CN114988416B - 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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- CN114988416B CN114988416B CN202210839359.2A CN202210839359A CN114988416B CN 114988416 B CN114988416 B CN 114988416B CN 202210839359 A CN202210839359 A CN 202210839359A CN 114988416 B CN114988416 B CN 114988416B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 306
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 145
- 239000004964 aerogel Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 46
- 239000002105 nanoparticle Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000002835 absorbance Methods 0.000 claims abstract description 25
- 238000002310 reflectometry Methods 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000006229 carbon black Substances 0.000 claims abstract description 15
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 13
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 12
- 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
- 238000010521 absorption reaction Methods 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 230000008020 evaporation Effects 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 238000009413 insulation Methods 0.000 claims abstract description 6
- 238000007146 photocatalysis Methods 0.000 claims abstract description 6
- 230000001699 photocatalysis Effects 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000006185 dispersion Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- 125000005375 organosiloxane group Chemical group 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 238000006068 polycondensation reaction Methods 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
- 230000031700 light absorption Effects 0.000 claims description 18
- 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 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000006460 hydrolysis reaction Methods 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
- 239000003054 catalyst Substances 0.000 claims description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000003377 acid catalyst Substances 0.000 claims description 10
- 238000009775 high-speed stirring Methods 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 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
- 239000011148 porous material Substances 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 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
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 230000007774 longterm 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
- 230000035484 reaction time Effects 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 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
- 239000003607 modifier Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 abstract description 4
- 239000000499 gel Substances 0.000 description 35
- 239000000463 material Substances 0.000 description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000003301 hydrolyzing effect Effects 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000004965 Silica aerogel Substances 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 5
- 239000003738 black carbon Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 239000002071 nanotube Substances 0.000 description 4
- 230000001105 regulatory effect Effects 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
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000004966 Carbon aerogel Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 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
- 239000012530 fluid Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000001755 magnetron sputter deposition 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
- 230000009467 reduction Effects 0.000 description 2
- 238000001878 scanning electron micrograph 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
- 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
- ZFSFDELZPURLKD-UHFFFAOYSA-N azanium;hydroxide;hydrate Chemical compound N.O.O ZFSFDELZPURLKD-UHFFFAOYSA-N 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
- 238000013329 compounding Methods 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
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000009776 industrial production 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
- 238000001579 optical reflectometry Methods 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
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000002210 supercritical carbon dioxide drying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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 silica-based super-black aerogel, a preparation method and application thereof. The silica-based super-black aerogel comprises a three-dimensional porous network structure formed by interconnecting nano light-absorbing particles and silica nanoparticles, wherein the particle size of the silica nanoparticles is 2-10 nm, the particle size of the nano light-absorbing particles is 2-100 nm, and the composition of the nano light-absorbing particles comprises nano carbon black, carbon nano tubes, graphene, nano metal gold, silver and the like; the silica-based super-black aerogel has ultra-wideband absorption performance, the absorbance in the wave band of 0.25-25 mu m is 98-99.9%, and the reflectivity is 0.1-2%. The silica-based super-black aerogel has high light absorptivity and low reflectivity, and meanwhile, the preparation process is simple, the reaction condition is mild, and the silica-based super-black aerogel has great 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 silicon oxide aerogel, in particular to silicon oxide-based super-black aerogel and a preparation method and application thereof, and belongs to the technical field of nano optical materials.
Background
As an information carrier or an energy carrier, light plays an important role in many civil facilities or military fields, and many optoelectronic devices implement regulation of device performance by transmitting, reflecting or absorbing light waves. The broad spectrum absorber has the characteristic of absorbing light waves in a wide frequency band, and plays an important role in the fields of solar energy utilization, sensing detection, precise optics, anti-counterfeiting stealth and the like. The porous super-black material can absorb solar energy for the fields of photo-thermal seawater evaporation, photo-thermal catalysis, thermoelectric conversion and the like. In addition, the broad spectrum absorber can also be used for shielding stray light, and improving the sensitivity and definition of the optical instrument and the photographic lens module. The relation among the reflectivity, the transmissivity and the absorptivity of the material is as follows: as can be seen from the formula r+t+a=1, if a super-black high-absorption material is to be obtained, reflection and transmission must be reduced as much as possible, and transmission can be eliminated simply, and transmission can be completely eliminated as long as the absorption layer is sufficiently thick. However, since interfacial reflection occurs only when there is a difference in refractive index between the absorber and air, it is extremely difficult to eliminate interfacial reflection, and it is only possible to make incident light enter the absorber as much as possible by reducing the refractive index of the absorber as much as possible.
The existing super-black materials mainly comprise two main types of metal materials and carbon-based materials. The ultra-black metal is made of aluminum, copper, nickel-phosphorus alloy and other materials, and the surface of the metal is etched to form a micro-nano structure by using a chemical corrosion method or magnetron sputtering, so that 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 preparation method thereof, wherein a metal or polymer is used for copying a template containing a tapered hole array and stripping to obtain a tapered array metal substrate or a tapered array polymer substrate, and then an iron film and a protective layer are sequentially sputtered on the tapered array metal substrate or the tapered array polymer substrate by using a magnetron sputtering method to obtain the black light absorbing film. The british scientist uses etching technology to soak nickel alloy containing proper amount of phosphorus element with nitric acid to produce super-black surface material with extremely low light reflectivity, which is the darkest metal material known in the world, and the reflectivity is reduced to 0.4%. However, the preparation of the super-black metal material has the defects of high production cost, complex process operation and dependence on specific metal or alloy materials.
The super black carbon-based material comprises carbon nano-tubes, graphene, carbon black and composite materials thereof, wherein the super black material Vantabelck developed by the British Sari nano-system company (Surrey Nano Systems) has an absorbance of up to 99.965 percent and consists of a vertical carbon nano-tube structure, the diameter of the nano-tube is only a few nanometers, and when light rays are incident on the nano-tube array, the nano-tube array continuously deflects and bounces until the nano-tube array is completely absorbed finally, and the reflectivity is lower than 0.045 percent. However, the chemical vapor deposition method requires high vacuum equipment and high temperature treatment. The reflectivity of the super-black paint taking carbon black as a black pigment is approximately 3-5%, and a certain gap is left between the super-black paint and the super-black paint. The current treatment method for reducing the surface reflectivity of the carbon black coating is mainly surface treatment. The corrosion or laser is used for generating corresponding shapes on the surface of the coating, and the back and forth reflection of light on the surface is enhanced, so that the light absorption effect is enhanced, but the method is often high in requirement, complex in step and unfavorable for the industrial production of the ultra-black coating. The addition of carbon nanotubes can enhance the absorbance of carbon black, for example, patent CN112011232a discloses a super-black coating and a preparation method thereof, wherein the super-black coating is obtained by coating and curing a carbon nanotube dispersion liquid, a carbon black dispersion liquid and an aqueous resin after mixing, but the addition of the resin reduces the thermal stability and aging performance of the super-black coating and also reduces the absorbance of the carbon nanotubes and the carbon black.
Therefore, the development of a simple and general method for synthesizing the high-quality super-black material has important practical significance. The super-black material depends on the intrinsic absorbance and the interface reflectivity of the material, the interface reflection can be reduced by reducing the refractive index difference between the material and the incident light medium, when light is incident on 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. Aerogel has extremely low apparent density (0.003-0.3 g/cm) 3 ) And high porosity (80-99.8%), ultra-black carbon aerogel has been confirmed to have extremely high absorbance, for example, patent CN105645382a discloses a method for preparing carbon aerogel having a broad spectrum anti-reflection structure, which comprises controlling gelation time, carbonization process temperature rising rate and sintering temperature by adjusting total mass fraction of resorcinol and formaldehyde, mass ratio of resorcinol and sodium carbonate to obtain carbon aerogel having a broad spectrum anti-reflection structure with density ranging from 20-60 mg/cm 3 The specific surface area is 1783-967 m 2 Per gram, in the ultraviolet-visible-near infrared band of 400-2000 nmThe reflectivity of the light is lower than 0.3%, and the absorbance is higher than 99.7%. Patent CN110451478A discloses a super-black carbon aerogel foam composite and a preparation method thereof, resorcinol formaldehyde aerogel is used as an organic precursor, and the super-black carbon aerogel foam composite with large area, integrity and high photo-thermal conversion efficiency is obtained through a pre-freezing technology and a high-temperature calcination technology. 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 devices, and has harsh preparation conditions and no universality.
Disclosure of Invention
The invention mainly aims to provide silica-based super-black aerogel, a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides silica-based super-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 nano light absorption particles is 2-100 nm, and the composition of the silicon oxide nano particles comprises any one or the combination of two of silicon dioxide and polymethyl silsesquioxane; the composition of the nano light absorption particles comprises any one or more than two of nano carbon black, carbon nano tube, graphene, nano metal gold and nano metal silver, and the nano light absorption particles have universality; the silica-based super-black aerogel has ultra-wideband absorption performance, the absorbance in the wave band of 0.25-25 mu m is 98-99.9%, and the reflectivity is 0.1-2%.
The embodiment of the invention also provides a preparation method of the silica-based super-black aerogel, which comprises the following steps:
1) Dissolving an organosiloxane precursor in a solvent, adding nano light absorption particles, and forming uniform dispersion liquid by high-speed stirring and ultrasonic treatment;
2) Adding or not adding an acid catalyst selectively into the dispersion liquid obtained in the step 1) to carry out hydrolysis reaction, and then adding an alkali catalyst and water to carry out hydrolysis polycondensation reaction to obtain silica-based super-black gel;
3) And (3) performing solvent replacement, optionally performing surface modification or not, and drying to obtain the silica-based super-black aerogel.
The embodiment of the invention also provides the silica-based super-black aerogel prepared by the preparation method.
The embodiment of the invention also provides application of the silica-based super-black aerogel in the fields of heat insulation and preservation, photo-thermal water evaporation, photo-thermal energy conversion, thermoelectric conversion, photocatalysis or 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 super-black aerogel provided by the invention is nanoscale particles, and has high light absorbance, low refractive index, low reflectivity and low thermal conductivity; the material has good mechanical properties in the range of-196 ℃ to 250 ℃ and can bear loads such as compression, impact and the like; the silica-based super-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 silica-based super-black aerogel provided by the invention takes the organosiloxane as a precursor, and can realize controllable preparation of the diameter of the nano-particles by regulating and controlling the components of the precursor and the solvent; the preparation process is simple, and light absorbing substances 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 that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a graph showing the desorption of nitrogen from silica-based super-black aerogel obtained in example 1 of the present invention;
FIG. 2 is a graph showing pore size distribution of silica-based super-black aerogel obtained in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of silica-based super black aerogel obtained in example 1 of the present invention;
FIG. 4 is a transmission electron micrograph of silica-based ultra-black aerogel obtained in example 1 of the present invention;
FIG. 5 is an optical photograph of silica-based super black aerogel obtained in example 1 of the present invention;
FIG. 6 is a scanning electron micrograph of silica-based super black aerogel obtained in example 2 of the present invention;
FIG. 7 is a transmission electron micrograph of silica-based ultra-black aerogel obtained in example 2 of the present invention;
FIG. 8 is a graph showing the thermogravimetric profile of silica-based ultra-black aerogel obtained in example 2 of the present invention;
FIG. 9 is a reflectance spectrum of silica-based super-black aerogel obtained in example 2 of the present invention;
FIG. 10 is a graph showing the absorptance spectrum of silica-based super-black aerogel obtained in example 2 of the present invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have conducted long-term studies and extensive practices and have unexpectedly found that compounding an aerogel with a highly light-absorbing substance (carbon-based or metal) is an ideal material for preparing a superblack material.
The silica aerogel is a low dielectric and low refractive index material, has excellent insulativity, can disperse light absorbing substances (carbon-based materials or metal nano particles) in a three-dimensional nano network skeleton of the silica aerogel although the light absorbing rate of the silica aerogel is low, has low interface reflection, and can maximally increase the light transmitting performance of the silica aerogel by controlling the gel nucleation and growth processes to enable the particle size of the silica nano particles to be 2-10 nm, so that the light absorbing rate of the light absorbing substances can be improved, and the reflectivity of the light absorbing substances can be reduced to maximize the light absorbing rate. In addition, the conductivity and the insulation superproperty of the material can be regulated and controlled by regulating and controlling the content of the carbon-based material or the metal nano particles in the silicon oxide aerogel. The method has the advantages of simple preparation process, low requirements on the types of light-absorbing substances, extremely strong universality and great significance for development of the super-black material.
Therefore, the technical scheme of the invention is provided, which is mainly characterized in that an organosiloxane precursor and light-absorbing nano particles are mixed, then hydrolyzed and polycondensed under the condition of a catalyst to form gel, and the silica-based super-black aerogel and a series of applications of the silica-based super-black aerogel are obtained through solvent replacement, modification and drying steps. The technical scheme, the implementation process, the principle and the like are further explained as follows.
The silica-based super-black aerogel provided by one aspect of the embodiment of the invention is composed of a three-dimensional porous network structure formed by mutually connecting nano light absorption particles and silica nanoparticles, wherein the composition of the silica nanoparticles comprises any one or two of silicon dioxide, polymethyl silsesquioxane and the like; the composition of the nano light absorbing particles comprises any one or more than two of nano carbon black, carbon nano tube, graphene, nano metal gold, nano metal silver and the like, but is not limited to the above.
In some embodiments, the silica-based ultra-black aerogel has ultra-wideband absorption properties, an absorbance in the 0.25-25 μm band of 98-99.9%, and a reflectance of 0.1-2%.
In some embodiments, the three-dimensional porous network structure includes micropores with pore diameters below 2nm, mesopores between 2nm and 50nm, and macropores between 50nm and 1 μm.
In some embodiments, the morphology of the silicon oxide 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 diameter of the silica nanoparticles is 2 to 10nm, preferably 4 to 8nm.
In some embodiments, the morphology of the nano light absorbing particles includes any one or a combination of two or more of spheres, flakes, tubes, irregularities, and the like, but is not limited thereto.
Further, the particle diameter of the light absorbing nanoparticle is 2 to 100nm, preferably 2 to 20nm.
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 super-black aerogel is 600-1200 m 2 Preferably 700 to 1000m 2 /g。
Further, the pore volume of the silica-based super-black aerogel is 0.1-3.0 cm 3 Preferably 1.5 to 2.5 cm/g 3 /g。
Further, the silica-based super-black aerogel has a porosity of 75 to 99%, preferably 90 to 95%.
Further, the hydrophobic angle of the silica-based super-black aerogel is 0-160 degrees.
Further, the long-term use temperature of the silica-based super-black aerogel is above 250 ℃.
In summary, the basic structural unit of the silica-based super-black aerogel is nano-scale particles, and has low reflectivity, high light absorbance, low reflectivity, low thermal conductivity, controllable density and excellent thermal stability. The silica-based super-black aerogel provided by the invention has good mechanical properties in the range of-196 ℃ to 250 ℃ and can bear loads such as compression, impact and the like.
The preparation method of the silica-based super-black aerogel provided by one aspect of the embodiment of the invention mainly comprises the following steps: and uniformly mixing the organic siloxane precursor and the light-absorbing nano particles, performing hydrolytic polycondensation under the condition of a catalyst to form gel, and performing solvent replacement, modification and drying steps to obtain the silica-based broadband absorption super-black aerogel.
In some embodiments, the method of preparation essentially comprises the steps of:
1) Dissolving an organosiloxane precursor in a solvent, adding nano light absorption particles, and forming uniform dispersion liquid by high-speed stirring and ultrasonic treatment;
2) Adding or not adding an acid catalyst selectively into the dispersion liquid obtained in the step 1) to carry out hydrolysis reaction, and then adding an alkali catalyst and water to carry out hydrolysis polycondensation reaction to obtain silica-based super-black gel;
3) And (3) performing solvent replacement, optionally performing surface modification or not, and drying treatment on the silica-based super-black gel obtained in the step (2) to obtain the silica-based super-black aerogel.
In some embodiments, in step 1), the organosiloxane precursor includes, but is not limited to, any one or a 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 solvent to organosiloxane precursor is 1 to 20:1, preferably 1 to 5:1.
In some embodiments, the mass ratio of the nano-light absorbing particles to the organosiloxane precursor is 0.001 to 1:1, preferably 0.01 to 0.1:1.
Further, the nano light absorbing particles include any one or a combination of two or more of nano carbon black, carbon nanotube, graphene, nano metallic gold, silver, etc., and are not limited thereto.
In some embodiments, in step 1), the high speed stirring is performed at a speed of 1000 to 50000 rpm, preferably 10000 to 20000 rpm, and the high speed stirring is performed for a time of 1 to 100 minutes, preferably 10 to 30 minutes; the time of the ultrasound is 1 to 1000 minutes, preferably 10 to 100 minutes.
In some embodiments, in step 2), the molar ratio of water to organosiloxane 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 acid catalyst is combined with an organosiloxane precursorMolar ratio of 0 to 10 -1 1:0 to 10 -3 ∶1。
Further, the base catalyst includes any one or a combination of two or more of ammonia water, 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 1:1, preferably 10 -2 ～10 -4 ∶1。
In some embodiments, the hydrolysis reaction is carried out for a period of time ranging from 0 to 24 hours and at a temperature ranging from 10 to 80 ℃.
In some embodiments, the hydrolytic polycondensation reaction time is 12 to 48 hours and the temperature of the hydrolytic polycondensation reaction is 10 to 80 ℃.
In some embodiments, in step 3), the solvent used for the solvent substitution includes any one or a combination of two or more of ethanol, tetrahydrofuran, acetone, n-hexane, etc., and is not limited thereto.
Further, the temperature of the solvent substitution is 20 to 80 ℃, preferably 20 to 40 ℃.
Further, the number of solvent substitutions is 1 to 10.
Further, in the step 3), the optional surface hydrophobic modifier used for the surface modification includes any one or a combination of two or more of trimethylchlorosilane, hexamethyldisilazane, 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 the preferred embodiments, the supercritical drying technology includes: replacing the liquid component inside the gel material with a supercritical fluid in a supercritical state, wherein the supercritical fluid comprises, but is not limited to, supercritical CO 2 (40 ℃,10 MPa), supercritical methanol (240 ℃,8 MPa), supercritical ethanol (240 ℃,7 MPa) and the like.
As one of preferable embodiments, the atmospheric drying includes: and replacing liquid in the gel with ethanol, n-hexane and other solvents, and placing the gel material under normal pressure or lower vacuum to raise the temperature so as to volatilize the solvents and obtain the silica-based super-black aerogel.
In summary, the silica-based super-black aerogel provided by the invention uses the organosiloxane as a precursor, and can realize controllable preparation of the diameter of the nano-particles by regulating and controlling the precursor and the solvent component; the preparation process is simple, the reaction condition is mild, the operation is easy, the energy consumption is low, the cost is low, the pollution is avoided, and the large-scale continuous production can be realized. Meanwhile, the light absorbing substances can be selected to meet different scene requirements.
In another aspect, the embodiment of the invention also provides a huge application prospect of the silica-based super-black aerogel in the fields of heat insulation and preservation, 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 super-black aerogel specifically comprises the following steps:
1) The three-dimensional network structure of the silica-based super-black aerogel endows the silica-based super-black aerogel with extremely high porosity and extremely high air content, and can be applied to thermal management under normal-temperature to high-temperature environments.
2) The high absorbance of the silicon-oxy-silicon-based super 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 means of the technical scheme, the silica-based super-black aerogel provided by the invention has high absorbance and low density, and has great prospect 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 solution of the present invention will be described in further detail below with reference to a number of preferred embodiments and accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. It should be noted that the examples described below are intended to facilitate the understanding of the present invention and are not intended to limit the present invention in any way. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer.
Example 1
(1) Tetraethyl orthosilicate, nano carbon black and ethanol are stirred at high speed (the rotating speed is 10000 revolutions per minute, the time is 100 minutes) and ultrasonic waves are carried out for 100 minutes to form a dispersion liquid, formic acid is added, then the mixture is mixed and stirred for 1 hour at 60 ℃ to hydrolyze, and then water and ammonia water are added to carry out polycondensation reaction (the time is 48 hours, the temperature is 30 ℃). Wherein the mol ratio of the tetraethyl orthosilicate, the ethanol, the formic acid, the water and the 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) hermetically storing the dispersion liquid in the step (1) in an oven at 60 ℃ for 24 hours to obtain the silica-based super-black gel.
(3) And (3) replacing the silica-based super black gel in the step (2) with ethanol for 10 times at 40 ℃, and modifying with trimethylchlorosilane and then adopting a normal pressure drying process to obtain the silica-based super black aerogel.
The silica-based ultra-black gel obtained in this example has a nitrogen adsorption and desorption curve shown in fig. 1, a pore size distribution shown in fig. 2, an sem structure shown in fig. 3, a tem image shown in fig. 4, and an optical photograph shown in fig. 5. The physical parameters of the silica nanoparticles of the silica-based super-black aerogel obtained in this example, such as particle size, absorbance, reflectivity, specific surface area and density, 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, the time is 10 minutes) and ultrasonic waves are carried out for 30 minutes to form dispersion liquid, then formic acid is added, mixing and stirring are carried out for 1 hour at 60 ℃ to carry out hydrolysis, and then water and ammonia water are added to carry out polycondensation reaction (the time is 24 hours, the temperature is 40 ℃). Wherein the mol ratio of the tetraethyl orthosilicate, the ethanol, the formic acid, the water and the 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) hermetically storing the dispersion liquid in the step (1) in an oven at 40 ℃ for 72 hours to obtain the silica-based super-black gel.
(3) And (3) replacing the silica-based super-black gel in the step (2) with ethanol for 3 times at 60 ℃, and performing hydrophobic modification on hexamethyldisilazane and then adopting a normal pressure drying process to obtain the silica-based super-black aerogel.
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. The physical parameters such as the particle size, specific surface area and density of the silica nanoparticles of the silica-based super-black aerogel obtained in this example are shown in table 1.
Example 3
(1) Tetramethyl orthosilicate, carbon nano tube and methanol are stirred at high speed (the rotation speed is 50000 r/min, the time is 1 min) and ultrasonic wave is carried out for 10 min to form dispersion liquid, hydrochloric acid is added, then mixing and stirring are carried out for 1 h at 60 ℃ to carry out hydrolysis, and then water and tetramethyl ammonium hydroxide are added to carry out polycondensation reaction (the time is 24h, the temperature is 60 ℃). Wherein the molar ratio of the tetramethyl orthosilicate, the methanol, the hydrochloric acid, the water and the tetramethyl ammonium hydroxide is 1:10:10 -2 ∶4∶10 -2 The mass ratio of the carbon nano tube to the tetramethyl orthosilicate is 0.001:1.
(2) And (3) hermetically storing the dispersion liquid in the step (1) in an oven at 50 ℃ for 24 hours to obtain the silica-based super-black gel.
(3) And (3) replacing the silica-based super-black gel in the step (2) with acetone for 5 times at 30 ℃, and obtaining the silica-based super-black aerogel by adopting a supercritical carbon dioxide process and a normal pressure drying process.
The physical parameters of the silica nanoparticles of the silica-based super-black aerogel obtained in this example, such as particle size, absorbance, reflectivity, specific surface area and density, are shown in table 1.
Example 4
(1) Stirring tetramethyl orthosilicate, carbon nanotube and methanol at high speed (rotation speed of 20000 rpm for 30 min), ultrasonic treating for 1000 min to obtain dispersion, adding hydrochloric acid, stirring at 30deg.C for 1 hr for hydrolysis, adding water and tetramethylammonium hydroxidePolycondensation (time 48 hours, temperature 10 ℃ C.). Wherein the molar 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 (3) hermetically storing the dispersion liquid in the step (1) in an oven at 60 ℃ for 24 hours to obtain the silica-based super-black gel.
(3) And (3) replacing the silica-based super-black gel in the step (2) with acetone for 5 times at 30 ℃, and obtaining the silica-based super-black aerogel by adopting a supercritical carbon dioxide process and a normal pressure drying process.
The physical parameters of the silica nanoparticles of the silica-based super-black aerogel obtained in this example, such as particle size, absorbance, reflectivity, specific surface area and density, are shown in table 1.
Example 5
(1) Methyltrimethoxysilane, graphene and tetrahydrofuran are stirred at a high speed (the rotating speed is 30000 r/min and the time is 20 min) and are subjected to ultrasonic treatment for 1000 min to form a dispersion liquid, sulfuric acid is added, the mixture is mixed and stirred for 1 hour at 30 ℃ to hydrolyze, and then water and sodium carbonate are added to carry out polycondensation reaction (the time is 12 hours and the temperature is 50 ℃). Wherein, the mol ratio of methyltrimethoxysilane, tetrahydrofuran, sulfuric acid, water and sodium carbonate is 1:1:0.1:4:0.1, and the mass ratio of graphene to methyltrimethoxysilane is 0.01:1.
(2) And (3) hermetically storing the dispersion liquid in the step (1) in an oven at 60 ℃ for 24 hours to obtain the silica-based super-black gel.
(3) And (3) replacing the silica-based super-black gel in the step (2) with tetrahydrofuran for 5 times at 40 ℃, and obtaining the silica-based super-black aerogel by adopting a supercritical carbon dioxide drying process.
The physical parameters of the silica nanoparticles of the silica-based super-black aerogel obtained in this example, such as particle size, absorbance, reflectivity, specific surface area and density, are shown in table 1.
Example 6
(1) Stirring methyltrimethoxysilane, graphene and tetrahydrofuran at high speed (rotation speed of 10000 rpm, time of 30 min) and ultrasonic treating for 1000 minTo form a dispersion, sulfuric acid was added thereto, and the mixture was stirred at 30℃for 1 hour to hydrolyze, and then water and sodium carbonate were added thereto to carry out polycondensation (the time was 48 hours, and the temperature was 50 ℃). Wherein the molar ratio of methyltrimethoxysilane, tetrahydrofuran, sulfuric acid, water and 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) hermetically storing the dispersion liquid in the step (1) in an oven at 60 ℃ for 24 hours to obtain the silica-based super-black gel.
(3) And (3) replacing the silica-based super-black gel in the step (2) with n-hexane for 5 times at 40 ℃, and adopting a normal pressure drying process to obtain the silica-based super-black aerogel.
The physical parameters of the silica nanoparticles of the silica-based super-black aerogel obtained in this example, such as particle size, absorbance, reflectivity, specific surface area and density, are shown in table 1.
Example 7
(1) Tetramethyl orthosilicate, nano metal gold and DMSO are stirred at high speed (rotation speed is 10000 r/min, time is 30 min) and ultrasonic wave is carried out for 1000 min to form dispersion liquid, then ammonia water and water are added, and then the mixture is mixed and stirred for 1 hour at 30 ℃ to carry out hydrolytic polycondensation reaction (the time is 48 hours, the temperature is 80 ℃). Wherein the molar ratio of the tetramethyl orthosilicate, the DMSO, the water and the ammonia water is 1:3:3:10 -5 The mass ratio of the nano metal gold to the tetramethyl orthosilicate is 1:1.
(2) And (3) hermetically storing the dispersion liquid in the step (1) in an oven at 60 ℃ for 24 hours to obtain the silica-based super-black gel.
(3) And (3) replacing the silica-based super-black gel in the step (2) with ethanol for 5 times at 30 ℃, and obtaining the silica-based super-black aerogel by adopting a supercritical carbon dioxide process and a normal pressure drying process.
The physical parameters of the silica nanoparticles of the silica-based super-black aerogel obtained in this example, such as particle size, absorbance, reflectivity, specific surface area and density, are shown in table 1.
Example 8
(1) Stirring tetramethyl orthosilicate, nano metal gold and DMSO at high speed (rotation speed 10000 rpm, time)30 minutes apart) was sonicated for 100 minutes to form a dispersion, and then triethylamine and water were added thereto, followed by mixing and stirring at 30℃for 1 hour to carry out hydrolytic polycondensation (time: 20 hours, temperature: 80 ℃). Wherein the molar 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 (3) hermetically storing the dispersion liquid in the step (1) in an oven at 60 ℃ for 24 hours to obtain the silica-based super-black gel.
(3) And (3) replacing the silica-based super-black gel in the step (2) with ethanol for 5 times at 30 ℃, and obtaining the silica-based super-black aerogel by adopting a supercritical carbon dioxide process and a normal pressure drying process.
The physical parameters of the silica nanoparticles of the silica-based super-black aerogel obtained in this example, such as particle size, absorbance, reflectivity, specific surface area and density, are shown in table 1.
Example 9
(1) Tetramethyl orthosilicate, nano metallic silver and DMSO are stirred at high speed (the rotating speed is 1000 rpm, the time is 30 minutes) and ultrasonic waves are carried out for 10 minutes to form dispersion liquid, then ammonia water and water are added, and then the mixture is mixed and stirred for 24 hours at 30 ℃ to carry out hydrolytic polycondensation reaction (the time is 30 hours, and the temperature is 50 ℃). Wherein the molar 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 metallic silver to the tetramethyl orthosilicate is 1:1.
(2) And (3) hermetically storing the dispersion liquid in the step (1) in an oven at 60 ℃ for 24 hours to obtain the silica-based super-black gel.
(3) And (3) replacing the silica-based super-black gel in the step (2) with ethanol for 5 times at 20 ℃, and obtaining the silica-based super-black aerogel by adopting a supercritical carbon dioxide process and a normal pressure drying process.
The physical parameters of the silica nanoparticles of the silica-based super-black aerogel obtained in this example, such as particle size, absorbance, reflectivity, specific surface area and density, are shown in table 1.
Example 10
(1) Stirring tetramethyl orthosilicate, nano silver metal and DMSO at high speed (rotation speed 15000 rpm, time 15 min)Clock) ultrasonic for 1 min to form dispersion, adding ammonia water and water, mixing and stirring at 30 deg.c for 24 hr to perform hydrolytic polycondensation reaction at 40 deg.c for 36 hr. Wherein the molar 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 metallic silver to the tetramethyl orthosilicate is 0.01:1.
(2) And (3) hermetically storing the dispersion liquid in the step (1) in an oven at 60 ℃ for 24 hours to obtain the silica-based super-black gel.
(3) And (3) replacing the silica-based super-black gel in the step (2) with DMSO for 5 times at 80 ℃, and obtaining the silica-based super-black aerogel by adopting a supercritical carbon dioxide process and a normal pressure drying process.
The physical parameters of the silica nanoparticles of the silica-based super-black aerogel obtained in this example, such as particle size, absorbance, reflectivity, specific surface area and density, are shown in table 1.
TABLE 1 Structure and Performance parameters of silica-based ultra-Black aerogels obtained in examples 1-10
Comparative example 1
(1) Tetraethyl orthosilicate, graphene and ethanol are stirred at a high speed (rotating speed: 10000 revolutions per minute, time: 60 minutes) and ultrasonic waves (10 minutes) to form a dispersion, formic acid is added, then the mixture is mixed and stirred at 60 ℃ for 1 hour to hydrolyze, and then water and ammonia water are added to carry out polycondensation reaction (time: 48 hours, temperature: 60 ℃). Wherein the mol ratio of tetraethyl orthosilicate, ethanol, formic acid, water and ammonia water is 1:1:0.1:4:0.01, and the mass ratio of graphene to tetraethyl orthosilicate is 0.01:1.
(2) And (3) hermetically storing the dispersion liquid in the step (1) in an oven at 60 ℃ for 24 hours to obtain silica-based black gel.
(3) And (3) replacing the silica-based black gel in the step (2) with ethanol for 10 times at 40 ℃, and modifying with trimethylchlorosilane and then adopting a normal pressure drying process to obtain the silica-based black aerogel.
The particle size of the nano particles of the silica-based aerogel is 30-50 nm, and the density is 1000mg/cm 3 Absorbance 90% and reflectance 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 silicon oxide-based black aerogel has the advantages that the interface scattering is strong due to the large particle size of the nano particles, and light is reflected, so that the silicon oxide-based black aerogel in comparative example 1 has low absorptivity and cannot meet the ultra-black standard.
In addition, the inventors also prepared a series of silica-based ultra-black aerogels by the method of examples 1-10, using other materials and process conditions as set forth herein. It was found that these silica-based superblack gels also have the excellent properties described in this specification.
It should be understood that the foregoing is only a few embodiments of the present invention, and it should be noted that other modifications and improvements can be made by those skilled in the art without departing from the inventive concept of the present invention, which fall within the scope of the present invention.
Claims (23)
1. The silica-based super-black aerogel is characterized by comprising a three-dimensional porous network structure formed by mutually connecting nano light absorption particles and silica nano particles, wherein the particle size of the silica nano particles is 2-10 nm; the particle size of the nano light absorption particles is 2-100 nm, and the composition of the silicon oxide nano particles comprises any one or two of silicon dioxide and polymethyl silsesquioxane; the composition of the nano light absorption particles comprises any one or more than two of nano carbon black, carbon nano tube, graphene, nano metal gold and nano metal silver;
the density of the silica-based super-black aerogel is 50-300 mg/cm 3 The specific surface of the silica-based super-black aerogelThe product is 600-1200 m 2 Per gram, the pore volume is 0.1-3.0 cm 3 G, wherein the porosity is 75-99%; the silica-based super-black aerogel has ultra-wideband absorption performance, the absorbance in a wave band of 0.25-25 mu m is 98-99.9%, and the reflectivity is 0.1-2%;
the preparation method of the silica-based super-black aerogel comprises the following steps:
1) Dissolving an organosiloxane precursor in a solvent, adding nano light absorption particles, and forming uniform dispersion liquid by high-speed stirring and ultrasonic treatment;
2) Adding or not adding an acid catalyst into the dispersion liquid obtained in the step 1) selectively to carry out hydrolysis reaction, wherein the time of the hydrolysis reaction is within 24 hours, the temperature of the hydrolysis reaction is 10-80 ℃, and the molar ratio of the acid catalyst to the organosiloxane precursor is 0-10 -1 :1, then adding a base catalyst and water to carry out polycondensation reaction, wherein the polycondensation reaction time is 12-48 h, the polycondensation reaction temperature is 10-80 ℃, and the molar ratio of the base catalyst to the organosiloxane precursor is 10 -1 ~10 -5 :1, obtaining silica-based super-black gel;
3) Performing solvent replacement, optionally performing surface modification or not, on the silica-based super-black gel obtained in the step 2), and then drying to obtain silica-based super-black aerogel;
wherein the molar ratio of the solvent to the organosiloxane precursor is 3-20: 1, wherein the mass ratio of the nano light absorption particles to the organic siloxane precursor is 0.01-1: 1.
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.
3. The silica-based ultra-black aerogel according to claim 1, wherein: the three-dimensional porous network structure comprises micropores with the aperture below 2nm, mesopores with the aperture of 2 nm-50 nm and macropores with the aperture of 50 nm-1 mu m.
4. The silica-based ultra-black aerogel according to claim 1, wherein: the morphology of the silicon oxide nano particles comprises any one or more than two of spheres, ellipsoids and irregularities.
5. The silica-based ultra-black aerogel according to claim 1, wherein: the nanometer light absorption particles are in any one or more than two of spheres, flakes, tubes and irregularities.
6. The silica-based ultra-black aerogel according to claim 1, wherein: the silicon oxide-based super-black aerogel has a long-term use temperature of higher than 250 ℃.
7. The silica-based ultra-black aerogel according to claim 1, wherein: the density of the silica-based super-black aerogel is 100-200 mg/cm 3 The specific surface area of the silica-based super-black aerogel is 700-1000 m 2 Per gram, the pore volume is 1.5-2.5 cm 3 And/g, wherein the porosity is 90-95%.
8. The method for preparing silica-based super black aerogel according to any of claims 1 to 7, comprising:
1) Dissolving an organosiloxane precursor in a solvent, adding nano light absorption particles, and forming uniform dispersion liquid by high-speed stirring and ultrasonic treatment;
2) Adding or not adding an acid catalyst into the dispersion liquid obtained in the step 1) selectively to carry out hydrolysis reaction, wherein the time of the hydrolysis reaction is within 24 hours, the temperature of the hydrolysis reaction is 10-80 ℃, and the molar ratio of the acid catalyst to the organosiloxane precursor is 0-10 -1 :1, then adding a base catalyst and water to carry out polycondensation reaction, wherein the polycondensation reaction time is 12-48 h, the polycondensation reaction temperature is 10-80 ℃, and the molar ratio of the base catalyst to the organosiloxane precursor is 10 -1 ~10 -5 :1, obtaining silica-based super-black gel;
3) Performing solvent replacement, optionally performing surface modification or not, on the silica-based super-black gel obtained in the step 2), and then drying to obtain silica-based super-black aerogel;
wherein the molar ratio of the solvent to the organosiloxane precursor is 3-20: 1, wherein the mass ratio of the nano light absorption particles to the organic siloxane precursor is 0.01-1: 1.
9. the method according to claim 8, wherein in step 1), the organosiloxane precursor includes any one or a combination of two or more of tetraethyl orthosilicate, tetramethyl orthosilicate, and methyltrimethoxysilane.
10. The method according to claim 8, wherein the solvent comprises any one or a combination of two or more of methanol, ethanol, tetrahydrofuran, and dimethyl sulfoxide.
11. The preparation method according to claim 8, wherein in the step 1), the rotation speed of the high-speed stirring is 1000-50000 rpm, and the time of the high-speed stirring is 1-100 minutes; and/or the ultrasonic treatment time is 1-1000 minutes.
12. The method of manufacturing according to claim 11, wherein: the rotating speed of the high-speed stirring is 10000-20000 revolutions per minute, and the time of the high-speed stirring is 10-30 minutes; and/or the ultrasonic treatment time is 10-100 minutes.
13. The method according to claim 8, wherein in step 2), the molar ratio of water to organosiloxane is 1 to 4:1.
14. the method according to claim 8, wherein the acid catalyst comprises any one or a combination of two or more of formic acid, sulfuric acid, nitric acid, and hydrochloric acid.
15. The method of claim 14, wherein the molar ratio of the acid catalyst to the organosiloxane precursor is 0 to 10 -3 ：1。
16. The method according to claim 8, wherein the base catalyst comprises any one or a combination of two or more of ammonia water, triethylamine, tetramethylammonium hydroxide, and sodium carbonate.
17. The method of claim 16, wherein the molar ratio of base catalyst to organosiloxane precursor is 10 -2 ~10 -4 ：1。
18. The preparation method according to claim 8, wherein in the step 3), the solvent used for the solvent replacement includes any one or a combination of two or more of ethanol, tetrahydrofuran, acetone and n-hexane, and the temperature of the solvent replacement is 20-80 ℃.
19. The method according to claim 8, wherein the number of solvent substitutions is 1 to 10.
20. The method according to claim 8, wherein the solvent substitution temperature is 20 to 40 ℃.
21. The method of manufacturing according to claim 8, wherein: in the step 3), the surface hydrophobic modifier used for surface modification comprises any one or more than two of trimethylchlorosilane, hexamethyldisilazane and fluorocarbon resin.
22. The method of manufacturing according to claim 8, wherein: the drying treatment includes any one of supercritical drying and atmospheric drying.
23. Use of the silica-based ultra-black aerogel according to any of claims 1 to 7 in the fields of thermal insulation, photo-thermal water evaporation, photo-thermal energy conversion, thermoelectric conversion, photocatalysis or optical instruments.
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