CN114988416A - Silica-based super-black aerogel, and preparation method and application thereof - Google Patents
Silica-based super-black aerogel, and preparation method and application thereof Download PDFInfo
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- CN114988416A CN114988416A CN202210839359.2A CN202210839359A CN114988416A CN 114988416 A CN114988416 A CN 114988416A CN 202210839359 A CN202210839359 A CN 202210839359A CN 114988416 A CN114988416 A CN 114988416A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 290
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 135
- 239000004964 aerogel Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 45
- 239000002105 nanoparticle Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000031700 light absorption Effects 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002310 reflectometry Methods 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 21
- 238000002835 absorbance Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000006229 carbon black Substances 0.000 claims abstract description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 12
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 12
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 12
- 238000010521 absorption reaction Methods 0.000 claims abstract description 11
- 230000003287 optical effect Effects 0.000 claims abstract description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052737 gold Inorganic materials 0.000 claims abstract description 9
- 239000010931 gold Substances 0.000 claims abstract description 9
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 9
- 239000004332 silver Substances 0.000 claims abstract description 9
- 230000008020 evaporation Effects 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 238000007146 photocatalysis Methods 0.000 claims abstract description 6
- 230000001699 photocatalysis Effects 0.000 claims abstract description 6
- 238000009413 insulation Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000006185 dispersion Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 238000006068 polycondensation reaction Methods 0.000 claims description 19
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 125000005375 organosiloxane group Chemical group 0.000 claims description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 239000003377 acid catalyst Substances 0.000 claims description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 7
- 238000009775 high-speed stirring Methods 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 claims description 3
- 238000000352 supercritical drying Methods 0.000 claims description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 2
- 230000007774 longterm Effects 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000004321 preservation Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 25
- 238000003756 stirring Methods 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 238000007789 sealing Methods 0.000 description 11
- 239000004965 Silica aerogel Substances 0.000 description 8
- 230000003301 hydrolyzing effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 5
- 239000003738 black carbon Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- ZFSFDELZPURLKD-UHFFFAOYSA-N azanium;hydroxide;hydrate Chemical compound N.O.O ZFSFDELZPURLKD-UHFFFAOYSA-N 0.000 description 2
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
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- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000307 polymer substrate Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002210 supercritical carbon dioxide drying Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/158—Purification; Drying; Dehydrating
- C01B33/1585—Dehydration into aerogels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
Abstract
The invention discloses a silica-based super-black aerogel, and a preparation method and application thereof. The silica-based ultra-black aerogel comprises a three-dimensional porous network structure formed by mutually connecting nano light absorption particles and silica nanoparticles, wherein the particle size of the silica nanoparticles is 2-10 nm, the particle size of the nano light absorption particles is 2-100 nm, and the nano light absorption particles comprise nano carbon black, carbon nanotubes, graphene, nano metal gold, silver and the like; the silica-based ultra-black aerogel has ultra-wideband absorption performance, and has an absorbance of 98-99.9% and a reflectivity of 0.1-2% in a 0.25-25 mu m wave band. The silica-based ultra-black aerogel disclosed by the invention has the advantages of high light absorption rate, low reflectivity, simple preparation process and mild reaction conditions, and has huge application prospects in the fields of heat insulation and preservation, photo-thermal water evaporation, photo-thermal energy conversion, thermoelectric conversion, photocatalysis, optical instruments and the like.
Description
Technical Field
The invention relates to a preparation method of silica aerogel, in particular to silica-based ultra-black aerogel and a preparation method and application thereof, belonging to the technical field of nano optical materials.
Background
As information carriers or energy carriers, light plays an important role in many civil facilities or military fields, and many optoelectronic devices regulate and control device performance by transmitting, reflecting or absorbing light waves. The wide-spectrum absorber has the characteristic of wide-band light wave absorption, and plays an important role in the fields of solar energy utilization, sensing detection, precise optics, anti-counterfeiting stealth and the like. The porous ultra-black material can also absorb solar energy and be used in the fields of photo-thermal seawater evaporation, photo-thermal catalysis, thermoelectric conversion and the like. In addition, the wide-spectrum absorber can be used for shielding stray light and improving the sensitivity and the definition of an optical instrument and a photographic lens module. The relationship between the reflectivity, transmittance and absorption of a material is: r + T + a is 1, and it can be seen from the formula that if a super black high absorption material is desired, reflection and transmission must be reduced as much as possible, the transmission is eliminated relatively simply, and the transmission can be eliminated completely as long as the absorption layer is thick enough. However, since interfacial reflection occurs if there is a difference in refractive index between the absorber and air, it is extremely difficult to eliminate interfacial reflection, and incident light can be made to enter the absorber as far as possible only by lowering the refractive index of the absorber as much as possible.
The existing ultra-black materials mainly comprise two types of metal materials and carbon-based materials. The ultra-black metal is formed by etching the surface of aluminum, copper, nickel-phosphorus alloy and other materials by a chemical corrosion method or magnetron sputtering to form a micro-nano structure, so that the interface impedance is eliminated, and the ultra-black metal has a good capturing effect on light. For example, patent CN104195518A discloses a black light-absorbing film and a method for preparing the same, which copies a template containing a tapered hole array with a metal or polymer and peels off the template to obtain a tapered array metal substrate or a tapered array polymer substrate, and then sequentially sputters an iron film and a protective layer on the tapered array metal substrate or the tapered array polymer substrate by a magnetron sputtering method to obtain the black light-absorbing film. British scientists use etching techniques to soak a nickel alloy containing a suitable amount of phosphorus in nitric acid to produce an ultra-black surface material with extremely low light reflectance, the darkest metallic substance known in the world, which is reduced to 0.4%. However, the preparation of the ultra-black metal material has the disadvantages of high production cost, complex process operation and dependence on specific metal or alloy materials.
The ultra-black carbon-based material comprises carbon nanotubes, graphene, carbon black and composite materials thereof, wherein the ultra-black material Vantablack developed by Surrey Nano Systems of British Say, Inc. has the light absorption rate of 99.965%, is composed of a vertical carbon nanotube structure, has the diameter of only a few nanometers, and can be continuously deflected and rebounded after light rays are incident on the nanotube array until the light rays are completely absorbed, and the reflectivity is lower than 0.045%. However, the chemical vapor deposition method has high requirements for vacuum equipment and also requires high-temperature treatment. The reflectivity of the ultra-black coating using carbon black as a black pigment is about 3-5%, and the ultra-black coating has a certain difference with ultra-black. The existing treatment method for reducing the surface reflectivity of the carbon black coating is mainly surface treatment. The surface of the coating is made into a corresponding shape by corrosion or laser, and the back-and-forth reflection of light on the surface is enhanced, so that the light absorption effect is enhanced. For example, patent CN112011232A discloses an ultra-black coating and a preparation method thereof, in which a carbon nanotube dispersion, a carbon black dispersion and an aqueous resin are mixed and then coated and cured to obtain the ultra-black coating, but the addition of the resin reduces the thermal stability and aging performance of the ultra-black coating, and also reduces the light absorbances of the carbon nanotubes and the carbon black.
Therefore, the development of a simple and universal method for synthesizing the high-quality ultra-black material has important practical significance. The ultra-black material depends on the intrinsic light absorption rate and the interface reflectivity of the material, the interface reflection can be reduced by reducing the refractive index difference between the material and an incident light medium, when light is incident to the surface of the material from air (the refractive index is 1.0003), the interface reflection can be effectively reduced by reducing the refractive index of the material, and the reduction of the refractive index of the material depends on the reduction of the density. The aerogel has extremely low apparent density (0.003-0.3 g/cm) 3 ) And high porosity (80-99.8%), and ultra-black carbon aerogel has been proved to have extremely high absorbance, for example, patent CN105645382A discloses a method for preparing carbon aerogel with broad spectrum antireflection structure, which comprises adjusting the total mass fraction of resorcinol and formaldehyde, the mass ratio of resorcinol and sodium carbonate, controlling the gelation time, the heating rate during carbonization and the sintering temperature thereof to obtain carbon aerogel with broad spectrum antireflection structure, and sealingThe degree range is 20-60 mg/cm 3 The specific surface area is 1783 to 967m 2 The reflectance of light in 400-2000 nm ultraviolet-visible-near infrared wave band is lower than 0.3%, and the absorbance is higher than 99.7%. Patent CN110451478A discloses a super-black carbon aerogel foam compound and a preparation method thereof, wherein resorcinol formaldehyde aerogel is used as an organic precursor, and a large-area, complete and high-efficiency photo-thermal conversion super-black carbon aerogel foam compound is obtained through a pre-freezing technology and a high-temperature calcination process. The ultra-black carbon aerogel is an ideal ultra-black material, but needs high-temperature carbonization treatment, has conductivity, cannot be used in some electronic equipment, is prepared under severe conditions, and has no universality.
Disclosure of Invention
The invention mainly aims to provide a silica-based ultra-black aerogel, a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a silica-based ultra-black aerogel, which comprises a three-dimensional porous network structure formed by mutually connecting nano light absorption particles and silica nanoparticles, wherein the particle size of the nanoparticles of the silica aerogel is 2-10 nm by controlling gel homogeneous nucleation and inhibiting nucleation growth processes; the particle size of the nanometer light absorption particles is 2-100 nm, and the silicon oxide nanometer particles comprise any one or combination of two of silicon dioxide and polymethylsilsesquioxane; the nano light absorption particles comprise any one or combination of more than two of nano carbon black, carbon nano tubes, graphene, nano metal gold and nano metal silver, and have universality; the silica-based ultra-black aerogel has ultra-wideband absorption performance, and has an absorbance of 98-99.9% and a reflectivity of 0.1-2% in a 0.25-25 mu m wave band.
The embodiment of the invention also provides a preparation method of the silica-based ultra-black aerogel, which comprises the following steps:
1) dissolving an organic siloxane precursor in a solvent, adding nano light absorption particles, and forming uniform dispersion liquid by high-speed stirring and ultrasound;
2) selectively adding or not adding an acid catalyst into the dispersion liquid obtained in the step 1) to carry out hydrolysis reaction, then adding an alkali catalyst and water to carry out hydrolytic polycondensation reaction to obtain silica-based ultra-black gel;
3) and 3) carrying out solvent replacement and selective surface modification or not on the silica-based ultra-black gel obtained in the step 2), and then drying to obtain the silica-based ultra-black aerogel.
The embodiment of the invention also provides the silica-based ultra-black aerogel prepared by the preparation method.
The embodiment of the invention also provides application of the silica-based ultra-black aerogel in the fields of heat insulation, photo-thermal water evaporation, photo-thermal energy conversion, thermoelectric conversion, photocatalysis, optical instruments and the like.
Compared with the prior art, the invention has the advantages that:
1) the basic structural unit of the silica-based ultra-black aerogel provided by the invention is nano-scale particles, and has high light absorption rate, low refractive index, low reflectivity and low thermal conductivity; the material shows good mechanical property in the range of-196 ℃ to 250 ℃, and can bear loads such as compression, impact and the like; moreover, the silica-based ultra-black aerogel has broadband absorption performance, the light absorption rate is 98-99.9% in a wave band of 0.25-25 mu m, and the reflectivity is 0.1-2%;
2) the silicon oxide-based super-black aerogel provided by the invention takes organic siloxane as a precursor, and controllable preparation of the diameter of nanoparticles can be realized by regulating and controlling the components of the precursor and a solvent; the preparation process is simple, and the light absorbing substance can be selected to meet the requirements of different scenes.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and it is also possible for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a nitrogen adsorption and desorption graph of silica-based ultra-black aerogel obtained in example 1 of the present invention;
FIG. 2 is a distribution diagram of the pore size of silica-based ultra-black aerogel obtained in example 1 of the present invention;
FIG. 3 is a SEM photograph of silica-based ultra-black aerogel obtained in example 1 of the present invention;
FIG. 4 is a TEM image of silica-based ultra-black aerogel obtained in example 1 of the present invention;
FIG. 5 is an optical photograph of a silica-based ultra black aerogel obtained in example 1 of the present invention;
FIG. 6 is a SEM photograph of silica-based ultra-black aerogel obtained in example 2 of the present invention;
FIG. 7 is a TEM image of silica-based ultra-black aerogel obtained in example 2 of the present invention;
FIG. 8 is a thermogravimetric plot of the silica-based ultra black aerogel obtained in example 2 of the present invention;
FIG. 9 is a reflectance spectrum of silica-based ultra-black aerogel obtained in example 2 of the present invention;
FIG. 10 is an absorption spectrum chart of silica-based ultra-black aerogel obtained in example 2 of the present invention.
Detailed Description
In view of the shortcomings in the prior art, the inventor of the present invention has found that the combination of aerogel and high-absorbance substance (carbon-based or metal) is an ideal material for preparing ultra-black material.
The silica aerogel is a low-dielectric and low-refractive index material, has excellent insulativity, although the silica aerogel has low light absorption rate, light absorption substances (carbon-based materials or metal nanoparticles) can be dispersed in a three-dimensional nano network framework of the silica aerogel, the silica aerogel has low interface reflection, and the light transmission performance of the silica aerogel can be maximally improved by controlling the nucleation and growth processes of the gel to enable the particle size of the silica nanoparticles to be 2-10 nm, so that the light absorption rate of the light absorption substances can be improved, the reflectivity of the light absorption substances is reduced, and the absorption rate is maximized. In addition, the content of the carbon-based material or the metal nanoparticles in the silica aerogel can be regulated to regulate the conductivity and the insulating property of the material. The method has the advantages of simple preparation process, low requirement on the type of the light-absorbing substance, strong universality and great significance for the development of the ultra-black material.
Therefore, the technical scheme provided by the invention is mainly that an organic siloxane precursor and light-absorbing nanoparticles are mixed, then the mixture is hydrolyzed and condensed to form gel under the condition of a catalyst, and the silica-based ultra-black aerogel is obtained through solvent replacement, modification and drying steps, and a series of applications of the silica-based ultra-black aerogel are provided. The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiments of the present invention provides a silica-based ultra-black aerogel, which is composed of a three-dimensional porous network structure formed by interconnecting nano light-absorbing particles and silica nanoparticles, where the silica nanoparticles are composed of any one or a combination of two of silica, polymethylsilsesquioxane, and the like; the composition of the nano light absorption particles includes any one or a combination of two or more of nano carbon black, carbon nanotubes, graphene, nano metal gold, nano metal silver and the like, but is not limited thereto.
In some embodiments, the silica-based ultra-black aerogel has ultra-wideband absorption performance, and has an absorbance of 98-99.9% and a reflectance of 0.1-2% in a 0.25-25 μm band.
In some embodiments, the three-dimensional porous network structure comprises micropores having a pore size below 2nm, mesopores of 2nm to 50nm, and macropores of 50nm to 1 μm.
In some embodiments, the morphology of the silica nanoparticles includes any one or a combination of two or more of spheres, ellipsoids, irregularities, and the like, but is not limited thereto.
Further, the particle size of the silicon oxide nanoparticles is 2-10 nm, and preferably 4-8 nm.
In some embodiments, the shape of the nano light absorbing particles includes any one or a combination of two or more of spheres, platelets, tubes, irregular shapes, and the like, but is not limited thereto.
Furthermore, the particle size of the light absorption nanoparticles is 2-100 nm, preferably 2-20 nm.
In some embodiments, the silica-based ultra-black aerogel has a density of 50 to 300mg/cm 3 Preferably 100 to 200mg/cm 3 。
Further, the specific surface area of the silica-based ultra-black aerogel is 600-1200 m 2 Preferably 700 to 1000 m/g 2 /g。
Further, the pore volume of the silica-based ultra-black aerogel is 0.1-3.0 cm 3 Preferably 1.5 to 2.5 cm/g 3 /g。
Further, the porosity of the silica-based ultra-black aerogel is 75-99%, and preferably 90-95%.
Further, the hydrophobic angle of silica-based super black aerogel is 0 ~ 160.
Further, the long-term service temperature of the silica-based ultra-black aerogel is above 250 ℃.
In conclusion, the basic structural units of the silica-based ultra-black aerogel are nanoscale particles, and the silica-based ultra-black aerogel has the advantages of low reflectivity, high light absorption rate, low reflectivity, low thermal conductivity, controllable density and excellent thermal stability. The silica-based ultra-black aerogel provided by the invention shows good mechanical properties in the range of-196 ℃ to 250 ℃, and can bear loads such as compression, impact and the like.
One aspect of the embodiment of the present invention provides a method for preparing the silica-based ultra-black aerogel, which mainly includes: the method comprises the following steps of uniformly mixing an organic siloxane precursor and light absorption nanoparticles, carrying out hydrolytic polycondensation under the condition of a catalyst to form gel, and carrying out solvent replacement, modification and drying to obtain the silica-based broadband absorption super-black aerogel.
In some embodiments, the method of making consists essentially of:
1) dissolving an organic siloxane precursor in a solvent, adding nano light absorption particles, and forming uniform dispersion liquid by high-speed stirring and ultrasound;
2) selectively adding or not adding an acid catalyst into the dispersion liquid obtained in the step 1) to carry out hydrolysis reaction, then adding an alkali catalyst and water to carry out hydrolysis polycondensation reaction to obtain silicon oxide-based ultra-black gel;
3) and (3) carrying out solvent replacement, selective surface modification or not, and drying treatment on the silica-based ultra-black gel obtained in the step 2) to obtain the silica-based ultra-black aerogel.
In some embodiments, in step 1), the organosiloxane precursor includes, but is not limited to, any one or combination of two or more of tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), methyltrimethoxysilane (MTMS), and the like.
Further, the solvent includes any one or a combination of two or more of methanol, ethanol, Tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), and the like, and is not limited thereto.
In some embodiments, the molar ratio of the solvent to the organosiloxane precursor is from 1 to 20: 1, preferably from 1 to 5: 1.
In some embodiments, the mass ratio of the nano light absorbing particles to the organosiloxane precursor is 0.001-1: 1, preferably 0.01-0.1: 1.
Further, the nano light absorbing particles include any one or a combination of two or more of nano carbon black, carbon nanotubes, graphene, nano metallic gold, silver, and the like, and are not limited thereto.
In some embodiments, in step 1), the rotation speed of the high-speed stirring is 1000 to 50000 rpm, preferably 10000 to 20000 rpm, and the time of the high-speed stirring is 1 to 100 minutes, preferably 10 to 30 minutes; the ultrasonic time is 1-1000 minutes, preferably 10-100 minutes.
In some embodiments, the molar ratio of water to organosiloxane in step 2) is 1 to 4: 1.
Further, the acid catalyst includes any one or a combination of two or more of formic acid, acetic acid, sulfuric acid, nitric acid, hydrochloric acid, and the like, and is not limited thereto.
Further, the molar ratio of the acid catalyst to the organic siloxane precursor is 0-10 -1 1, preferably 0 to 10 -3 ∶1。
Further, the base catalyst includes any one or a combination of two or more of ammonia, triethylamine, tetramethylammonium hydroxide, sodium carbonate, and the like, and is not limited thereto.
Further, the molar ratio of the base catalyst to the organosiloxane precursor is 10 -1 ～10 -5 1, preferably 10 -2 ～10 -4 ∶1。
In some embodiments, the time of the hydrolysis reaction is 0-24 hours, and the temperature of the hydrolysis reaction is 10-80 ℃.
In some embodiments, the time of the hydrolytic polycondensation reaction is 12-48 h, and the temperature of the hydrolytic polycondensation reaction is 10-80 ℃.
In some embodiments, the solvent used for the solvent replacement in step 3) includes any one or a combination of two or more of ethanol, tetrahydrofuran, acetone, n-hexane, and the like, and is not limited thereto.
Further, the temperature of the solvent replacement is 20-80 ℃, and preferably 20-40 ℃.
Further, the number of times of solvent replacement is 1 to 10 times.
Further, in step 3), the optional surface hydrophobic modifier for surface modification includes any one or a combination of two or more of trimethylchlorosilane, hexamethyldisilazane and fluorocarbon resin, and the like, and is not limited thereto.
In some embodiments, the drying process includes any one of supercritical drying, atmospheric drying, and the like.
As one of preferable solutions, the supercritical drying technique includes: replacing liquid components inside the gel material with supercritical fluid under supercritical state, namely silica-based ultra-black aerogel, wherein the supercritical fluid used includes but is not limited to supercritical CO 2 (40 ℃, 10MPa), supercritical methanol (240 ℃, 8 MP)a) And supercritical ethanol (240 ℃, 7 MPa).
As one of the preferable schemes, the atmospheric drying comprises: and (3) replacing the liquid in the gel with solvents such as ethanol, normal hexane and the like, and placing the gel material at normal pressure or low vacuum to increase the temperature so as to volatilize the solvents to obtain the silica-based ultra-black aerogel.
In conclusion, the silica-based ultra-black aerogel provided by the invention takes organosiloxane as a precursor, and controllable preparation of the diameter of the nano particles can be realized by regulating and controlling the components of the precursor and a solvent; the preparation process is simple, the reaction condition is mild, the operation is easy, the energy consumption is low, the cost is low, the preparation method is green and pollution-free, and the large-scale continuous production can be realized. Meanwhile, light absorbing substances can be selected to meet different scene requirements.
In another aspect, the embodiment of the invention further provides a huge application prospect of the silica-based ultra-black aerogel in the fields of thermal insulation, photo-thermal water evaporation, photo-thermal energy conversion, thermoelectric conversion, photocatalysis or optical instruments and the like.
As one of the preferable schemes, the application of the silica-based ultra-black aerogel specifically comprises:
1) the three-dimensional network structure of the silica-based ultra-black aerogel endows the silica-based ultra-black aerogel with extremely high porosity and air content, and can be applied to thermal management in normal temperature and high temperature environments.
2) The high absorptivity of the gas silica-based ultra-black aerogel can be applied to one or more application fields of photo-thermal water evaporation, photo-thermal energy conversion, thermoelectric conversion, photocatalysis and optical instruments, but is not limited to the application fields.
By the technical scheme, the silica-based ultra-black aerogel provided by the invention has high absorptivity and low density, and has great prospects in the fields of heat insulation and preservation, photo-thermal water evaporation, photo-thermal energy conversion, thermoelectric conversion, photocatalysis, optical instruments and the like.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. It is to be noted that the following examples are intended to facilitate the understanding of the present invention and do not set any limit on the scope thereof. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.
Example 1
(1) Tetraethyl orthosilicate, nano carbon black and ethanol are stirred at high speed (the rotating speed is 10000 rpm and the time is 100 minutes) and subjected to ultrasonic treatment for 100 minutes to form dispersion liquid, formic acid is added, the mixture is mixed and stirred at 60 ℃ for 1 hour for hydrolysis, and water and ammonia water are added for polycondensation reaction (the time is 48 hours and the temperature is 30 ℃). Wherein the mol ratio of tetraethyl orthosilicate, ethanol, formic acid, water and ammonia water is 1: 20: 0.1: 4: 0.1, and the mass ratio of the nano carbon black to the tetraethyl orthosilicate is 1: 1.
(2) And (3) sealing and storing the dispersion liquid in the step (1) in an oven at 60 ℃ for 24 hours to obtain the silica-based ultra-black gel.
(3) And (3) replacing the silica-based ultra-black gel in the step (2) with ethanol for 10 times at 40 ℃, modifying the trimethylchlorosilane, and then obtaining the silica-based ultra-black aerogel by adopting a normal-pressure drying process.
The nitrogen adsorption and desorption curve of the silica-based ultra-black gel obtained in the example is shown in fig. 1, the pore size distribution is shown in fig. 2, the SEM structure is shown in fig. 3, the TEM image is shown in fig. 4, and the optical photograph is shown in fig. 5. The physical parameters of the silica nanoparticles, such as particle size, absorbance, reflectivity, specific surface area, and density, of the silica-based ultra-black aerogel obtained in this example are shown in table 1.
Example 2
1) Tetraethyl orthosilicate, nano carbon black and ethanol are stirred at high speed (the rotating speed is 20000 revolutions per minute and the time is 10 minutes) and are ultrasonically treated for 30 minutes to form dispersion liquid, formic acid is added, then the mixture is mixed and stirred at 60 ℃ for 1 hour for hydrolysis, and water and ammonia water are added for polycondensation reaction (the time is 24 hours and the temperature is 40 ℃). Wherein the mol ratio of tetraethyl orthosilicate, ethanol, formic acid, water and ammonia water is 1: 5: 10 -3 ∶3∶10 -2 The mass ratio of the nano carbon black to the tetraethyl orthosilicate is 0.001: 1.
(2) And (3) sealing and storing the dispersion liquid in the step (1) in an oven at 40 ℃ for 72 hours to obtain the silica-based ultra-black gel.
(3) And (3) replacing the silica-based ultra-black gel in the step (2) with ethanol for 3 times at 60 ℃, and performing hydrophobic modification on hexamethyldisilazane to obtain the silica-based ultra-black aerogel by adopting a normal-pressure drying process.
The SEM structure of the silica-based ultra black gel obtained in this example is shown in fig. 6, the TEM image is shown in fig. 7, the thermogravimetric analysis image is shown in fig. 8, the reflectance is shown in fig. 9, and the absorbance is shown in fig. 10. Please refer to table 1 for physical parameters of the silica nanoparticles, such as particle size, specific surface area, and density of the silica-based ultra-black aerogel obtained in this example.
Example 3
(1) Stirring tetramethyl orthosilicate, carbon nano tube and methanol at high speed (the rotation speed is 50000 r/min, the time is 1 min) and carrying out ultrasonic treatment for 10 min to form dispersion, adding hydrochloric acid, mixing and stirring at 60 ℃ for 1 h to hydrolyze, adding water and tetramethyl ammonium hydroxide to carry out polycondensation reaction (the time is 24h, and the temperature is 60 ℃). Wherein the mol ratio of the tetramethyl orthosilicate, the methanol, the hydrochloric acid, the water and the tetramethyl ammonium hydroxide is 1: 10 -2 ∶4∶10 -2 The mass ratio of the carbon nano tube to the tetramethyl orthosilicate is 0.001: 1.
(2) And (3) sealing and storing the dispersion liquid in the step (1) in an oven at 50 ℃ for 24 hours to obtain the silica-based ultra-black gel.
(3) And (3) replacing the silica-based ultra-black gel in the step (2) with acetone for 5 times at 30 ℃, and obtaining the silica-based ultra-black aerogel by adopting a supercritical carbon dioxide process and a normal pressure drying process.
The physical parameters of the silica nanoparticles, such as particle size, absorbance, reflectivity, specific surface area, and density, of the silica-based ultra-black aerogel obtained in this example are shown in table 1.
Example 4
(1) Stirring tetramethyl orthosilicate, carbon nanotube and methanol at high speed (rotation speed of 20000 r/min for 30 min)Clock) ultrasonic treatment for 1000 minutes to form a dispersion, adding hydrochloric acid, mixing and stirring at 30 ℃ for 1 hour to hydrolyze, adding water and tetramethylammonium hydroxide to perform polycondensation reaction (time is 48 hours, temperature is 10 ℃). Wherein the mol ratio of the tetramethyl orthosilicate, the methanol, the hydrochloric acid, the water and the tetramethyl ammonium hydroxide is 1: 3: 10 -3 ∶3∶10 -2 The mass ratio of the carbon nano tube to the tetramethyl orthosilicate is 0.1: 1.
(2) And (2) sealing and storing the dispersion liquid obtained in the step (1) in an oven at the temperature of 60 ℃ for 24 hours to obtain the silicon oxide-based ultra-black gel.
(3) And (3) replacing the silica-based ultra-black gel in the step (2) with acetone for 5 times at 30 ℃, and obtaining the silica-based ultra-black aerogel by adopting a supercritical carbon dioxide process and a normal pressure drying process.
The physical parameters of the silica nanoparticles, such as particle size, absorbance, reflectivity, specific surface area, and density, of the silica-based ultra-black aerogel obtained in this example are shown in table 1.
Example 5
(1) Stirring methyltrimethoxysilane, graphene and tetrahydrofuran at high speed (the rotating speed is 30000 r/min, the time is 20 min) and carrying out ultrasonic treatment for 1000 min to form a dispersion, adding sulfuric acid, mixing and stirring at 30 ℃ for 1 h to hydrolyze, adding water and sodium carbonate to carry out polycondensation reaction (the time is 12 h, and the temperature is 50 ℃). Wherein the molar ratio of the methyltrimethoxysilane to the tetrahydrofuran to the sulfuric acid to the water to the sodium carbonate is 1: 0.1: 4: 0.1, and the mass ratio of the graphene to the methyltrimethoxysilane is 0.01: 1.
(2) And (3) sealing and storing the dispersion liquid in the step (1) in an oven at 60 ℃ for 24 hours to obtain the silica-based ultra-black gel.
(3) And (3) replacing the silica-based ultra-black gel in the step (2) with tetrahydrofuran for 5 times at 40 ℃, and obtaining the silica-based ultra-black aerogel by adopting a supercritical carbon dioxide drying process.
The physical parameters of the silica nanoparticles, such as particle size, absorbance, reflectivity, specific surface area, and density, of the silica-based ultra-black aerogel obtained in this example are shown in table 1.
Example 6
(1) Stirring methyltrimethoxysilane, graphene and tetrahydrofuran at a high speed (10000 r/min for 30 min) and performing ultrasonic treatment for 1000 min to form a dispersion, adding sulfuric acid, mixing and stirring at 30 ℃ for 1 h for hydrolysis, adding water and sodium carbonate for polycondensation (48 h at 50 ℃). Wherein the mol ratio of the methyltrimethoxysilane to the tetrahydrofuran to the sulfuric acid to the water to the sodium carbonate is 1: 3: 10 -3 ∶3∶10 -2 The mass ratio of the graphene to the methyltrimethoxysilane is 0.001: 1.
(2) And (3) sealing and storing the dispersion liquid in the step (1) in an oven at 60 ℃ for 24 hours to obtain the silica-based ultra-black gel.
(3) And (3) replacing the silica-based ultra-black gel in the step (2) with n-hexane for 5 times at 40 ℃, and obtaining the silica-based ultra-black aerogel by adopting a normal-pressure drying process.
The physical parameters of the silica nanoparticles, such as particle size, absorbance, reflectivity, specific surface area, and density, of the silica-based ultra-black aerogel obtained in this example are shown in table 1.
Example 7
(1) Stirring tetramethyl orthosilicate, nano metal gold and DMSO at high speed (the rotation speed is 10000 r/min, the time is 30 min) for 1000 min by ultrasound to form dispersion, adding ammonia water and water, mixing and stirring at 30 ℃ for 1 h to carry out hydrolytic polycondensation reaction (the time is 48h, the temperature is 80 ℃). Wherein the mol ratio of the tetramethyl orthosilicate, the DMSO, the water and the ammonia water is 1: 3: 10 -5 The mass ratio of the nano metal gold to the tetramethyl orthosilicate is 1: 1.
(2) And (3) sealing and storing the dispersion liquid in the step (1) in an oven at 60 ℃ for 24 hours to obtain the silica-based ultra-black gel.
(3) And (3) replacing the silica-based ultra-black gel in the step (2) with ethanol for 5 times at 30 ℃, and obtaining the silica-based ultra-black aerogel by adopting a supercritical carbon dioxide process and a normal pressure drying process.
The physical parameters of the silica nanoparticles, such as particle size, absorbance, reflectivity, specific surface area, and density, of the silica-based ultra-black aerogel obtained in this example are shown in table 1.
Example 8
(1) Stirring tetramethyl orthosilicate, nano metal gold and DMSO at high speed (the rotation speed is 10000 r/min, the time is 30 min) for 100 min by ultrasound to form dispersion, adding triethylamine and water, mixing and stirring at 30 ℃ for 1 h to carry out hydrolytic polycondensation reaction (the time is 20 h, the temperature is 80 ℃). Wherein the mol ratio of the tetramethyl orthosilicate, the DMSO, the water and the ammonia water is 1: 10: 4: 10 -3 The mass ratio of the nano metal gold to the tetramethyl orthosilicate is 0.1: 1.
(2) And (2) sealing and storing the dispersion liquid obtained in the step (1) in an oven at the temperature of 60 ℃ for 24 hours to obtain the silicon oxide-based ultra-black gel.
(3) And (3) replacing the silica-based ultra-black gel in the step (2) with ethanol for 5 times at 30 ℃, and obtaining the silica-based ultra-black aerogel by adopting a supercritical carbon dioxide process and a normal pressure drying process.
The physical parameters of the silica nanoparticles, such as particle size, absorbance, reflectivity, specific surface area, and density, of the silica-based ultra-black aerogel obtained in this example are shown in table 1.
Example 9
(1) Stirring tetramethyl orthosilicate, nano metal silver and DMSO at high speed (the rotation speed is 1000 r/min, the time is 30 min) for 10 min by ultrasound to form dispersion, adding ammonia water and water, mixing and stirring at 30 ℃ for 24h to carry out hydrolytic polycondensation reaction (the time is 30 h, the temperature is 50 ℃). Wherein the mol ratio of the tetramethyl orthosilicate, the DMSO, the water and the ammonia water is 1: 3: 1: 10 -5 The mass ratio of the nano metal silver to the tetramethyl orthosilicate is 1: 1.
(2) And (3) sealing and storing the dispersion liquid in the step (1) in an oven at 60 ℃ for 24 hours to obtain the silica-based ultra-black gel.
(3) And (3) replacing the silica-based ultra-black gel obtained in the step (2) with ethanol for 5 times at 20 ℃, and obtaining the silica-based ultra-black aerogel by adopting a supercritical carbon dioxide process and a normal pressure drying process.
The physical parameters of the silica nanoparticles, such as particle size, absorbance, reflectivity, specific surface area, and density, of the silica-based ultra-black aerogel obtained in this example are shown in table 1.
Example 10
(1) Stirring tetramethyl orthosilicate, nano metal silver and DMSO at high speed (the rotation speed is 15000 r/min, the time is 15 min) for 1 min by ultrasound to form dispersion, adding ammonia water and water, mixing and stirring at 30 ℃ for 24h to carry out hydrolytic polycondensation reaction (the time is 36 h, the temperature is 40 ℃). Wherein the mol ratio of the tetramethyl orthosilicate, the DMSO, the water and the ammonia water is 1: 8: 4: 10 -2 The mass ratio of the nano metal silver to the tetramethyl orthosilicate is 0.01: 1.
(2) And (3) sealing and storing the dispersion liquid in the step (1) in an oven at 60 ℃ for 24 hours to obtain the silica-based ultra-black gel.
(3) And (3) replacing the silica-based ultra-black gel in the step (2) with DMSO for 5 times at 80 ℃, and obtaining the silica-based ultra-black aerogel by adopting a supercritical carbon dioxide process and a normal pressure drying process.
The physical parameters of the silica nanoparticles, such as particle size, absorbance, reflectivity, specific surface area, and density, of the silica-based ultra-black aerogel obtained in this example are shown in table 1.
TABLE 1 Structure and Performance parameters of the silica-based ultra-black aerogels obtained in examples 1 to 10
Comparative example 1
(1) Tetraethyl orthosilicate, graphene and ethanol are stirred at high speed (the rotating speed is 10000 r/min, the time is 60 min) and subjected to ultrasound (10 min) to form dispersion, formic acid is added, the mixture is mixed and stirred at 60 ℃ for 1 h for hydrolysis, and water and ammonia water are added for polycondensation reaction (the time is 48h, the temperature is 60 ℃). Wherein the mol ratio of tetraethyl orthosilicate to ethanol to formic acid to water to ammonia water is 1: 0.1: 4: 0.01, and the mass ratio of graphene to tetraethyl orthosilicate is 0.01: 1.
(2) And (2) sealing and storing the dispersion liquid in the step (1) in an oven at 60 ℃ for 24 hours to obtain the silica-based black gel.
(3) And (3) replacing the silica-based black gel in the step (2) with ethanol for 10 times at 40 ℃, modifying the trimethylchlorosilane, and then obtaining the silica-based black aerogel by adopting a normal-pressure drying process.
The particle size of the silica-based aerogel nanoparticles is 30-50 nm, and the density of the silica-based aerogel nanoparticles is 1000mg/cm 3 The light absorption rate is 90%, and the reflectivity is 10%.
Comparative example 1 is similar to example 1, but the silica-based black aerogel has a high density resulting in a high refractive index and high interfacial reflection. In addition, the silica-based black aerogel in comparative example 1 has low absorptivity and cannot reach the ultra-black standard because the interface scattering is strong and light is reflected due to the large particle size of the nanoparticles of the silica-based black aerogel.
In addition, the inventor also prepares a series of silica-based ultra-black aerogels by adopting other raw materials and process conditions listed in the specification and referring to the modes of examples 1-10. Tests show that the silica-based ultra-black gel also has the excellent properties mentioned in the specification.
It should be understood that the above describes only some embodiments of the present invention and that various other changes and modifications may be affected therein by one of ordinary skill in the related art without departing from the scope or spirit of the invention.
Claims (10)
1. The silicon oxide-based ultra-black aerogel is characterized by comprising a three-dimensional porous network structure formed by mutually connecting nano light absorption particles and silicon oxide nanoparticles, wherein the particle size of the silicon oxide nanoparticles is 2-10 nm; the particle size of the nanometer light absorption particles is 2-100 nm, and the silicon oxide nanometer particles comprise any one or combination of two of silicon dioxide and polymethylsilsesquioxane; the nano light absorption particles comprise any one or a combination of more than two of nano carbon black, carbon nano tubes, graphene, nano metal gold and nano metal silver; the silica-based ultra-black aerogel has ultra-wideband absorption performance, and has an absorbance of 98-99.9% and a reflectivity of 0.1-2% in a 0.25-25 mu m wave band.
2. The silica-based ultra black aerogel according to claim 1, wherein: the particle size of the silicon oxide nano particles is 4-8 nm, and the particle size of the nano light absorption particles is 2-20 nm;
and/or the three-dimensional porous network structure comprises micropores with the pore diameter of below 2nm, mesopores with the diameter of 2 nm-50 nm and macropores with the diameter of 50 nm-1 mu m;
and/or the shape of the silicon oxide nano-particles comprises any one or the combination of more than two of spheres, ellipsoids and irregular bodies; and/or the shape of the nanometer light absorption particles comprises any one or the combination of more than two of spheres, sheets, tubular bodies and irregular bodies.
3. The silica-based ultra black aerogel according to claim 1, wherein: the density of the silica-based ultra-black aerogel is 50-300 mg/cm 3 Preferably 100 to 200mg/cm 3 ；
And/or the specific surface area of the silica-based ultra-black aerogel is 600-1200 m 2 Preferably 700 to 1000 m/g 2 A pore volume of 0.1 to 3.0cm 3 A preferred concentration is 1.5 to 2.5cm 3 The porosity is 75-99%, preferably 90-95%; the hydrophobic angle is 0-160 degrees, and the long-term use temperature is higher than 250 ℃.
4. The method for preparing the silica-based ultra black aerogel according to any one of claims 1 to 3, comprising:
1) dissolving an organic siloxane precursor in a solvent, adding nano light absorption particles, and forming uniform dispersion liquid by high-speed stirring and ultrasound;
2) selectively adding or not adding an acid catalyst into the dispersion liquid obtained in the step 1) to carry out hydrolysis reaction, then adding an alkali catalyst and water to carry out polycondensation reaction to obtain silica-based ultra-black gel;
3) and (3) carrying out solvent replacement and selective surface modification or not on the silica-based ultra-black gel obtained in the step 2), and then drying to obtain the silica-based ultra-black aerogel.
5. The preparation method according to claim 4, wherein in step 1), the organosiloxane precursor comprises any one or a combination of two or more of tetraethyl orthosilicate, tetramethyl orthosilicate and methyltrimethoxysilane; and/or the solvent comprises any one or the combination of more than two of methanol, ethanol, tetrahydrofuran and dimethyl sulfoxide; and/or the molar ratio of the solvent to the organosiloxane precursor is 1-20: 1, preferably 1-5: 1;
and/or the mass ratio of the nano light absorption particles to the organosiloxane precursor is 0.001-1: 1, preferably 0.01-0.1: 1.
6. The preparation method according to claim 4, wherein in the step 1), the rotation speed of the high-speed stirring is 1000-50000 rpm, preferably 10000-20000 rpm, and the time of the high-speed stirring is 1-100 minutes, preferably 10-30 minutes; and/or the ultrasonic time is 1-1000 minutes, preferably 10-100 minutes.
7. The preparation method according to claim 4, wherein in the step 2), the molar ratio of the water to the organosiloxane is 1-4: 1; and/or the acid catalyst comprises any one or the combination of more than two of formic acid, sulfuric acid, nitric acid and hydrochloric acid; and/or the molar ratio of the acid catalyst to the organosiloxane precursor is 0-10 -1 1, preferably 0 to 10 -3 1: mixing; and/or the alkali catalyst comprises one or the combination of more than two of ammonia water, triethylamine, tetramethyl ammonium hydroxide and sodium carbonate; and/or the molar ratio of the base catalyst to the organosiloxane precursor is 10 -1 ～10 -5 1, preferably 10 -2 ～10 -4 1: 1; and/or the time of the hydrolysis reactionWithin 24 hours, the temperature of the hydrolysis reaction is 10-80 ℃; and/or the time of the polycondensation reaction is 12-48 h, and the temperature of the polycondensation reaction is 10-80 ℃.
8. The preparation method according to claim 4, wherein in the step 3), the solvent used for solvent replacement comprises any one or a combination of two or more of ethanol, tetrahydrofuran, acetone and n-hexane, and the temperature of solvent replacement is 20-80 ℃, preferably 20-40 ℃; and/or the number of times of solvent replacement is 1-10.
9. The method of claim 4, wherein: in the step 3), the surface hydrophobic modifier used for surface modification comprises any one or a combination of more than two of trimethylchlorosilane, hexamethyldisilazane and fluorocarbon resin;
and/or the drying treatment comprises any one of supercritical drying and atmospheric drying.
10. Use of the silica-based ultra black aerogel according to any one of claims 1 to 3 in the fields of thermal insulation, photo-thermal water evaporation, photo-thermal energy conversion, thermoelectric conversion, photocatalysis, or optical instruments.
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