WO2023000429A1 - Composite material capable of achieving photothermal blending, preparation method therefor, and application thereof - Google Patents
Composite material capable of achieving photothermal blending, preparation method therefor, and application thereof Download PDFInfo
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- WO2023000429A1 WO2023000429A1 PCT/CN2021/113944 CN2021113944W WO2023000429A1 WO 2023000429 A1 WO2023000429 A1 WO 2023000429A1 CN 2021113944 W CN2021113944 W CN 2021113944W WO 2023000429 A1 WO2023000429 A1 WO 2023000429A1
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- composite material
- photothermal
- carbonaceous material
- carbon
- photothermal composite
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- 239000002131 composite material Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000002156 mixing Methods 0.000 title claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005519 non-carbonaceous material Substances 0.000 claims abstract description 18
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- 229920000128 polypyrrole Polymers 0.000 claims description 21
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 229960003638 dopamine Drugs 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 2
- 229920002307 Dextran Polymers 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims description 2
- 239000010432 diamond Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920001690 polydopamine Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000007962 solid dispersion Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims description 2
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 230000020169 heat generation Effects 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 230000005284 excitation Effects 0.000 description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 238000000608 laser ablation Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- 238000004020 luminiscence type Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- -1 Cerium Sulfate-Carbon Chemical compound 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- BGMHGWBCHOENFP-UHFFFAOYSA-H [C+4].[OH-].[Sr+2].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [C+4].[OH-].[Sr+2].[OH-].[OH-].[OH-].[OH-].[OH-] BGMHGWBCHOENFP-UHFFFAOYSA-H 0.000 description 2
- DYHOFCVNOKHRNT-FAOVPRGRSA-N [O-2].[Zn+2].O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO Chemical compound [O-2].[Zn+2].O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO DYHOFCVNOKHRNT-FAOVPRGRSA-N 0.000 description 2
- 238000002679 ablation Methods 0.000 description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 2
- 230000005461 Bremsstrahlung Effects 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000008621 organismal health Effects 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012857 radioactive material Substances 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 150000002909 rare earth metal compounds Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/54—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/57—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/60—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing iron, cobalt or nickel
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/60—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing iron, cobalt or nickel
- C09K11/602—Chalcogenides
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/671—Chalcogenides
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
- C09K11/701—Chalcogenides
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
- C09K11/7727—Sulfates
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
- G03B21/00—Projectors or projection-type viewers; Accessories therefor
- G03B21/14—Details
- G03B21/20—Lamp housings
- G03B21/2006—Lamp housings characterised by the light source
- G03B21/2033—LED or laser light sources
- G03B21/204—LED or laser light sources using secondary light emission, e.g. luminescence or fluorescence
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Definitions
- the invention relates to the fields of luminescent materials and photothermal materials, in particular to a composite material capable of realizing photothermal adjustment, its preparation method and application.
- Luminescent materials are materials that absorb energy in some way, converting it into light radiation. When the material is excited by an external force (ray, electron beam, electric field, etc.), the material is in an excited state, and the energy in the excited state is released in the form of light and heat.
- various piezoelectric luminescent and photoluminescent materials have been developed. Among them, materials that generate light and heat through laser excitation can remotely control the light and heat of the material.
- radioactive materials are usually added to the material. , such as cobalt, radium, tritium, etc. If these substances are not properly handled, they will seriously affect the health of organisms and pollute the environment.
- the present invention provides a composite material capable of photothermal deployment, the preparation method is simple, and the composite material can realize instantaneous fixed-point light emission and heat generation under the irradiation of laser light, and can be controlled by adjusting The type and content of the material and the intensity of the laser are used to adjust the light and heat, which has a good application prospect in the field of luminescent and heating materials.
- the present invention provides the following technical solutions:
- the first aspect of the present invention provides a method for preparing a photothermal composite material, including method (1) or method (2):
- the carbonaceous material is a simple substance of carbon and/or a carbon-containing polymer material; the non-carbonaceous material is a simple substance of a rare earth metal and its compound and/or a simple substance of a transition metal and its compound.
- Carbonaceous materials can emit light and generate heat under laser excitation, but carbonaceous materials have poor thermal stability. Adding non-carbonaceous materials can enhance the thermal stability of carbonaceous materials (such as carbon dots-titanium dioxide composites, carbon will be Embedded inside the titania lattice, which acts as a framework to stabilize the carbon structure).
- the simple carbon substance is one or more of carbon dots, carbon nanotubes, graphite, diamond, and footballene.
- the carbon-containing polymer material includes a carbon-containing polymer monomer and a carbon-containing polymer; the carbon-containing polymer monomer is one or more of pyrrole, glucose, dopamine, and aniline; the The carbon-containing polymer is one or more of polypyrrole, dextran, polydopamine, and polyaniline.
- the rare earth metal compound is a salt, alloy, complex, oxide or hydroxide containing rare earth metal atoms.
- the transition metal compound is a transition metal-containing salt, alloy, complex, oxide or hydroxide.
- the non-carbonaceous material is preferably one of Fe 2 O 3 , Co(OH) 2 , H 3 PO 4 ⁇ 12MoO 3 , cerium sulfate, TiO 2 , strontium hydroxide, manganese carbonate, copper acetate or iron powder or Various.
- the oxidizing agent described in method (1) is one of iron salt, copper salt, chlorate, perchlorate, nitrate, permanganate, concentrated sulfuric acid, manganese dioxide, such as hexahydrate chloride Iron; the addition of oxidizing agents promotes the polymerization of carbon-containing macromolecular monomers.
- the second aspect of the present invention provides the application of the photothermal composite material described in the first aspect in target lighting and local heating.
- the photothermal composite material generates light and heat under the action of laser light.
- the third aspect of the present invention provides the application of the photothermal composite material described in the first and second aspects in directional light emission.
- the non-carbonaceous material in the photothermal composite material is titanium dioxide.
- the mass fraction of the carbonaceous material in the photothermal composite material is 5wt%-60wt%.
- the carbonaceous material-titanium dioxide composite material generates directional white light under the action of laser light.
- the carbonaceous material in the carbonaceous material-titanium dioxide composite material is used as the emission center. Based on bremsstrahlung, under the action of the laser, the carbonaceous material encapsulated in the titanium dioxide produces white light and is reflected in the microcavity of the titanium dioxide. Based on this microcavity amplification Titanium dioxide amplifies the white light emitted by carbonaceous materials. After the amplified light exceeds a certain threshold, it escapes from the titanium dioxide microcavity. Due to the phased array effect of the composite material, the escaped white light has directionality.
- the wavelength of the laser is in the near-infrared band, specifically 780nm-2000nm.
- the present invention prepares a photothermal composite material by ultrasonic centrifugation or grinding of carbonaceous materials and non-carbonaceous materials.
- the preparation method is simple, the conditions are mild, and there are many kinds of reactants available, which is suitable for mass production.
- a photothermal composite material prepared by the present invention can emit light and generate heat instantaneously under laser excitation, and has a long luminous time and high heating temperature, which can be as high as thousands of degrees, and the compound is stable and difficult to decompose.
- the present invention can irradiate the composite material at a fixed point with a laser to achieve target lighting and local heating. It can control the type and content of each material in the composite material and the intensity of the laser for photothermal deployment to meet the specific needs of luminescence and heat generation.
- the carbonaceous material-titanium dioxide composite material can produce white light with a specific direction when excited by laser, but it is not omnidirectional, and can be applied to projection equipment. Therefore, this type of composite material has broad application prospects in the field of luminescent and photothermal materials.
- Figure 1 is the photos of Fe 2 O 3 -polypyrrole photothermal composite material before and after being excited by infrared laser;
- Figure 2 shows the temperature changes of TiO 2 -polypyrrole composites under pulsed laser irradiation and continuous laser irradiation respectively, where the two curves in Figure b are the sample temperature changes under different laser intensities;
- Fig. 3 is the white light emission spectrum of carbon dot-titania composite material
- Figure 4 is the luminous etendue of the carbon dot-titanium dioxide composite material when it is excited by near-infrared light;
- Figure 5 shows the application of carbon dots-titanium dioxide composite materials in target lighting and projection devices.
- Example 1 Fe 2 O 3 -polypyrrole photothermal composite material
- Fe 2 O 3 -polypyrrole photothermal composite material emits bright light and generates a lot of heat under infrared laser ablation and excitation.
- the brightness time can reach several months, and the heat generation can reach thousands of degrees.
- Example 3 H 3 PO 4 ⁇ 12MoO 3 -polypyrrole photothermal composite material
- H 3 PO 4 ⁇ 12MoO 3 -polypyrrole photothermal composite material emits light and generates a lot of heat under infrared laser ablation and excitation.
- cerium sulfate-carbon dot photothermal composite material emits light and generates a lot of heat under infrared laser ablation and excitation.
- Example 5 TiO 2 -polypyrrole photothermal composite material
- TiO 2 dispersion 10mL of TiO 2 dispersion, 2mL of pyrrole, and 10mL of deionized water into a beaker, then add 2.7g of FeCl 3 6H 2 O, mix, ultrasonicate for 5min, and then centrifuge, wash away impurities with deionized water, and remove the blue precipitate in the lower layer
- the material was taken out and dried, and the obtained TiO 2 -polypyrrole photothermal composite material was ablated and excited by an 808nm infrared laser to emit light and generate a large amount of heat.
- the prepared TiO 2 -polypyrrole photothermal composite material was irradiated by pulsed laser and continuous laser respectively, as shown in Figure 2,
- Figure 2a is the temperature change diagram obtained by pulsed laser irradiation of the composite material, as can be seen from the figure,
- the temperature of the composite material can be as high as 1200K under pulsed laser irradiation; the temperature change of the composite material is shown in Figure 2b when the composite material is irradiated with continuous laser light with different light powers.
- Curves 1 and 2 in Figure 2b are the continuous The temperature change curve obtained by laser irradiation, it can be seen from the figure that the temperature can be as high as above 1000°C with 2W continuous laser irradiation for about 12s, and the temperature is nearly 900K with 1W continuous laser irradiation for the same time, so it can be seen that by adjusting the laser The light power can adjust the heating temperature of the composite material.
- strontium hydroxide weigh 4g of strontium hydroxide and 17mg of carbon dots in a mortar and grind for 3 minutes.
- the obtained strontium hydroxide-carbon dot photothermal composite material emits light and generates a lot of heat under infrared laser ablation and excitation.
- Embodiment 7 manganese carbonate-polypyrrole thermal composite material
- Example 8 Copper acetate-polypyrrole photothermal composite material
- iron powder-polypyrrole photothermal composite material emits light and generates a lot of heat under infrared laser ablation and excitation.
- Embodiment 10 polyaniline-zinc oxide photothermal composite material
- Embodiment 11 dopamine-zinc oxide photothermal composite material
- dopamine-zinc oxide photothermal composite material emits light and generates a lot of heat under the ablation and excitation of 808nm laser during drying.
- Embodiment 12 glucose-zinc oxide photothermal composite material
- glucose-zinc oxide photothermal composite material emits light and generates a lot of heat under the ablation and excitation of 808 nm laser during drying.
- Embodiment 13 Carbon dots-titanium dioxide photothermal composite material
- the carbon dot-titanium dioxide composite material produces white light under the excitation of 980nm near-infrared light (5W/cm 2 ), and its emission spectrum is shown in Figure 3, and Figure 4 shows the emission spectrum of the composite material when it is excited by near-infrared light
- the luminescence angle of the carbon dot-titanium dioxide composite material under photoluminescence is 60°, which further shows that the composite material can achieve directional luminescence instead of omnidirectional luminescence under the action of laser.
- Embodiment 14 Application of carbon dots-titanium dioxide photothermal composite material
- the carbon dot-titanium dioxide photothermal composite material prepared in Example 10 was placed on a glass sheet and covered with a layer of glass sheet, as shown in Figure 5a-c, a light-emitting source was prepared, which can be used for target illumination by combining it with a laser device ( Figure 5d-f), in addition, the light source can be used in projection devices, as shown in 5g-i, the laser light is irradiated on the light source to generate directional white light, which is irradiated on the picture of the projection film, and projected onto the screen through the condenser lens to complete the projection .
- a composite material with photothermal properties can be prepared from simple carbon or polypyrrole as a carbonaceous material, with transition metal oxides, hydroxides, complexes, salts, simple substances, and salts of rare earth metals.
- Materials, and the prepared various photothermal composite materials can emit light and generate a lot of heat under the excitation of infrared lasers, and the local temperature can be as high as thousands of degrees, which can be applied to lighting and local heating devices.
- Carbon dots-titanium dioxide composites can achieve directional light emission and have potential applications in target lighting and projection.
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Abstract
A composite material capable of achieving photothermal blending, a preparation method therefor, and an application thereof. The preparation method comprises method (1) or method (2). Method (1) comprises adding a first carbonaceous material and a first non-carbonaceous material to water, directly mixing or adding an oxidant and mixing, ultrasonicating, centrifuging, and washing after mixing, removing a precipitate, and drying to obtain a composite material. Method (2) comprises grinding a second carbonaceous material and a second non-carbonaceous material to obtain a photothermal composite material. The described preparation method is simple and has many kinds of reactants, the costs are relatively low, and the prepared composite material can achieve instant fixed-point light emission and heat generation under laser light irradiation. The intensity, time and generated temperature of light emission can be adjusted by adjusting the type and content of material as well as laser intensity. In addition, a carbonaceous material-titanium dioxide composite material can achieve directional light emission, which has application potential in projection, target lighting, etc.
Description
本发明涉及发光材料及光热材料领域，具体涉及一种可实现光热调配的复合材料及其制备方法与应用。The invention relates to the fields of luminescent materials and photothermal materials, in particular to a composite material capable of realizing photothermal adjustment, its preparation method and application.
发光材料是指能以某种方式吸收能力，将其转化为光辐射的材料。当材料收到外接作用力(射线、电子束、电场等)激发后，材料处于激发态，激发态的能量通过光、热的形式释放出来。近年来研发出各种压电发光、光致发光材料，其中通过激光激发而产生光热的材料，可远距离调控材料发光发热，但为提升材料的发光亮度，通常会在材料中添加放射性材料，例如钴、镭、氚等，这类物质若得不到妥善处理会严重影响生物的健康以及污染环境。Luminescent materials are materials that absorb energy in some way, converting it into light radiation. When the material is excited by an external force (ray, electron beam, electric field, etc.), the material is in an excited state, and the energy in the excited state is released in the form of light and heat. In recent years, various piezoelectric luminescent and photoluminescent materials have been developed. Among them, materials that generate light and heat through laser excitation can remotely control the light and heat of the material. However, in order to improve the luminous brightness of the material, radioactive materials are usually added to the material. , such as cobalt, radium, tritium, etc. If these substances are not properly handled, they will seriously affect the health of organisms and pollute the environment.
此外，目前大量的发光材料需经过烧结再破碎的过程，烧结需在氮气和氢气混合气体中进行，设备复杂且操作难度高，由于在氢气下高温烧结，反应过程存在安全隐患，烧结后再破碎成粉体，由于高温烧结得到的块体硬度高，难以破碎，需使用相关设备加以辅助得到均匀的粉体，制备过程复杂且对设备、反应条件要求较高，因此生产成本相对较高。In addition, at present, a large number of luminescent materials need to go through the process of sintering and crushing. The sintering needs to be carried out in a mixed gas of nitrogen and hydrogen. Forming into powder, due to the high hardness of the block obtained by high-temperature sintering, it is difficult to break, and it needs to be assisted by related equipment to obtain a uniform powder. The preparation process is complicated and requires high equipment and reaction conditions, so the production cost is relatively high.
如何通过安全、普遍的材料以及简单的制备方法制备发光、光热材料，并且可以通过参数控制来调节光热材料的发光以及发热性能，以满足不同应用的特殊需求，是急需解决且具有实用价值的研究课题。How to prepare luminescent and photothermal materials through safe and common materials and simple preparation methods, and how to adjust the luminescence and heat generation properties of photothermal materials through parameter control to meet the special needs of different applications is an urgent need to solve and has practical value research topics.
发明内容Contents of the invention
为克服现有技术的缺点和不足，本发明提供了一种可实现光热调配的复合 材料，制备方法简单，且该复合材料在激光的照射下可实现瞬间定点发光、发热，并可通过调控材料的种类、含量以及激光的强度进行光热调配，在发光发热材料领域具有很好的应用前景。In order to overcome the shortcomings and deficiencies of the prior art, the present invention provides a composite material capable of photothermal deployment, the preparation method is simple, and the composite material can realize instantaneous fixed-point light emission and heat generation under the irradiation of laser light, and can be controlled by adjusting The type and content of the material and the intensity of the laser are used to adjust the light and heat, which has a good application prospect in the field of luminescent and heating materials.
为了解决上述技术问题，本发明提供了如下所述的技术方案：In order to solve the above technical problems, the present invention provides the following technical solutions:
本发明第一方面提供了一种光热复合材料的制备方法，包括方法(1)或方法(2):The first aspect of the present invention provides a method for preparing a photothermal composite material, including method (1) or method (2):
(1)将第一碳质材料和第一非碳质材料加至水中，直接混合或加入氧化剂混合，混合后超声、离心、洗涤，取出沉淀物，干燥后得到一种光热复合材料；所述第一碳质材料与第一非碳质材料至少有一种为液体或固体分散液；(1) adding the first carbonaceous material and the first non-carbonaceous material to water, directly mixing or adding an oxidant to mix, after mixing, ultrasonication, centrifugation, washing, taking out the precipitate, and drying to obtain a photothermal composite material; At least one of the first carbonaceous material and the first non-carbonaceous material is a liquid or solid dispersion;
(2)将第二碳质材料和第二非碳质材料置于容器中，研磨后得到一种光热复合材料；所述第二碳质材料和第二非碳质材料均为固体；(2) placing a second carbonaceous material and a second non-carbonaceous material in a container, and grinding to obtain a photothermal composite material; both the second carbonaceous material and the second non-carbonaceous material are solid;
所述碳质材料为碳单质和/或含碳高分子材料；所述非碳质材料为稀土金属的单质及其化合物和/或过渡金属的单质及其化合物。The carbonaceous material is a simple substance of carbon and/or a carbon-containing polymer material; the non-carbonaceous material is a simple substance of a rare earth metal and its compound and/or a simple substance of a transition metal and its compound.
碳质材料在激光激发作用下可以发光发热，但碳质材料热稳定性差，加入非碳质材料可以增强碳质材料的热稳定性(例如碳点-二氧化钛的复合材料，碳在激光作用下会嵌入二氧化钛晶格内部，晶格作为框架可以稳固碳的结构)。Carbonaceous materials can emit light and generate heat under laser excitation, but carbonaceous materials have poor thermal stability. Adding non-carbonaceous materials can enhance the thermal stability of carbonaceous materials (such as carbon dots-titanium dioxide composites, carbon will be Embedded inside the titania lattice, which acts as a framework to stabilize the carbon structure).
进一步地，所述碳单质为碳点、碳纳米管、石墨、金刚石、足球烯中的一种或多种。Further, the simple carbon substance is one or more of carbon dots, carbon nanotubes, graphite, diamond, and footballene.
进一步地，所述含碳高分子材料包括含碳高分子单体和含碳高分子聚合物；所述含碳高分子单体为吡咯、葡萄糖、多巴胺、苯胺中的一种多种；所述含碳高分子聚合物为聚吡咯、葡聚糖、聚多巴胺、聚苯胺中的一种或多种。Further, the carbon-containing polymer material includes a carbon-containing polymer monomer and a carbon-containing polymer; the carbon-containing polymer monomer is one or more of pyrrole, glucose, dopamine, and aniline; the The carbon-containing polymer is one or more of polypyrrole, dextran, polydopamine, and polyaniline.
进一步地，所述稀土金属的化合物为含稀土金属原子的盐、合金、络合物、氧化物或氢氧化物。Further, the rare earth metal compound is a salt, alloy, complex, oxide or hydroxide containing rare earth metal atoms.
进一步地，所述过渡金属的化合物为含过渡金属的盐、合金、络合物、氧化物或氢氧化物。Further, the transition metal compound is a transition metal-containing salt, alloy, complex, oxide or hydroxide.
进一步地，非碳质材料优选Fe
2O
3、Co(OH)
2、H
3PO
4·12MoO
3、硫酸铈、TiO
2、氢氧化锶、碳酸锰、乙酸铜或铁粉中的一种或多种。
Further, the non-carbonaceous material is preferably one of Fe 2 O 3 , Co(OH) 2 , H 3 PO 4 ·12MoO 3 , cerium sulfate, TiO 2 , strontium hydroxide, manganese carbonate, copper acetate or iron powder or Various.
进一步地，方法(1)所述氧化剂为铁盐、铜盐、氯酸盐、高氯酸盐、硝酸盐、高锰酸盐、浓硫酸、二氧化锰中的一种，例如六水合氯化铁；氧化剂的加入促使含碳高分子单体发生聚合反应。Further, the oxidizing agent described in method (1) is one of iron salt, copper salt, chlorate, perchlorate, nitrate, permanganate, concentrated sulfuric acid, manganese dioxide, such as hexahydrate chloride Iron; the addition of oxidizing agents promotes the polymerization of carbon-containing macromolecular monomers.
本发明第二方面提供了第一方面所述的一种光热复合材料在目标照明及局部加热方面的应用。The second aspect of the present invention provides the application of the photothermal composite material described in the first aspect in target lighting and local heating.
进一步地，所述光热复合材料在激光作用下产生光和热。Further, the photothermal composite material generates light and heat under the action of laser light.
本发明第三方面提供了第一、二方面所述的一种光热复合材料在定向发光方面的应用。The third aspect of the present invention provides the application of the photothermal composite material described in the first and second aspects in directional light emission.
进一步地，所述光热复合材料中的非碳质材料为二氧化钛。Further, the non-carbonaceous material in the photothermal composite material is titanium dioxide.
进一步地，所述光热复合材料中的碳质材料的质量分数为5wt％-60wt％。Further, the mass fraction of the carbonaceous material in the photothermal composite material is 5wt%-60wt%.
进一步地，所述碳质材料-二氧化钛的复合材料在激光的作用下产生定向白光。Further, the carbonaceous material-titanium dioxide composite material generates directional white light under the action of laser light.
碳质材料-二氧化钛复合材料中碳质材料作为发射中心，基于轫致辐射，在激光作用下，封装在二氧化钛内部的碳质材料产生白光并在二氧化钛的微腔内反射，基于这种微腔放大效应，二氧化钛对碳质材料发出的白光进行放大，放大后的光超过一定的阈值后，从二氧化钛微腔中逃逸，由于复合材料的相控阵效应，使逃逸的白光具有方向性。The carbonaceous material in the carbonaceous material-titanium dioxide composite material is used as the emission center. Based on bremsstrahlung, under the action of the laser, the carbonaceous material encapsulated in the titanium dioxide produces white light and is reflected in the microcavity of the titanium dioxide. Based on this microcavity amplification Titanium dioxide amplifies the white light emitted by carbonaceous materials. After the amplified light exceeds a certain threshold, it escapes from the titanium dioxide microcavity. Due to the phased array effect of the composite material, the escaped white light has directionality.
进一步地，所述激光的波长为近红外光波段，具体为780nm-2000nm。Further, the wavelength of the laser is in the near-infrared band, specifically 780nm-2000nm.
与现有技术相比，本发明的有益效果在于：Compared with prior art, the beneficial effect of the present invention is:
1.本发明通过将碳质材料与非碳质材料通过超声离心或研磨的方法制备得到一种光热复合材料，制备方法简单、条件温和、可用的反应物种类多，适合大批量生产。1. The present invention prepares a photothermal composite material by ultrasonic centrifugation or grinding of carbonaceous materials and non-carbonaceous materials. The preparation method is simple, the conditions are mild, and there are many kinds of reactants available, which is suitable for mass production.
2.本发明制备的一种光热复合材料，在激光的激发下可瞬间发光、发热，且发光时间长、发热温度高，可高达上千度，复合物性质稳定不易分解。2. A photothermal composite material prepared by the present invention can emit light and generate heat instantaneously under laser excitation, and has a long luminous time and high heating temperature, which can be as high as thousands of degrees, and the compound is stable and difficult to decompose.
3.本发明可通过激光定点照射复合材料以达到目标照明和局部加热的作用，可通过控制复合材料中各材料的种类、含量以及激光的强度进行光热调配，以满足特定发光发热的需求，其中碳质材料-二氧化钛复合材料由激光激发可产生具有特定方向的白光，并非全向发光，可应用于投影设备，因此该类复合材料在发光、光热材料领域具有广泛的应用前景。3. The present invention can irradiate the composite material at a fixed point with a laser to achieve target lighting and local heating. It can control the type and content of each material in the composite material and the intensity of the laser for photothermal deployment to meet the specific needs of luminescence and heat generation. Among them, the carbonaceous material-titanium dioxide composite material can produce white light with a specific direction when excited by laser, but it is not omnidirectional, and can be applied to projection equipment. Therefore, this type of composite material has broad application prospects in the field of luminescent and photothermal materials.
图1是Fe
2O
3-聚吡咯光热复合材料被红外激光激发前、后的照片；
Figure 1 is the photos of Fe 2 O 3 -polypyrrole photothermal composite material before and after being excited by infrared laser;
图2是TiO
2-聚吡咯复合材料分别在脉冲激光照射和连续激光照射下的温度变化，其中图b的两个曲线分别是不同激光强度下的样品温度变化；
Figure 2 shows the temperature changes of TiO 2 -polypyrrole composites under pulsed laser irradiation and continuous laser irradiation respectively, where the two curves in Figure b are the sample temperature changes under different laser intensities;
图3是碳点-二氧化钛复合材料的白光发射光谱；Fig. 3 is the white light emission spectrum of carbon dot-titania composite material;
图4是碳点-二氧化钛复合材料被近红外光激发时的发光集光率；Figure 4 is the luminous etendue of the carbon dot-titanium dioxide composite material when it is excited by near-infrared light;
图5是碳点-二氧化钛复合材料在目标照明和投影装置中的应用。Figure 5 shows the application of carbon dots-titanium dioxide composite materials in target lighting and projection devices.
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, so that those skilled in the art can better understand the present invention and implement it, but the examples given are not intended to limit the present invention.
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术 语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field of the invention. The terminology used herein in the description of the present invention is for the purpose of describing specific embodiments only, and is not intended to limit the present invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
下述实施例中所使用的实验方法如无特殊说明，均为常规方法，所用的材料、试剂等，如无特殊说明，均可从商业途径得到。The experimental methods used in the following examples are conventional methods unless otherwise specified, and the materials and reagents used can be obtained from commercial sources unless otherwise specified.
实施例1：Fe
2O
3-聚吡咯光热复合材料
Example 1: Fe 2 O 3 -polypyrrole photothermal composite material
分别称取4g Fe
2O
3、2mL吡咯、10mL去离子水于烧杯中，再加入2.7g FeCl
3·6H
2O，混合、超声5min后离心，用去离子水洗去杂质，将下层黑色沉淀物取出后干燥，得到的Fe
2O
3-聚吡咯光热复合材料在红外激光烧蚀并激发下发出亮光并产生大量热，亮度时间可达数月，发热可达上千度。
Weigh 4g Fe 2 O 3 , 2mL pyrrole, and 10mL deionized water into a beaker, then add 2.7g FeCl 3 6H 2 O, mix, ultrasonicate for 5min and centrifuge, wash away impurities with deionized water, and remove the black precipitate in the lower layer After being taken out and dried, the obtained Fe 2 O 3 -polypyrrole photothermal composite material emits bright light and generates a lot of heat under infrared laser ablation and excitation. The brightness time can reach several months, and the heat generation can reach thousands of degrees.
如图1a所示，将少量Fe
2O
3-聚吡咯光热复合材料放置玻璃片上，用红外激光照射，结果如图1b所示，被照射的复合材料发光。
As shown in Figure 1a, a small amount of Fe 2 O 3 -polypyrrole photothermal composite material was placed on a glass plate and irradiated with an infrared laser. As shown in Figure 1b, the irradiated composite material emitted light.
实施例2：Co(OH)
2-聚吡咯光热复合材料
Example 2: Co(OH) 2 -polypyrrole photothermal composite material
分别称取3g Co(OH)
2、2mL吡咯、10mL去离子水于烧杯中，再加入2.7g FeCl
3·6H
2O，混合、超声5min后离心，用去离子水洗去杂质，将下层蓝色沉淀物取出干燥，得到的Co(OH)
2-聚吡咯光热复合材料在红外激光烧蚀并激发下发光并产大量热。
Weigh 3g Co(OH) 2 , 2mL pyrrole, and 10mL deionized water into a beaker, then add 2.7g FeCl 3 6H 2 O, mix, sonicate for 5min and centrifuge, wash with deionized water to remove impurities, and remove the blue The precipitate is taken out and dried, and the obtained Co(OH) 2 -polypyrrole photothermal composite material emits light and generates a lot of heat under infrared laser ablation and excitation.
实施例3：H
3PO
4·12MoO
3-聚吡咯光热复合材料
Example 3: H 3 PO 4 ·12MoO 3 -polypyrrole photothermal composite material
分别称取4g磷钼酸、2mL吡咯、10mL去离子水于烧杯中，再加入2.7g FeCl
3·6H
2O，混合、超声5min后离心，用去离子水洗去杂质，将下层蓝色沉淀物取出干燥，得到的H
3PO
4·12MoO
3-聚吡咯光热复合材料在红外激光烧蚀并激发下发光并产大量热。
Weigh 4g of phosphomolybdic acid, 2mL of pyrrole, and 10mL of deionized water into a beaker, then add 2.7g of FeCl 3 6H 2 O, mix, sonicate for 5 minutes, and then centrifuge, wash away impurities with deionized water, and remove the blue precipitate in the lower layer After taking out and drying, the obtained H 3 PO 4 ·12MoO 3 -polypyrrole photothermal composite material emits light and generates a lot of heat under infrared laser ablation and excitation.
实施例4：硫酸铈-碳点光热复合材料Example 4: Cerium Sulfate-Carbon Dot Photothermal Composite Material
分别称取3g硫酸铈、17mg碳点于研钵中，研磨3min，得到的硫酸铈-碳点光热复合材料在红外激光烧蚀并激发下发光并产大量热。Weigh 3g of cerium sulfate and 17mg of carbon dots in a mortar and grind for 3 minutes. The obtained cerium sulfate-carbon dot photothermal composite material emits light and generates a lot of heat under infrared laser ablation and excitation.
实施例5：TiO
2-聚吡咯光热复合材料
Example 5: TiO 2 -polypyrrole photothermal composite material
分别称取10mL TiO
2分散液、2mL吡咯、10mL去离子水于烧杯中，再加入2.7g FeCl
3·6H
2O，混合、超声5min后离心，用去离子水洗去杂质，将下层蓝色沉淀物取出干燥，得到的TiO
2-聚吡咯光热复合材料在808nm红外激光烧蚀并激发下发光并产大量热。
Weigh 10mL of TiO 2 dispersion, 2mL of pyrrole, and 10mL of deionized water into a beaker, then add 2.7g of FeCl 3 6H 2 O, mix, ultrasonicate for 5min, and then centrifuge, wash away impurities with deionized water, and remove the blue precipitate in the lower layer The material was taken out and dried, and the obtained TiO 2 -polypyrrole photothermal composite material was ablated and excited by an 808nm infrared laser to emit light and generate a large amount of heat.
将制备得到的TiO
2-聚吡咯光热复合材料分别使用脉冲激光照射和连续激光照射，如图2所示，图2a为脉冲激光照射复合材料得到的温度变化图，从图中可以看出，复合材料在脉冲激光照射下，温度可高达1200K；使用不同光照功率的连续激光照射复合材料，其温度变化如图2b所示，图2b中曲线①、②分别为光照功率为2W、1W的连续激光照射得到的温度变化曲线图，由图可知，用2W连续激光照射12s左右温度可高达1000℃以上，用光照功率为1W的连续激光照射相同的时间，温度近900K，由此可知通过调节激光的光照功率可调控复合材料发热的温度。
The prepared TiO 2 -polypyrrole photothermal composite material was irradiated by pulsed laser and continuous laser respectively, as shown in Figure 2, Figure 2a is the temperature change diagram obtained by pulsed laser irradiation of the composite material, as can be seen from the figure, The temperature of the composite material can be as high as 1200K under pulsed laser irradiation; the temperature change of the composite material is shown in Figure 2b when the composite material is irradiated with continuous laser light with different light powers. Curves ① and ② in Figure 2b are the continuous The temperature change curve obtained by laser irradiation, it can be seen from the figure that the temperature can be as high as above 1000°C with 2W continuous laser irradiation for about 12s, and the temperature is nearly 900K with 1W continuous laser irradiation for the same time, so it can be seen that by adjusting the laser The light power can adjust the heating temperature of the composite material.
实施例6：氢氧化锶-碳点光热复合材料Example 6: Strontium Hydroxide-Carbon Dot Photothermal Composite Material
分别称取4g氢氧化锶、17mg碳点于研钵中，研磨3min，得到的氢氧化锶-碳点光热复合材料在红外激光烧蚀并激发下发光并产大量热。Weigh 4g of strontium hydroxide and 17mg of carbon dots in a mortar and grind for 3 minutes. The obtained strontium hydroxide-carbon dot photothermal composite material emits light and generates a lot of heat under infrared laser ablation and excitation.
实施例7：碳酸锰-聚吡咯热复合材料Embodiment 7: manganese carbonate-polypyrrole thermal composite material
分别称取4g碳酸锰、2mL吡咯、10mL去离子水于烧杯中，再加入2.7g FeCl
3·6H
2O，混合、超声5min后离心，用去离子水洗去杂质，将下层黑色沉淀物取出干燥，得到的碳酸锰-聚吡咯热复合材料在红外激光烧蚀并激发下发光并产大量热。
Weigh 4g of manganese carbonate, 2mL of pyrrole, and 10mL of deionized water into a beaker, then add 2.7g of FeCl 3 6H 2 O, mix, ultrasonicate for 5 minutes, and then centrifuge, wash with deionized water to remove impurities, and take out the black precipitate in the lower layer to dry , the obtained manganese carbonate-polypyrrole thermal composite material emits light and produces a large amount of heat under infrared laser ablation and excitation.
实施例8：乙酸铜-聚吡咯光热复合材料Example 8: Copper acetate-polypyrrole photothermal composite material
分别称取5g乙酸铜、2mL吡咯、10mL去离子水于烧杯中，再加入2.7g FeCl
3·6H
2O，混合、超声5min后离心，用去离子水洗去杂质，将下层蓝色沉淀物取出干燥，得到的乙酸铜-聚吡咯光热复合材料在红外激光烧蚀并激发下发 光并产大量热。
Weigh 5g of copper acetate, 2mL of pyrrole, and 10mL of deionized water into a beaker, then add 2.7g of FeCl 3 6H 2 O, mix, ultrasonicate for 5 minutes and centrifuge, wash away impurities with deionized water, and take out the blue precipitate in the lower layer After drying, the obtained copper acetate-polypyrrole photothermal composite material emits light and produces a large amount of heat under infrared laser ablation and excitation.
实施例9：铁粉-聚吡咯光热复合材料Example 9: Iron powder-polypyrrole photothermal composite material
分别称取5g铁粉、2mL吡咯、10mL去离子水于烧杯中，再加入2.7g FeCl
3·6H
2O，混合、超声5min后离心，用去离子水洗去杂质，将下层褐色沉淀物取出干燥，得到的铁粉-聚吡咯光热复合材料在红外激光烧蚀并激发下发光并产大量热。
Weigh 5g of iron powder, 2mL of pyrrole, and 10mL of deionized water into a beaker, then add 2.7g of FeCl 3 6H 2 O, mix, ultrasonicate for 5 minutes, then centrifuge, wash with deionized water to remove impurities, and take out the lower brown precipitate and dry it. , the obtained iron powder-polypyrrole photothermal composite material emits light and generates a lot of heat under infrared laser ablation and excitation.
实施例10:聚苯胺-氧化锌光热复合材料Embodiment 10: polyaniline-zinc oxide photothermal composite material
取2mL的苯胺放入10mL氧化锌水分散液中，向里面加入1mL的HCl，逐步滴加氧化剂3g的FeCl
3·6H
2O，并不断搅拌，冷水浴搅拌24h，离心后洗去杂质，将沉淀物取出干燥，得到的聚苯胺-氧化锌光热复合材料在烘干用808nm激光烧蚀并激发下发光并产大量热。
Take 2mL of aniline and put it into 10mL of zinc oxide water dispersion, add 1mL of HCl into it, gradually add 3g of FeCl 3 6H 2 O as an oxidant dropwise, and keep stirring, stir in a cold water bath for 24h, centrifuge and wash away impurities. The precipitate is taken out and dried, and the obtained polyaniline-zinc oxide photothermal composite material is ablated and excited by an 808nm laser to emit light and generate a lot of heat.
实施例11:多巴胺-氧化锌光热复合材料Embodiment 11: dopamine-zinc oxide photothermal composite material
取2mL的多巴胺放于10mL氧化锌水分散液中搅拌30min均匀，随后干燥，得到的多巴胺-氧化锌光热复合材料在烘干用808nm激光烧蚀并激发下发光并产大量热。Take 2mL of dopamine in 10mL of zinc oxide aqueous dispersion and stir for 30min evenly, then dry. The obtained dopamine-zinc oxide photothermal composite material emits light and generates a lot of heat under the ablation and excitation of 808nm laser during drying.
实施例12:葡萄糖-氧化锌光热复合材料Embodiment 12: glucose-zinc oxide photothermal composite material
取2mL的葡萄糖于10mL氧化锌水分散液中搅拌30min，随后干燥，得到的葡萄糖-氧化锌光热复合材料在烘干用808nm激光烧蚀并激发下发光并产大量热。Take 2 mL of glucose in 10 mL of zinc oxide aqueous dispersion and stir for 30 minutes, then dry. The obtained glucose-zinc oxide photothermal composite material emits light and generates a lot of heat under the ablation and excitation of 808 nm laser during drying.
实施例13:碳点-二氧化钛光热复合材料Embodiment 13: Carbon dots-titanium dioxide photothermal composite material
分别称取10mL TiO
2分散液、17mg碳点、10mL去离子水于烧杯中，混合、超声5min后离心，用去离子水洗去杂质，将沉淀物取出干燥，得到的碳点-二氧化钛光热复合材料在808nm红外激光烧蚀并激发下发光并产大量热。
Weigh 10mL of TiO 2 dispersion, 17mg of carbon dots, and 10mL of deionized water in a beaker, mix, ultrasonicate for 5 minutes and centrifuge, wash away impurities with deionized water, take out the precipitate and dry it, and the obtained carbon dots-titanium dioxide photothermal composite The material emits light and generates a lot of heat under 808nm infrared laser ablation and excitation.
在77K的温度下，碳点-二氧化钛复合材料在980nm近红外光激发下 (5W/cm
2)产生白光，其发射光谱如图3所示，图4为该复合材料被近红外光激发时的发光集光率，由图可知，碳点-二氧化钛复合材料在光致发光下的发光角为60°，进而说明该复合材料在激光作用下可实现定向发光而非全向发光。
At a temperature of 77K, the carbon dot-titanium dioxide composite material produces white light under the excitation of 980nm near-infrared light (5W/cm 2 ), and its emission spectrum is shown in Figure 3, and Figure 4 shows the emission spectrum of the composite material when it is excited by near-infrared light As for the etendue of luminescence, it can be seen from the figure that the luminescence angle of the carbon dot-titanium dioxide composite material under photoluminescence is 60°, which further shows that the composite material can achieve directional luminescence instead of omnidirectional luminescence under the action of laser.
实施例14:碳点-二氧化钛光热复合材料的应用Embodiment 14: Application of carbon dots-titanium dioxide photothermal composite material
将实施例10制备得到的碳点-二氧化钛光热复合材料放置玻璃片上，并覆盖一层玻璃片，如图5a-c所示，制备得到发光源，将其与激光装置结合可用于目标照明(图5d-f)，此外，该发光源可用于投影装置，如5g-i所示，激光照射到发光源上产生定向白光，照射到投影片的图片上，经过聚光镜投射到屏幕上，完成投影。The carbon dot-titanium dioxide photothermal composite material prepared in Example 10 was placed on a glass sheet and covered with a layer of glass sheet, as shown in Figure 5a-c, a light-emitting source was prepared, which can be used for target illumination by combining it with a laser device ( Figure 5d-f), in addition, the light source can be used in projection devices, as shown in 5g-i, the laser light is irradiated on the light source to generate directional white light, which is irradiated on the picture of the projection film, and projected onto the screen through the condenser lens to complete the projection .
由上述实施例可知，由碳单质或聚吡咯作为碳质材料，与过渡金属的氧化物、氢氧化物、络合物、盐、单质以及稀土金属的盐均能制备得到具有光热性能的复合材料，且制备得到的各种光热复合材料在红外激光的激发下，均能发光并产生大量的热，局部温度可高达上千度，可应用于照明以及局部加热等器械装置中，此外，碳点-二氧化钛复合材料可实现定向发光，在目标照明以及投影方面均具有应用潜能。From the above examples, it can be known that a composite material with photothermal properties can be prepared from simple carbon or polypyrrole as a carbonaceous material, with transition metal oxides, hydroxides, complexes, salts, simple substances, and salts of rare earth metals. Materials, and the prepared various photothermal composite materials can emit light and generate a lot of heat under the excitation of infrared lasers, and the local temperature can be as high as thousands of degrees, which can be applied to lighting and local heating devices. In addition, Carbon dots-titanium dioxide composites can achieve directional light emission and have potential applications in target lighting and projection.
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例，本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换，均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。The above-mentioned embodiments are only preferred embodiments for fully illustrating the present invention, and the protection scope of the present invention is not limited thereto. Equivalent substitutions or transformations made by those skilled in the art on the basis of the present invention are all within the protection scope of the present invention. The protection scope of the present invention shall be determined by the claims.
Claims (10)
- 一种光热复合材料的制备方法，其特征在于，所述复合材料由碳质材料与非碳质材料组成，其制备方法包括方法(1)或方法(2):A preparation method of photothermal composite material is characterized in that, described composite material is made up of carbonaceous material and non-carbonaceous material, and its preparation method comprises method (1) or method (2):(1)将第一碳质材料和第一非碳质材料加至水中，直接混合或加入氧化剂混合，混合后超声、离心、洗涤，取出沉淀物，干燥后得到一种光热复合材料；所述第一碳质材料与第一非碳质材料至少有一种为液体或固体分散液；(1) adding the first carbonaceous material and the first non-carbonaceous material to water, directly mixing or adding an oxidant to mix, after mixing, ultrasonication, centrifugation, washing, taking out the precipitate, and drying to obtain a photothermal composite material; At least one of the first carbonaceous material and the first non-carbonaceous material is a liquid or solid dispersion;(2)将第二碳质材料和第二非碳质材料研磨后得到一种光热复合材料；所述第二碳质材料和第二非碳质材料均为固体；(2) Grinding the second carbonaceous material and the second non-carbonaceous material to obtain a photothermal composite material; both the second carbonaceous material and the second non-carbonaceous material are solid;所述碳质材料为碳单质和/或含碳高分子材料；所述非碳质材料为稀土金属的单质及其化合物和/或过渡金属的单质及其化合物。The carbonaceous material is a simple substance of carbon and/or a carbon-containing polymer material; the non-carbonaceous material is a simple substance of a rare earth metal and its compound and/or a simple substance of a transition metal and its compound.
- 根据权利要求1所述的一种光热复合材料的制备方法，其特征在于，所述碳单质为碳点、碳纳米管、石墨、金刚石、足球烯中的一种或多种。The method for preparing a photothermal composite material according to claim 1, wherein the simple carbon substance is one or more of carbon dots, carbon nanotubes, graphite, diamond, and footballene.
- 根据权利要求1所述的一种光热复合材料的制备方法，其特征在于，所述含碳高分子材料包括含碳高分子单体和含碳高分子聚合物；所述含碳高分子单体为吡咯、葡萄糖、多巴胺、苯胺中的一种或多种；所述含碳高分子聚合物为聚吡咯、葡聚糖、聚多巴胺、聚苯胺中的一种或多种。A method for preparing a photothermal composite material according to claim 1, wherein the carbon-containing polymer material comprises a carbon-containing polymer monomer and a carbon-containing polymer; the carbon-containing polymer unit The body is one or more of pyrrole, glucose, dopamine, and aniline; the carbon-containing polymer is one or more of polypyrrole, dextran, polydopamine, and polyaniline.
- 根据权利要求1所述的一种光热复合材料的制备方法，其特征在于，所述稀土金属的化合物为含稀土金属原子的盐、合金、络合物、氧化物或氢氧化物；所述过渡金属的化合物为含过渡金属原子的盐、合金、络合物、氧化物或氢氧化物。A method for preparing a photothermal composite material according to claim 1, wherein the compound of the rare earth metal is a salt, alloy, complex, oxide or hydroxide containing rare earth metal atoms; Compounds of transition metals are salts, alloys, complexes, oxides or hydroxides containing transition metal atoms.
- 根据权利要求1所述的一种光热复合材料的制备方法，其特征在于，方法(1)中，所述氧化剂为铁盐、铜盐、氯酸盐、高氯酸盐、硝酸盐、高锰酸盐、浓硫酸、二氧化锰中的一种。The preparation method of a kind of photothermal composite material according to claim 1, is characterized in that, in method (1), described oxidizing agent is iron salt, copper salt, chlorate, perchlorate, nitrate, high One of manganate, concentrated sulfuric acid, and manganese dioxide.
- 权利要求1-5任一项所述的一种光热复合材料在目标照明及局部加热方面的应用，其特征在于，所述光热复合材料在激光作用下产生光和热。The application of a photothermal composite material in any one of claims 1-5 in object illumination and local heating, characterized in that the photothermal composite material generates light and heat under the action of laser light.
- 权利要求1-6任一项所述的一种光热复合材料在定向发光方面的应用，其特征在于，所述光热复合材料中的非碳质材料为二氧化钛。The application of a photothermal composite material in directional light emission according to any one of claims 1-6, characterized in that the non-carbonaceous material in the photothermal composite material is titanium dioxide.
- 根据权利要求7所述的一种光热复合材料在定向发光方面的应用，其特征在于，所述光热复合材料中的碳质材料的质量分数为5wt％-60wt％。The application of a photothermal composite material in directional light emission according to claim 7, characterized in that the mass fraction of the carbonaceous material in the photothermal composite material is 5wt%-60wt%.
- 根据权利要求7所述的一种光热复合材料在定向发光方面的应用，其特征在于，所述光热复合材料在激光作用下产生定向白光。The application of a photothermal composite material in directional light emission according to claim 7, characterized in that the photothermal composite material generates directional white light under the action of laser light.
- 根据权利要求6或9所述的一种光热复合材料的应用，其特征在于，所述激光的波长为近红外波段。The application of a photothermal composite material according to claim 6 or 9, characterized in that the wavelength of the laser is in the near-infrared band.
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