oven for drying for 12h at constant temperature, and removing the obtained 4-aminophenylporphyrin/graphene oxide film from the filter film to obtain the heat-conducting composite film.
CsPbBr 3 Preparation of quantum dots
In the synthesis of CsPbBr 3 Before quantum dots, precursor solution is prepared, and 0.5mmol CsBr and 0.4mmol PbBr are added 2 The powder was dissolved in 10mL of DMSO solvent, then 0.5mL of HBr was rapidly injected into the solution to facilitate the dissolution of CsBr, and stirring was continued for 1 hour until the precursor powder was completely dissolved. Then, 1.0mL of Oleic Acid (OA) and 0.4mL of oleylamine (OAm) were added to the above solution, and mixed well with stirring, OA and OAm serving as surface ligands for protecting the subsequent oversaturated precipitated quantum dots. CsPbBr 3 Synthesis step of Quantum dotsThe following were used: 10mL of toluene was measured as a solvent, and 1mL of the above precursor solution was quickly added to a vigorously stirred toluene solvent. Within a few seconds CsPbBr 3 The perovskite is rapidly crystallized in a nonpolar toluene solvent, the reaction solution is light yellow, and the generation of granular colloidal precipitate, namely CsPbBr is observed 3 And (4) quantum dots. Continuously stirring the solution for 10min, centrifuging, pouring out supernatant, adding a certain amount of toluene, mixing, centrifuging again, removing supernatant, and collecting CsPbBr at the bottom 3 The perovskite precipitate was dispersed in 5mL of toluene for use. All experimental procedures described above were performed at room temperature.
Perovskite quantum dot/4-aminophenylporphyrin/graphene oxide composite
Compounding the perovskite quantum dots with 4-aminophenylporphyrin and graphene oxide, uniformly coating a toluene dispersion liquid of the perovskite quantum dots on the surface of the 4-aminophenylporphyrin/graphene oxide composite heat-conducting film in a 5mL sample bottle, and naturally drying to obtain the perovskite quantum dots/4-aminophenylporphyrin/graphene oxide composite heat-conducting film.
Example 2
Synthesis of 4-aminophenylporphyrins
Adding stirring magneton into a 250mL three-neck round-bottom flask, installing a reflux device, performing three-pumping and three-charging, adding TNPP (0.4 g, 0.503mmol) and SnCl 2 (1.5g, 7.93mmol), triple pumping and triple charging, adding 20mL concentrated hydrochloric acid by a conduit, carrying out oil bath reaction at 80 ℃ for 2h, sucking the half-tube liquid by a rubber head dropper, filtering by a conical suction funnel, putting filter paper into a small beaker, adding 2mL triethylamine, adding a small amount of dichloromethane into the filter cake with the adjusted pH value for dissolving, adding MgSO 2 4 Drying, washing the filter cake with distilled water for removing excessive stannous chloride, dissolving the filter cake with 5% NaOH, adjusting pH to show alkalinity with pH test paper for further removing unreacted concentrated hydrochloric acid, filtering with Buchner funnel, washing with distilled water, drying the filter cake on a watch glass, wrapping the dried filter cake with filter paper, and using CH 2 Cl 2 Soxhlet extraction was carried out as a solvent until colorless, and vacuum-dried to obtain 0.23g of a solid.
Preparation of graphene oxide
Graphite oxide was first obtained by a modified Hummers method. 1g of natural graphite and 1g of sodium nitrate (NaNO) 3 ) Put into a 500ml big beaker, and 46ml of 98% concentrated sulfuric acid (concentrated HSO) is slowly added 4 ) A black solution is obtained, the stirring is continuously carried out in an ice bath for 4 hours, then 6g of potassium permanganate is slowly added in an ice bath environment (the process is an exothermic process and needs to be slow) to obtain a dark green solution, the ice bath stirring is continuously carried out for 2 hours, and then 92ml of distilled water is slowly added (the process is also an exothermic process and needs to be slow) to obtain a dark brown solution. Subsequently, the mixed solution was diluted with 350ml of warm water (40 to 60 ℃) at about 50 ℃ and 20ml of 30% hydrogen peroxide (H) 2 0 2 ) Removing residual potassium permanganate (KMnO) 4 ) A bright yellow solution was obtained. And finally filtering the solution, washing the obtained product with dilute hydrochloric acid and distilled water respectively until the solution is neutral, and standing the solution for later use.
Preparation of composite heat conduction film of 4-aminophenylporphyrin and graphene oxide
5mg of 4-aminophenylporphyrin was added to 10mL of a suspension of 2mg/mLGO and magnetically stirred for 2h until dissolution was complete. And then, dispersing the mixed solution in an ultrasonic dispersion machine for 1h to obtain a uniform dispersion liquid of 4-aminophenylporphyrin and graphene oxide. Accurately measuring a certain volume of dispersion liquid by using a liquid transfer gun, obtaining a composite heat-conducting film on a PVDF film (0.48 mu m) by using a vacuum filtration method, placing the composite heat-conducting film in a 50 ℃ drying oven for drying for 12h at constant temperature, and removing the obtained 4-aminophenylporphyrin/graphene oxide film from the filter film to obtain the heat-conducting composite film.
CsPbI 3 Preparation of quantum dots
In the synthesis of CsPbI 3 Before quantum dots, precursor solution is prepared, and 0.5mmol CsI and 0.4mmol PbI are added 2 The powder was dissolved in 10mL of DMSO solvent, then 0.5mL of HI was rapidly injected into the solution to facilitate the dissolution of the CsI, stirring was continued for 1 hour until the precursor powder was completely dissolved. Then, 1.0mL Oleic Acid (OA) and 0.4mL oleylamine (OAm) were added to the above solution, and mixed well with stirring, OA and OAm being surface ligands for protecting the subsequently oversaturated and precipitated quantaAnd (4) point. CsPbI 3 The quantum dot synthesis steps are as follows: 10mL of toluene was measured as a solvent, and 1mL of the above precursor solution was quickly added to a vigorously stirred toluene solvent. Within a few seconds, csPbI 3 The perovskite rapidly crystallizes in a nonpolar toluene solvent, the reaction solution is light yellow, and granular colloidal precipitates are observed to be generated, namely CsPbI 3 And (4) quantum dots. Continuously stirring the solution for 10min, centrifuging, pouring out supernatant, adding a certain amount of toluene, mixing, centrifuging again, removing supernatant, and collecting CsPbI at the bottom 3 The perovskite precipitate was dispersed in 5mL of toluene for use. All experimental procedures described above were performed at room temperature.
Perovskite quantum dot/4-aminophenylporphyrin/graphene oxide composite
The perovskite quantum dots, 4-aminophenylporphyrin and graphene oxide are compounded, in a 5mL sample bottle, toluene dispersion liquid of the perovskite quantum dots is uniformly coated on the surface of the 4-aminophenylporphyrin/graphene oxide composite heat-conducting film, and the obtained product is the perovskite quantum dot/4-aminophenylporphyrin/graphene oxide composite heat-conducting film after the mixture is naturally dried.
Example 3
Synthesis of 4-aminophenylporphyrins
Adding stirring magneton into a 250mL three-neck round-bottom flask, installing a reflux device, performing three-pumping and three-charging, adding TNPP (0.4 g, 0.503mmol) and SnCl 2 (1.5g, 7.93mmol), triple pumping and triple charging, adding 20mL concentrated hydrochloric acid by a conduit, carrying out oil bath reaction at 80 ℃ for 2h, sucking the half-tube liquid by a rubber head dropper, filtering by a conical suction funnel, putting filter paper into a small beaker, adding 2mL triethylamine, adding a small amount of dichloromethane into the filter cake with the adjusted pH value for dissolving, adding MgSO 2 4 Drying, washing the filter cake with distilled water for removing excessive stannous chloride, dissolving the filter cake with 5% NaOH, adjusting pH to show alkalinity with pH test paper for further removing unreacted concentrated hydrochloric acid, filtering with Buchner funnel, washing with distilled water, drying the filter cake on a watch glass, wrapping the dried filter cake with filter paper, and using CH 2 Cl 2 Soxhlet extraction of solventColorless, and dried in vacuo to give a solid, 0.23g.
Preparation of graphene oxide
Graphite oxide was first obtained by a modified Hummers method. 1g of natural graphite and 1g of sodium nitrate (NaNO) 3 ) Put into a 500ml big beaker, and 46ml of 98% concentrated sulfuric acid (concentrated HSO) is slowly added 4 ) A black solution is obtained, the stirring is continuously carried out in an ice bath for 4 hours, then 6g of potassium permanganate is slowly added in an ice bath environment (the process is an exothermic process and needs to be slow) to obtain a dark green solution, the ice bath stirring is continuously carried out for 2 hours, and then 92ml of distilled water is slowly added (the process is also an exothermic process and needs to be slow) to obtain a dark brown solution. Subsequently, the mixed solution was diluted with 350ml of warm water (40 to 60 ℃) at about 50 ℃ and 20ml of 30% hydrogen peroxide (H) 2 0 2 ) Removing residual potassium permanganate (KMnO) 4 ) A bright yellow solution was obtained. And finally filtering the solution, washing the obtained product with dilute hydrochloric acid and distilled water respectively until the solution is neutral, and standing the solution for later use.
Preparation of composite heat conduction film of 4-aminophenylporphyrin and graphene oxide
5mg of 4-aminophenylporphyrin was added to 10mL of a suspension of 2mg/mLGO, and the solution was stirred magnetically for 2h until dissolution was complete. And then, dispersing the mixed solution in an ultrasonic dispersion machine for 1h to obtain a uniform dispersion liquid of 4-aminophenylporphyrin and graphene oxide. Accurately measuring a certain volume of dispersion liquid by using a liquid transfer gun, obtaining a composite heat-conducting membrane on a PVDF membrane (0.48 mu m) by using a vacuum filtration method, putting the composite heat-conducting membrane into a 50 ℃ oven for drying for 12h at a constant temperature, and removing the obtained 4-aminophenylporphyrin/graphene oxide membrane from the filter membrane to obtain the heat-conducting composite membrane.
CsPbCl 3 Preparation of quantum dots
In the synthesis of CsPbCl 3 Before quantum dots, precursor solution is prepared, and 0.5mmol CsCl and 0.4mmol PbCl are added 2 The powder was dissolved in 10mL of DMSO solvent, then 0.5mL of HCl was rapidly injected into the solution to facilitate the dissolution of CsCl, and stirring was continued for 1 hour until the precursor powder was completely dissolved. Then, 1.0mL of Oleic Acid (OA) and 0.4mL of oleylamine (OAm) were added to the above solution, and mixed well with stirring, OA and OAm being the surfaceThe ligand is used for protecting the subsequent supersaturation precipitated quantum dots. CsPbCl 3 The quantum dot synthesis steps are as follows: 10mL of toluene was measured as a solvent, and 1mL of the above precursor solution was quickly added to a vigorously stirred toluene solvent. Within a few seconds CsPbCl 3 The perovskite rapidly crystallizes in a nonpolar toluene solvent, the reaction solution is light yellow, and the generation of granular colloidal precipitates, namely CsPbCl, is observed 3 And (4) quantum dots. Continuously stirring the solution for 10min, centrifuging, pouring out supernatant, adding a certain amount of toluene, mixing, centrifuging again, removing supernatant, and collecting CsPbCl at the bottom 3 The perovskite precipitate was dispersed in 5mL of toluene for use. All experimental procedures described above were performed at room temperature.
Perovskite quantum dot/4-aminophenylporphyrin/graphene oxide composite
The perovskite quantum dots, 4-aminophenylporphyrin and graphene oxide are compounded, in a 5mL sample bottle, toluene dispersion liquid of the perovskite quantum dots is uniformly coated on the surface of the 4-aminophenylporphyrin/graphene oxide composite heat-conducting film, and the obtained product is the perovskite quantum dot/4-aminophenylporphyrin/graphene oxide composite heat-conducting film after the mixture is naturally dried.
Comparative example 1
The perovskite-free quantum dot (CsPbBr 3) is removed, and the 4-aminophenylporphyrin/graphene oxide composite material is prepared by the same steps as in example 1.
Comparative example 2
Graphene is not contained, and the steps are the same as those in the embodiment 1, so that the perovskite quantum dot/4-aminophenylporphyrin composite heat conduction film is prepared.
Comparative example 3
The method is characterized in that perovskite quantum dots and 4-aminophenylporphyrin are not contained, and the graphene thermal conduction film is prepared by the same steps as in the embodiment 1.
The perovskite quantum dot/4-aminophenylporphyrin/graphene oxide composite heat-conducting film prepared in the examples 1 to 3 and the comparative materials of the comparative examples 1 to 3 were subjected to analytical tests:
SEM scanning electron microscope results of the perovskite quantum dot/4-aminophenylporphyrin/graphene oxide composite heat conductive films of examples 1, 2, and 3 are shown in fig. 1, 2, and 3, respectively, where the scale is 20 μm. The cross section of the composite heat conduction film is regularly arranged, and the film formed by the heat conduction film of the composite material during suction filtration has high orientation degree, wherein the graphene is tightly combined with the perovskite quantum dots and the 4-aminophenylporphyrin, so that the graphene has good plane orientation.
The conductivity test was performed using a four-probe method, and the test results are shown in the following table. The conclusion is that the pure graphene heat-conducting film has the smallest surface resistance and better electric conductivity, but the perovskite quantum dot/4-aminophenylporphyrin/graphene oxide composite heat-conducting film has higher carrier mobility and better electric conductivity compared with the graphene heat-conducting film.
The heat transfer performance test results are shown in the following table:
experimental results show that the perovskite quantum dot/4-aminophenylporphyrin/graphene oxide composite heat-conducting film has high electrical conductivity and high thermal conductivity. The method is suitable for the preparation and application of electronic devices, and the fields of aerospace heat-conducting elements and the like.
It should be noted that the technical features such as the scanning electron microscope and the like related to the patent application of the present invention should be regarded as the prior art, and the specific structure, the operation principle, the control mode and the spatial arrangement mode of the technical features may be selected conventionally in the field, and should not be regarded as the invention point of the patent of the present invention, and the patent of the present invention is not further specifically described in detail.
Having described preferred embodiments of the present invention in detail, it is to be understood that modifications and variations may be resorted to without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. The preparation method of the perovskite quantum dot/4-aminophenylporphyrin/graphene oxide high-thermal-conductivity composite membrane is characterized by comprising the following steps of:
step one, synthesizing 4-aminophenylporphyrin, adding a stirring magneton into a three-neck round-bottom flask, installing a reflux device, and adding a certain amount of trisnonylphenyl phosphite and SnCl 2 Adding a certain amount of concentrated hydrochloric acid into a conduit, carrying out oil bath reaction at a certain temperature for a period of time, sucking the half-tube liquid by using a rubber head dropper, filtering by using a conical suction filter funnel, putting filter paper into a small beaker, adding a certain amount of triethylamine, adding a small amount of dichloromethane for dissolution, and adding MgSO 4 Drying, washing the filter cake with distilled water, dissolving the filter cake with 5% NaOH solution, adjusting pH to show alkalinity, filtering with Buchner funnel, washing with distilled water, drying the filter cake on watch glass, wrapping the filter cake after drying, and adopting CH 2 Cl 2 Soxhlet extraction is carried out on the solvent until the solvent is colorless, and vacuum drying is carried out to obtain 4-aminophenylporphyrin solid;
step two, preparing graphene oxide, namely putting a certain amount of natural graphite and sodium nitrate into a big beaker, slowly adding a certain amount of concentrated sulfuric acid to obtain a black solution, continuously stirring for a period of time in an ice bath, then slowly adding a certain amount of potassium permanganate to obtain a dark green solution, continuously stirring for a period of time in the ice bath, then slowly adding a certain amount of distilled water to obtain a tan solution, then diluting the tan solution with a certain amount of warm water, removing residual potassium permanganate with a certain amount of hydrogen peroxide to obtain a bright yellow solution, finally filtering the solution, washing the obtained solution with dilute hydrochloric acid and distilled water respectively until the solution is neutral, drying and grinding to obtain graphite oxide, centrifugally washing the product with hydrochloric acid and distilled water to near neutrality, then dialyzing the product to be neutral, and standing the solution for later use;
step three, compounding 4-aminophenylporphyrin and graphene oxide, namely adding a certain amount of 4-aminophenylporphyrin into a certain amount of graphene oxide turbid liquid, magnetically stirring until the dissolution is completed, then putting the mixed solution into an ultrasonic dispersion machine for dispersion to obtain a uniform dispersion liquid of the 4-aminophenylporphyrin and the graphene oxide, measuring a certain volume of the dispersion liquid by using a liquid transfer gun, obtaining a composite heat conduction film on a PVDF film by using a vacuum filtration method, putting the composite heat conduction film into an oven, and drying the composite heat conduction film for a period of time at a constant temperature, and taking off the obtained 4-aminophenylporphyrin/graphene oxide film from the filter film;
step four, preparing the perovskite quantum dot CsPbBr 3 Quantum dots, csPbI 3 Quantum dots and CsPbCl 3 Dispersing the prepared perovskite quantum dots in a certain amount of toluene to obtain toluene dispersion liquid of the perovskite quantum dots for later use;
and step five, compounding the perovskite quantum dots/4-aminophenylporphyrin/graphene oxide, uniformly coating a toluene dispersion liquid of the perovskite quantum dots on the surface of the 4-aminophenylporphyrin/graphene oxide composite heat-conducting membrane in a sample bottle, and naturally drying to obtain the perovskite quantum dots/4-aminophenylporphyrin/graphene oxide high-heat-conducting composite membrane.
2. The preparation method of the perovskite quantum dot/4-aminophenylporphyrin/graphene oxide high thermal conductivity composite film according to claim 1, wherein the perovskite quantum in the step 4 is CsPbBr 3 The quantum dot is prepared by the following steps: preparing precursor solution, adding certain amount of CsBr and PbBr 2 Dissolving the powder in a volume of dimethyl sulfoxide solvent, rapidly injecting a volume of HBr into the solution to promote CsBr dissolution, stirring for a period of time until the precursor powder is completely dissolved, adding a volume of oleic acid and oleylamine to the solution, and mixing with stirringHomogenizing to obtain precursor solution; measuring a certain amount of toluene as a solvent, quickly adding a certain amount of the precursor solution into the toluene solvent which is vigorously stirred, continuously stirring the solution for a period of time, centrifuging, pouring out the supernatant, adding a certain amount of toluene again, fully mixing, centrifuging again, removing the supernatant, and finally adding CsPbBr at the bottom of the solution 3 And dispersing the perovskite precipitate in a certain amount of toluene to obtain a toluene dispersion liquid of the perovskite quantum dots for later use.
3. The preparation method of the perovskite quantum dot/4-aminophenylporphyrin/graphene oxide high thermal conductivity composite film according to claim 2, wherein in the first step, trisnonylphenyl phosphite and SnCl 2 The mass ratio of (2) is 4: sodium nitrate: concentrated sulfuric acid: the weight ratio of potassium permanganate is 1; the weight ratio of the 4-aminophenylporphyrin to the graphene oxide suspension in the third step is 1; csBr and PbBr in the fourth step 2 And the weight ratio of dimethyl sulfoxide to HBr is 1:1.27:30:5.3; and in the fifth step, the coating thickness of the toluene dispersion liquid of the perovskite quantum dots on the surface of the 4-aminophenylporphyrin/graphene oxide composite heat-conducting film is 30-60 mu m.
4. The preparation method of the perovskite quantum dot/4-aminophenylporphyrin/graphene oxide high thermal conductivity composite membrane according to claim 3, wherein in the first step, the pH of the filter cake is adjusted to 7.5 by using potassium carbonate.
5. The preparation method of the perovskite quantum dot/4-aminophenylporphyrin/graphene oxide high thermal conductivity composite film according to claim 4, wherein in the first step, a stirring magneton is added into a three-neck round-bottom flask, a reflux device is installed, and 0.4g of trisnonylphenyl phosphite and 1.5g of SnCl are added 2 Adding 20ml of concentrated hydrochloric acid into a catheter, carrying out oil bath reaction at the temperature of 80 ℃ for 2h, sucking the half-tube liquid by using a rubber head dropper, filtering by using a conical suction filter funnel, putting filter paper with a filter material into a small beaker, and adding2ml of triethylamine, adjusting the pH value of the filter cake by using potassium carbonate solution, adding the filter cake with the adjusted pH value into a small amount of dichloromethane for dissolving, and then adding MgSO 4 Drying, washing the filter cake with distilled water, dissolving the filter cake with 5% NaOH solution, adjusting pH to show alkalinity with potassium carbonate, filtering with Buchner funnel, washing with distilled water, naturally drying the filter cake on a watch glass, wrapping the dried filter cake with filter paper, and adding CH 2 Cl 2 Soxhlet extraction is carried out on the solvent until the solvent is colorless, and vacuum drying is carried out to obtain 4-aminophenylporphyrin solid; putting 1g of natural graphite and 1g of sodium nitrate into a big beaker, slowly adding 46ml of 98% concentrated sulfuric acid to obtain a black solution, continuously stirring for 4 hours in an ice bath, then slowly adding 6g of potassium permanganate to obtain a dark green solution, continuously stirring for 2 hours in the ice bath, then slowly adding 92ml of distilled water to obtain a tan solution, then diluting the tan solution by 350ml of warm water at 40-60 ℃, removing residual potassium permanganate by 20ml of 30% hydrogen peroxide to obtain a bright yellow solution, finally filtering the solution, washing the obtained solution by using dilute hydrochloric acid and distilled water respectively until the solution is neutral, drying and grinding to obtain graphite oxide, centrifugally washing the product to near neutrality by using hydrochloric acid and distilled water, then dialyzing the product to neutrality, and standing the solution for later use; adding 5mg of 4-aminophenylporphyrin into 10ml of graphene oxide turbid liquid in the third step, magnetically stirring for 2 hours until the dissolution is completed, then putting the mixed solution into an ultrasonic dispersion machine for dispersion for 1 hour to obtain a uniform dispersion liquid of the 4-aminophenylporphyrin and the graphene oxide, measuring a certain volume of the dispersion liquid by using a liquid transfer gun, obtaining a composite heat-conducting membrane on a PVDF membrane with the thickness of 0.48 mu m by using a vacuum filtration method, putting the composite heat-conducting membrane into a 50 ℃ oven for constant-temperature drying for 12 hours, and removing the obtained 4-aminophenylporphyrin/graphene oxide membrane from the filter membrane; in the fourth step, when preparing the precursor solution, 0.5mmol CsBr and 0.4mmol PbBr are added 2 The powder was dissolved in 10ml of dimethyl sulfoxide solvent, then 0.5ml of HBr was rapidly injected into the solution to promote the dissolution of CsBr, stirring was continued for 1h until the powder was completely dissolved, 1.0ml of oleic acid and 0.4ml of oleylamine were added to the solution, and mixing was performed with sufficient stirringMixing uniformly to obtain a precursor solution; measuring 10ml of toluene as solvent, quickly adding 1ml of the precursor solution into the toluene solvent which is vigorously stirred, continuously stirring the solution for 10min, centrifuging, pouring out the supernatant, adding a certain amount of toluene again, fully mixing, centrifuging again, removing the supernatant, and finally adding CsPbBr at the bottom of the solution 3 And dispersing the perovskite precipitate in 5ml of toluene to obtain a toluene dispersion liquid of perovskite quantum dots for later use.
6. The perovskite quantum dot/4-aminophenylporphyrin/graphene oxide high-thermal-conductivity composite film is characterized by being prepared by the preparation method of any one of claims 1 to 5.
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