CN104689784B - SiO2 composite aerogel material loaded with photocatalyst and preparation method of SiO2 composite aerogel material - Google Patents
SiO2 composite aerogel material loaded with photocatalyst and preparation method of SiO2 composite aerogel material Download PDFInfo
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- CN104689784B CN104689784B CN201510079810.5A CN201510079810A CN104689784B CN 104689784 B CN104689784 B CN 104689784B CN 201510079810 A CN201510079810 A CN 201510079810A CN 104689784 B CN104689784 B CN 104689784B
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- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 239000004964 aerogel Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 title abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract 20
- 229910052681 coesite Inorganic materials 0.000 title abstract 10
- 229910052906 cristobalite Inorganic materials 0.000 title abstract 10
- 239000000377 silicon dioxide Substances 0.000 title abstract 10
- 229910052682 stishovite Inorganic materials 0.000 title abstract 10
- 229910052905 tridymite Inorganic materials 0.000 title abstract 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011148 porous material Substances 0.000 claims abstract description 35
- 230000008021 deposition Effects 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000012986 modification Methods 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims abstract description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 88
- 239000000499 gel Substances 0.000 claims description 72
- 239000003054 catalyst Substances 0.000 claims description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 229920000297 Rayon Polymers 0.000 claims description 45
- 238000000151 deposition Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- 239000011240 wet gel Substances 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 230000005070 ripening Effects 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical group 0.000 claims description 4
- 239000013589 supplement Substances 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000017 hydrogel Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000005046 Chlorosilane Substances 0.000 claims 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 20
- 238000001179 sorption measurement Methods 0.000 abstract description 17
- 238000007598 dipping method Methods 0.000 abstract description 3
- 238000011282 treatment Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 52
- 239000002253 acid Substances 0.000 description 32
- 238000003756 stirring Methods 0.000 description 32
- 229940043267 rhodamine b Drugs 0.000 description 31
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 30
- 239000008367 deionised water Substances 0.000 description 23
- 229910021641 deionized water Inorganic materials 0.000 description 23
- 238000007146 photocatalysis Methods 0.000 description 17
- 238000005342 ion exchange Methods 0.000 description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- 238000005286 illumination Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- 235000019353 potassium silicate Nutrition 0.000 description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 10
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000003292 glue Substances 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 229910000348 titanium sulfate Inorganic materials 0.000 description 6
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000003729 cation exchange resin Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001473 noxious effect Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 125000005624 silicic acid group Chemical group 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241001400064 Valeria Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000802 evaporation-induced self-assembly Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229940073561 hexamethyldisiloxane Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- -1 silicon Oxygen alkane Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention relates to a SiO2 composite aerogel material loaded with a photocatalyst and a preparation method of the SiO2 composite aerogel material, and belongs to the technical field of adsorption/photocatalytic materials. The preparation method of the SiO2 composite aerogel material loaded with the photocatalyst comprises the step of preparing composite gel: dipping SiO2 gel into photocatalyst sol or solution to obtain photocatalyst/SiO2 composite gel; carrying out deposition aging treatment on the obtained photocatalyst/SiO2 composite gel by utilizing alkyl organic solvents, wherein the alkyl organic solvents are hexamethyldisiloxane, alcohol and alkane solvents, and the alkyl organic solvents are respectively hexamethyldisiloxane, alcohol (such as ethanol or isopropanol) and alkane (such as n-hexane or heptane) solvents; then carrying out surface modification and ambient pressure drying to obtain a photocatalyst/SiO2 composite aerogel material; and the prepared photocatalyst/SiO2 composite aerogel is of a mesoporous structure, with a pore diameter of 8-20 nm, a specific surface area of 200-700 m<2>/g, and a pore volume of 0.5-2.0 cm<3>/g.
Description
Technical field
The present invention relates to a kind of sio of loaded optic catalyst2Aerogel composite and preparation method thereof, belong to absorption/
Catalysis material technical field.
Background technology
sio2Aeroge has the network structure of mesoporous nano, has low-density, high-specific surface area and high porosity feature,
Therefore sio2Aeroge has broad application prospects at aspects such as insulation, gas absorption and catalyst carriers.tio2Have
Good photocatalytic activity, by tio2With sio2Aeroge is combined preparation sio2-tio2Composite aerogel, can play gas simultaneously
The efficient absorption effect of gel structure and tio2Good photocatalysis performance.However, due to tio2Higher energy gap makes it
Have and just there is high photocatalysis efficiency under ultraviolet light, tio in addition2The high recombination rate of photo-generate electron-hole pair is also in certain journey
Tio be have impact on degree2Photocatalytic activity.Therefore, for the sio that can play suction-operated and photocatalysis simultaneously2-
tio2For composite aerogel, it is very necessary for improving its absorption/photocatalysis synergy effect under sunshine further
's.
Research shows, by tio2With wo3Deng semiconductors coupling, can effectively widen tio2Spectral response range and raising
The separative efficiency of compound system photo-generated carrier is such that it is able to improve tio further2Photocatalytic activity and its under visible light
Photocatalysis effect.Valeria puddu etc. is with tioso4(nh4)6h2w12o40·nh2O is raw material, using hydro-thermal method preparation
Tungsten titanium composite nano powder (chemical communications, 2007 (45): 4749-4751)；Liu Yang etc. is with p25 powder
For presoma, it is prepared for the wo with bigger serface and high ultraviolet catalytic performance using hydrothermal-sintering process3-tio2Complex light is urged
Agent (catalysis journal), 2010,31 (4): 485-489).Miao Hui etc. is with tio2The powder and ammonium tungstate wo that has been raw material Hydrothermal Synthesiss3Mix
Miscellaneous tio2Nanotube, substantially increases its photocatalysis performance (spectrographic laboratory, 2013,30 (2): 599-603).Made above
Wo3-tio2Although composite photo-catalyst has certain visible light photocatalysis effect, and photocatalysis performance is improved,
It is the presence due to not having hole, almost do not have absorption property to pollutant.Meanwhile, in catalytic process, catalyst failure is very fast,
Can not effectively degrade for dense pollutant.Huang Yan etc. is with p123 for template with the method for evaporation-induced self-assembly
It is prepared for the order mesoporous wo of two-dimentional six side p6mm3/tio2Composite (catalysis journal, 2012,33 (2): 309-316), prepared
Mesoporous wo3/tio2Although composite has certain absorption property, its absorption property still awaits improving further.
Additionally, document shows, bi2o3-tio2、fe3+-tio2、v-tio2、co-tio2And m-tio2(m is that la, ce etc. are dilute
Earth metal) be respectively provided with higher photocatalysis performance (Chinese invention patent cn 102125831a, material Leader: a research piece, 2010,
24 (12): 56-58；Artificial lens journal, 2010,39 (5): 1243-1248；Acta PhySico-Chimica Sinica, 2011,27 (10): 2406-
2410；Journal of Inorganic Materials, 2011,26 (7): 739-746.)
In recent years, by wet gel is carried out surface modification often press dry drying process preparation there is absorption property and light simultaneously
The sio of catalytic effect2-tio2The research of composite aerogel causes the concern of people.For example, by sio2-tio2Compound wet solidifying
Glue carries out surface modification, can prepare sio by constant pressure and dry2-tio2Composite aerogel (Chinese invention patent cn
100574863c；Chinese invention patent cn102671586a；Tongji University's journal (natural science edition), 2005,33:1078-
1082；SCI, 2004,25 (2): 325-329；Journal of Inorganic Materials, 2010,25 (9): 911-915).So
And, sio2-tio2Though composite aerogel has higher absorption property, it can only play its higher light under ultraviolet light and urge
Change performance.In addition, other is had polynary photochemical catalyst and the sio of high photocatalysis efficiency or visible light catalytic performance2Aeroge
Compound, then will be because of sio2The efficient absorption efficiency of aeroge and the synergy of photochemical catalyst and make it have highly efficient
Remove the effect of noxious pollutant.
Content of the invention
It is an object of the invention to provide a kind of sio of loaded optic catalyst2Aerogel composite and preparation method thereof, this
Invent the sio of addressed loaded optic catalyst2Composite aerogel has the high efficiency of additive capability of porous aerogel and many simultaneously
The visible light catalytic performance of first photochemical catalyst, absorption/visible light catalytic acts synergistically, can be in daily sunshine or visible ray
According under more effectively remove noxious pollutant in empty gas and water or surrounding environment, thus have more in depollution of environment field
Wide application prospect.
Of the present invention and loaded optic catalyst sio2Relate to utilize sio in the preparation method of composite aerogel2Water
Gel piece is dipped in polynary photocatalyst sol or solution, obtains photochemical catalyst/sio2Plural gel, passes through in alkane afterwards again
Carry out water-bath deposition ageing and solvent thermal reaction deposition and modified, drying steps in base organic solvent and obtain load photocatalysis
The sio of agent2Composite aerogel catalysis material.This preparation method can not only obtain has high porous volume and bloom is urged simultaneously
The sio of the loaded optic catalyst of agent deposition and suitable crystalline phase2Aerogel composite, and be suitable to prepare multiple differences
Loaded optic catalyst sio2Aerogel composite, it is to avoid former by compound wet gel block exchange of solvent-table
Photochemical catalyst deposition present in the constant pressure and dry preparation technology of face modification is not high and modification liquid and some raw material systems
There is the problem of adverse effect in standby plural gel block；And, with directly adopt sio2Aerogel products are in wo3-tio2Compound molten
Carry out immersion absorption in glue to compare, the sio of the loaded optic catalyst of preparation method preparation that patent of the present invention is addressed2Compound gas
Gel has substantially high pore volume and adsorption capacity.
A kind of sio of loaded optic catalyst2The preparation method of aerogel composite, including photochemical catalyst/sio2Compound solidifying
The step of glue preparation:
By sio2Immersing hydrogels, in photocatalyst sol or solution, obtain photochemical catalyst/sio2Plural gel；By gained
Photochemical catalyst/sio2Plural gel carries out depositing ripening using alkyl organic solvent；
Described alkyl organic solvent is HMDO, alcohols and alkanes solvent.
In technique scheme, described alcohols solvent is preferably ethanol or isopropanol；Described alkanes solvent is preferably hexane
Or heptane.
In technique scheme, described photochemical catalyst is to have the oxide of photocatalysis performance, polynary disclosed in this area
Composite oxides, composite oxide of metal, preferably wo3-tio2、bi2o3-tio2、co-tio2、fe2o3-tio2、v2o5-tio2、
m-tio2、atio3And other have the photochemical catalyst of visible light catalysis activity, wherein, m is rare earth metal, such as la, ce etc.；a
For alkaline-earth metal, such as ca, sr, ba etc..
In technique scheme, the consumption of described photocatalyst sol or solution can be according to sio2The amount of gel determines, makes
Obtain sio2Gel can submerge below photocatalyst sol or liquid level of solution completely.Due to sio2Gel is lighter, at the dipping initial stage
Float on photocatalyst sol, with the carrying out of dipping, it can slowly sink down into container bottom.
Photochemical catalyst/sio of the present invention2The deposition ripening of plural gel can be carried out one of as follows:
I-1. by gained photochemical catalyst/sio2Plural gel is placed in alkyl organic solvent, old under 50～100 DEG C of water-baths
Change, until photochemical catalyst/sio2Plural gel is changed into white from Transparent color；Then, continue to be aged 0 under the water-bath of room temperature～95 DEG C
～24h；
I-2. by gained photochemical catalyst/sio2Plural gel is placed in alkyl organic solvent, carries out molten in 100～200 DEG C
Agent heat deposition is reacted, until photochemical catalyst/sio2Plural gel is changed into white from Transparent color；Then, continue in room temperature～95 DEG C
It is aged 0～24h under water-bath.
The present invention is preferably by block sio2Gel adds to photocatalyst sol or solution, until it is molten to float on photochemical catalyst
Glue or the sio of solution surface2Gel all submerges below photocatalyst sol or liquid level of solution, obtains photochemical catalyst/sio2Compound
Gel.
The preferably described sio of the present invention2Gel is obtained as follows: by modulus be 3.0～3.5 industrial waterglass by vWaterglass: vWater=1:2～1:12 deionized water dilution, is then passed through styrene cationic ion-exchange resin and carries out ion exchange, obtain
The silicic acid of ph=2～3；Take silicic acid and with concentrated ammonia liquor strong alkali solutions such as (or) naoh adjust ph value between 5～7 so as to glue
Solidifying；Or adjust ph value between 12～14, then adjusting ph with watery hydrochloric acid is 7～8 with concentrated ammonia liquor strong alkali solutions such as (or) naoh
Between, static placement.
In above-mentioned later approach, silicic acid forms gel within 5min, and has some strength, disclosure satisfy that later
Absorption, ageing, surface modification etc. are processed；And it includes certain alkaline solution, during being conducive to depositing ripening below
The deposition of photochemical catalyst.
The sio of the preferably described loaded optic catalyst of the present invention2The preparation method of aerogel composite includes old in deposition
The step being modified after change, specifically can be carried out one of as follows:
Ii-1. to the photochemical catalyst/sio after deposition ageing2Add in plural gel blob of viscose liquid and with blob of viscose volume ratio be
0.05～1.0 trim,ethylchlorosilane is modified, and every 24h suctions out the water separating out；According to water yield and blob of viscose in modifying agent
Situation about suspending judges whether to continue to supplement trim,ethylchlorosilane, if water yield is less than the water volume in blob of viscose and blob of viscose is not complete
Float on the water surface of modified precipitation, then continue to add into the trim,ethylchlorosilane modification 24 being 0.05～1.0 with blob of viscose volume ratio
～72h, till not having elutriation to go out；
Ii-2. to the photochemical catalyst/sio after deposition ageing2HMDO or alkane is added in plural gel blob of viscose
Class solvent and the mixed solution of trim,ethylchlorosilane, the addition of HMDO or alkanes organic solvent can for blob of viscose
Being submerged into completely in solution is minimum, and the additional proportion of trim,ethylchlorosilane is vtmcs: vBlob of viscose=0.05:1～1:1, soaks
The modified water separating out is suctioned out after 24h；Judge whether to continue to supplement three according to the situation that water yield and blob of viscose suspend in modifying agent
Methylchlorosilane, if less than the water volume in blob of viscose and blob of viscose does not float on the water surface of modified precipitation water yield completely, continues
Add be equivalent to 0.2～1 times of blob of viscose volume trim,ethylchlorosilane modified, repeat above step until no longer have elutriation go out for
Only, wherein, the preferred n-hexane of alkanes solvent or heptane.
Photocatalyst sol of the present invention or solution are prepared as follows: accordingly urged from hydrolyzing generation accordingly
The presoma of agent, is dissolved in ethanol, water or ethanol water, obtains corresponding photocatalyst sol or solution.
For example, bi2o3-tio2Or fe2o3-tio2The compound method of colloidal sol or solution is as follows: by bismuth nitrate or fecl3Add
The ticl being 0.1～6mol/l to concentration4Solution or ti (so4)2Solution or the tio being prepared by butyl titanate2In colloidal sol, can divide
Xing Cheng not bi2o3-tio2Or fe2o3-tio2Colloidal sol or solution；
wo3-tio2Photocatalyst sol or solution are prepared as follows:
Iii-1. wolframic acid is added to the ticl that concentration is 1～6mol/l4In solution, form wo3-tio2Colloidal sol；
Wolframic acid is added to ti (so that concentration is 0.1～5mol/l by iii-24)2In solution, form wo3-tio2Colloidal sol.
Optionally, to wo3-tio2Add and wo in colloidal sol3-tio2Sol volume is than the concentrated ammonia liquor for 0～0.5.
Above-mentioned concentrated ammonia liquor refers to the ammoniacal liquor that concentration is 10～28%, commercially available, preferably the ammoniacal liquor of concentration 25～28%.
Silicate solution of the present invention, ticl4The compound method of the aqueous solution and tungstic acid press patent cn100574863c,
The method preparation referring in cn 102070195b, cn 102091589b, cn 102671586a；Especially, the preferred institute of the present invention
State wolframic acid, ticl4Solution, titanium sulfate solution are prepared as follows.
The compound method of wolframic acid: compound concentration is the na of 0.1～1.0mol/l first2wo4Solution, preferably prepares 0.5mol/
The na of l2wo4Solution, be then passed through styrene cationic ion-exchange resin carry out ion exchange obtain ph=1.5～3 wolframic acid molten
Liquid.
ticl4The compound method of solution: by ticl4Slowly be added drop-wise on ice cube, ice melting after start stir, treat ticl4
It is stirred for 30min so as to being sufficiently mixed and cooling down after all adding.Ticl in the present invention4The concentration of solution is 1～6mol/l,
Preferably 2～4mol/l.
The preparation of titanium sulfate solution: weigh ti (so4)2It is subsequently adding deionized water to stir at room temperature～70 DEG C, prepare dense
Spend the titanium sulfate solution for 0.1～5mol/l.
The sio of the preferably described loaded optic catalyst of the present invention2The preparation method of aerogel composite is included after modification
The step being dried: constant pressure and dry process is carried out to modified wet gel, is warming up to 100 DEG C with 0.3～5 DEG C/min, protect
Warm 2h；It is warming up to 150 DEG C again, be incubated 2h, obtain the sio of loaded optic catalyst2Composite aerogel.
The present invention is by sio2Aeroge impregnated in photocatalyst sol or solution, sio2The adsorption photochemical catalysis agent of gel elder generation is molten
Glue or solution reach saturation, through water-bath ageing or solvent thermal reaction deposition, obtain photochemical catalyst/sio2Plural gel, then
Modified again, constant pressure and dry obtains composite aerogel, by this method (sio2Soak absorption, depositing photocatalytic agent) answering of preparing
Close aeroge and ensure that photochemical catalyst has certain deposition and sio2The integrity degree of gel network, is conducive to acquisition to have simultaneously
There are high porous volume and the photochemical catalyst/sio of high photochemical catalyst deposition2Composite aerogel.
It is a further object of the present invention to provide the sio of the loaded optic catalyst being obtained by said method2Composite aerogel material
Material
A kind of sio of loaded optic catalyst2Aerogel composite, described photochemical catalyst/sio2Composite aerogel is in mesoporous
Structure, bore dia 8～20nm, specific surface area is 200～700m2/ g, pore volume is 0.5～2.0cm3/g.
In technique scheme, preferably described photochemical catalyst is wo3-tio2、bi2o3-tio2、co-tio2、fe2o3-tio2、
v2o5-tio2、m-tio2、atio3, wherein, m is rare earth metal, a is alkaline-earth metal.
Further, it is preferable to described photochemical catalyst is wo3-tio2, and w/ti mol ratio is 1:100～10:100, further
, described w/ti mol ratio is 2:100～5:100.
The sio of the loaded optic catalyst that the present invention provides2Aerogel composite has absorption and photocatalytic degradation simultaneously
Pollutant function.
The sio of the loaded optic catalyst of present invention preparation2Composite aerogel has mesopore network structure and high pore volume,
There is excellent absorption property.Adsorb and deposit ageing and then the polynary photocatalysis of load of surface modification drying preparation by soak
The sio of agent2Composite aerogel can obtain higher photochemical catalyst deposition and suitable sharp titanium under suitable process conditions simultaneously
Ore deposit tio2Crystalline phase and high porous volume, high-specific surface area and larger aperture feature.Therefore, under sunshine, can have simultaneously
Excellent absorption property and good photocatalysis performance, absorption/photocatalysis synergy is simultaneously mutually promoted, and can effectively remove water
With the noxious pollutant in air and surrounding environment, there is in terms of wastewater treatment, water purification and air cleaning wide answering
With prospect and market prospects.And, the present invention prepares the sio of loaded optic catalyst using constant pressure and dry technology2Composite aerogel,
This preparation method does not need that supercritical drying, raw material and process costs are low, and the production cycle is shorter, can improve the product of aeroge
Amount, facilitates implementation scale industrial production.
Brief description
The adsorption/desorption isotherms of Fig. 1 embodiment 1～10；A, water-bath deposits embodiment 1～6；B, solvent heat deposition is implemented
Example 7～10；
The pore size distribution curve of Fig. 2 embodiment 1～10；A, water-bath deposits embodiment 1～6；B, solvent heat deposition embodiment 7
～10.
Sample corresponding to Fig. 3 embodiment 1～10 adsorption curve to rhodamine b after 750 DEG C of heat treatment 2h；A, water-bath
Deposition embodiment 1～6；B, solvent heat deposition embodiment 7～10.
In illumination after sample adsorption rhodamine b after 750 DEG C of heat treatment 2h for the sample corresponding to Fig. 4 embodiment 7～10
Under photocatalytic degradation rhodamine b comparison diagram；A, embodiment 7；B, embodiment 8；C, embodiment 9；D, embodiment 10.
After sample corresponding to Fig. 5 embodiment 1～6 absorption rhodamine b after 750 DEG C of heat treatment 2h, light under light illumination is urged
Change degraded rhodamine b comparison diagram；A, embodiment 6；B, embodiment 5；C, embodiment 4；D, embodiment 3；E, embodiment 2；F, implements
Example 1.
The sem photo of sample corresponding to Fig. 6 embodiment 1～6；A, embodiment 1；B, embodiment 2；C, embodiment 3；D, implements
Example 4；E, embodiment 5；F, embodiment 6.
The sem photo of sample corresponding to Fig. 7 embodiment 7～10；A, embodiment 7；B, embodiment 8；C, embodiment 9；D, real
Apply example 10.
Specific embodiment
Following non-limiting examples can make those of ordinary skill in the art that the present invention is more fully understood, but not with
Any mode limits the present invention.
Test method described in following embodiments, if no special instructions, is conventional method；Described reagent and material, such as
No specified otherwise, all commercially obtains.
One of specific embodiment, wo3-tio2/sio2The preparation method of plural gel:
1. prepare ticl respectively4The aqueous solution, titanium sulfate, silicic acid and tungstic acid.
The preparation of silicic acid: by modulus be 3.0～3.5 industrial waterglass by vWaterglass: vWater=1:2～1:12 deionized water
Dilution, preferably vWaterglass: vWater=1:4～1:8, is then passed through styrene cationic ion-exchange resin and carries out ion exchange, obtain ph=2
～3 silicic acid.
The preparation of wolframic acid: compound concentration is the na of 0.1～1.0mol/l first2wo4Solution, preferably prepares 0.5mol/l's
na2wo4Solution, is then passed through styrene cationic ion-exchange resin and carries out the tungstic acid that ion exchange obtains ph=1.5～3.
ticl4The preparation of solution: by a certain amount of ticl4Slowly be added drop-wise on ice cube, ice melting after start stir, treat
ticl4It is stirred for 30min so as to being sufficiently mixed and cooling down, compound concentration is the ticl of 3mol/l after all adding4Solution.
The preparation of titanium sulfate solution: weigh a certain amount of ti (so4)2It is subsequently adding deionized water to stir at room temperature～70 DEG C
Mix, compound concentration is the titanium sulfate solution of 0.1～5mol/l.
2. prepare sio2Colloidal sol and gel.
Take silicic acid and adjust ph value between 12～14, then using watery hydrochloric acid with concentrated ammonia liquor strong alkali solutions such as (or) naoh
Ph is adjusted to be static placement between 7～8.Silicic acid forms gel within 5min, and has some strength, disclosure satisfy that later
Absorption, ageing, surface modification etc. are processed.
3. prepare wo3-tio2Colloidal sol, a certain amount of wolframic acid is added to ticl4(1～5mol/l, preferably 3mol/l) solution
In, white precipitate occurs, precipitation disappears after stirring after a while, form faint yellow colloidal sol, be subsequently further continued for stirring
30min；Or a certain amount of wolframic acid is added to ti (so4)2In solution (0.1～2.5mol/l), stir 30min, form wo3-
tio2Colloidal sol.To wo3-tio2Add in colloidal sol with sol volume than the concentrated ammonia liquor for 0～0.5, promote hydrolysis.
4. prepare wo3-tio2/sio2Plural gel: by sio2Gel is cut into small pieces, and adds wo3-tio2Complex sol is carried out
Soak absorption, just started due to sio soaking2Gel piece density is less than colloidal sol density, and blob of viscose all floats over colloidal sol top, waits to soak
After the completion of bubble absorption, all blob of viscoses sink to colloidal sol bottom.
5. solvent heat deposition: the wo that absorption obtains will be soaked3-tio2/sio2Plural gel takes out, and puts in autoclave,
And add absolute ethyl alcohol more than blob of viscose volume, the addition of absolute ethyl alcohol so that submergence gel piece can be crossed for minimum addition,
Then solvent heat deposition 10min～24h between 100～200 DEG C, blob of viscose is changed into white.
6. modified: blob of viscose is taken out from autoclave, puts in beaker, be then added thereto to HMDO or
Alkanes organic solvent and being modified with the trim,ethylchlorosilane that blob of viscose volume ratio is 0.05～1.0, modification in 24h completes.Its
In, the preferred n-hexane of alkanes organic solvent or heptane, the addition of HMDO or alkanes organic solvent is soaking
Gel piece was not had to be minimum addition.Addition due to ethanol in solvent heat deposition process allows modifying agent to be introduced into glue
Inside block, and there is alcoholysis in the presence of ethanol so that occurring the surface of methyl substitution reaction to be greatly improved, thus
So that modified speed is greatly improved.
7. constant pressure and dry process is carried out to modified wet gel, slow heat up (0.3～5 DEG C/min), to 100 DEG C, is incubated
2h；It is warming up to 150 DEG C again, be incubated 2h, obtain photochemical catalyst/sio2Composite aerogel.
Two, wo of specific embodiment3-tio2/sio2The preparation method of plural gel:
One of other steps and specific embodiment are identical, and 5. step replaces with " 5. water-bath deposition ageing: gained light is urged
Agent/sio2Plural gel is placed in alkyl organic solvent, ageing deposition under 50～100 DEG C of water-baths, until photochemical catalyst/
sio2Plural gel is changed into white from Transparent color；Then, continue to be aged 0～24h under the water-bath of room temperature～95 DEG C；
In example below, to prepared photochemical catalyst/sio2The performance measurement of composite aerogel is as follows:
(1) using with n2Ssa-4200 type bet aperture for carrier gas and specific surface area analysis instrument measure photochemical catalyst/sio2
The specific surface area of composite aerogel, pore-size distribution, pore volume and average pore size.
(2) adopt jeol jsm-6460lv type SEM to prepared mesoporous wo3-tio2/sio2Compound
Aerogel material carries out Analysis of Surface Topography.
(4) pass through the sio that absorption/degraded rhodamine b solution evaluates loaded optic catalyst2Absorption/the light of composite aerogel
Catalytic performance.Because of the sio through the loaded optic catalyst prepared by 150 DEG C of dryings2Composite aerogel presents stronger hydrophobicity,
In order to test the sio of prepared loaded optic catalyst2Aerogel composite to the absorption of rhodamine b dyestuff in the aqueous solution/
Photocatalytic Degradation, by prepared photochemical catalyst/sio2Composite aerogel carries out being heat-treated 2h at 750 DEG C, so that its
It is changed into hydrophily.Absorption/light-catalysed test process is as follows: by the loaded optic catalyst through 750 DEG C of heat treatments for the 0.1g
sio2It is 2 × 10 that composite aerogel puts into 100ml concentration-5In the rhodamine b solution of mol/l, darkroom is adsorbed 1h；Then
Mixed liquor carries out suction filtration, takes out filter paper, and now its surface is paved with the full composite aerogel closing of absorption, and adsorption saturation is compound
Aeroge is placed on illumination 3h under Metal halogen lamp together with filter paper.In absorption phase, extract mixed liquor every 10min, in 10000r/min
Lower centrifugation 3min, measures extinction at 560nm for the supernatant rhodamine b solution with uv-751gd ultraviolet/visible spectrophotometer
Degree, and the concentration of now rhodamine b solution is obtained by absorbance-concentration straight line.In photostage, every 30min to compound
Aeroge carries out sampling of taking pictures, by the color change of composite aerogel come the photocatalysis effect of analysis of material.
Embodiment 1
1. silicic acid, ticl are prepared respectively4The aqueous solution and tungstic acid.
Prepare silicic acid: after taking 10ml waterglass to mix with 60ml deionized water, through ion exchange obtain ph=2～
3 silicic acid.
Prepare ticl4Solution: be slowly added dropwise 250ml ticl in 500g ice4Solution, then stirs 30min, is loaded into
In Brown Glass Brown glass bottles and jars only, its concentration is 3mol/l.
Prepare wolframic acid: take 3.3g na2wo4It is added thereto to 20ml deionized water, then by 20ml na2wo4Solution is carried out
Ion exchange, obtains the wolframic acid for 1.5～3 for the ph value.
2. prepare sio2Colloidal sol and gel.
Take 50ml silicic acid and with concentrated ammonia liquor adjust ph value be 13 about, then with concentration be 2.5mol/l watery hydrochloric acid adjust ph
Between 7～8, static a period of time, silicic acid forms gel within 5min and has some strength.
3. prepare wo3-tio2Colloidal sol, the wolframic acid of 7.2ml is added to the ticl that 60ml concentration is 3mol/l4In solution, go out
Existing white precipitate, after stirring after a while, precipitation disappears, and forms faint yellow colloidal sol, is subsequently further continued for stirring 30min；Then
It is added thereto to 30ml concentrated ammonia liquor, promote hydrolysis.
4. prepare wo3-tio2/sio2Plural gel: by sio2Gel is cut into small pieces, and adds wo3-tio2Complex sol is carried out
Soak absorption, just started due to sio soaking2Gel piece density is less than colloidal sol density, and blob of viscose all floats over colloidal sol top, waits to soak
After the completion of bubble absorption, all blob of viscoses sink to colloidal sol bottom.
5. water-bath deposition ageing: the wo that absorption is obtained3-tio2/sio2Plural gel takes out, and adds 100ml hexamethyl
Disiloxane, is aged 1h under 80 DEG C of water-baths, blob of viscose gradually becomes white by Transparent color；Then proceed to ageing under 50 DEG C of water-baths
24h.
6. modified: to add 5ml trim,ethylchlorosilane to be modified in the plural gel block liquid after ageing, every 24h suctions out
The modified water separating out, and the trim,ethylchlorosilane into 5～10ml is added according to water yield, till not having elutriation to go out, modified
Time is 3d.
7. constant pressure and dry process is carried out to modified wet gel, slowly heat up 5 DEG C/min to 100 DEG C, be incubated 2h；Rise again
Temperature, to 150 DEG C, is incubated 2h, obtains wo3-tio2/sio2Composite aerogel.
After measured, the wo of the method preparation3-tio2/sio2Its specific surface area of composite aerogel is 312.5m2/ g, pore volume
For 0.69cm3/ g, average pore diameter is 8.84nm.Under darkroom, absorption 1h is 59.12% to rhodamine b adsorption rate, illumination 3h
Interior to rhodamine b degradation rate such as Fig. 5-f.
Embodiment 2
Step 1., 2. with embodiment 1 step 1., 2..
3. prepare wo3-tio2Colloidal sol, the wolframic acid of 14.4ml is added to the ticl that 60ml concentration is 3mol/l4In solution,
White precipitate occurs, precipitation disappears after stirring after a while, form faint yellow colloidal sol, be subsequently further continued for stirring 30min；So
After be added thereto to 30ml concentrated ammonia liquor, promote hydrolysis.
Step 4., 5., 6., 7. with embodiment 1 step 4., 5., 6., 7..
After measured, the wo of the method preparation3-tio2/sio2Its specific surface area of composite aerogel is 280.9m2/ g, pore volume
For 0.65cm3/ g, average pore diameter is 9.38nm.Under darkroom, absorption 1h is 56.52% to rhodamine b adsorption rate, illumination 3h
Interior to rhodamine b degradation rate such as Fig. 5-e.
Embodiment 3
Step 1., 2. with embodiment 1 step 1., 2..
3. prepare wo3-tio2Colloidal sol, the wolframic acid of 14.4ml is added to the ticl that 60ml concentration is 3mol/l4In solution,
White precipitate occurs, precipitation disappears after stirring after a while, form faint yellow colloidal sol, be subsequently further continued for stirring 30min；So
After be added thereto to 25ml concentrated ammonia liquor, promote hydrolysis.
Step 4., 5., 6., 7. with embodiment 1 step 4., 5., 6., 7..
After measured, the wo of the method preparation3-tio2/sio2Its specific surface area of composite aerogel is 279.6m2/ g, pore volume
For 1.18cm3/ g, average pore diameter is 16.84nm.Under darkroom, absorption 1h is 59.18% to rhodamine b adsorption rate, illumination 3h
Interior to rhodamine b degradation rate such as Fig. 5-d.
Embodiment 4
Step 1., 2. with embodiment 1 step 1., 2..
3. prepare wo3-tio2Colloidal sol, the wolframic acid of 14.4ml is added to the ticl that 60ml concentration is 3mol/l4In solution,
White precipitate occurs, precipitation disappears after stirring after a while, form faint yellow colloidal sol, be subsequently further continued for stirring 30min；So
After be added thereto to 20ml concentrated ammonia liquor, promote hydrolysis.
Step 4., 5., 6., 7. with embodiment 1 step 4., 5., 6., 7..
After measured, the wo of the method preparation3-tio2/sio2Its specific surface area of composite aerogel is 228.1m2/ g, pore volume
For 0.74cm3/ g, average pore diameter is 13.00nm.Under darkroom, absorption 1h is 59.18% to rhodamine b adsorption rate, illumination 3h
Interior to rhodamine b degradation rate such as Fig. 5-c.
Embodiment 5
Step 1., 2. with embodiment 1 step 1., 2..
3. prepare wo3-tio2Colloidal sol, the wolframic acid of 14.4ml is added to the ticl that 60ml concentration is 3mol/l4In solution,
White precipitate occurs, precipitation disappears after stirring after a while, form faint yellow colloidal sol, be subsequently further continued for stirring 30min；So
After be added thereto to 10ml concentrated ammonia liquor, promote hydrolysis.
Step 4., 5., 6., 7. with embodiment 1 step 4., 5., 6., 7..
After measured, the wo of the method preparation3-tio2/sio2Its specific surface area of composite aerogel is 314.71m2/ g, pore volume
Amass as 1.33cm3/ g, average pore diameter is 16.84nm.Under darkroom, absorption 1h is 60.85% to rhodamine b adsorption rate, illumination
To rhodamine b degradation rate such as Fig. 5-b in 3h.
Embodiment 6
Step 1., 2. with embodiment 1 step 1., 2..
3. prepare wo3-tio2Colloidal sol, the wolframic acid of 14.4ml is added to the ticl that 60ml concentration is 3mol/l4In solution,
White precipitate occurs, precipitation disappears after stirring after a while, form faint yellow colloidal sol, be subsequently further continued for stirring 30min；
Step 4., 5., 6., 7. with embodiment 1 step 4., 5., 6., 7..
After measured, the wo of the method preparation3-tio2/sio2Its specific surface area of composite aerogel is 458.2m2/ g, pore volume
For 1.22cm3/ g, average pore diameter is 10.68nm.Under darkroom, absorption 1h is 77.18% to rhodamine b adsorption rate, illumination 3h
Interior to rhodamine b degradation rate such as Fig. 5-a.
Embodiment 7
1. silicic acid, ti (so are prepared respectively4)2The aqueous solution and tungstic acid.
Prepare silicic acid: after taking 10ml waterglass to mix with 60ml deionized water, through ion exchange obtain ph=2～
3 silicic acid.
Prepare ti (so4)2Solution: weigh ti (so of certain mass4)2, it is added in deionized water, stirs, be made into
Concentration is ti (so of 0.5mol/l4)2Solution.
Prepare wolframic acid: take 3.3g na2wo4It is added thereto to 20ml deionized water, then by 20ml na2wo4Solution is carried out
Ion exchange, obtains the wolframic acid for 1.5～3 for the ph value.
Step is 2. with step in embodiment 1 2..
3. prepare wo3-tio2Colloidal sol, the wolframic acid of 2ml is added to ti (so that 50ml concentration is 0.5mol/l4)2Solution stirs
Mix 30min, form wo3-tio2Colloidal sol.
4. prepare wo3-tio2/sio2Plural gel: by sio2Gel is cut into small pieces, and adds wo3-tio2Complex sol is carried out
Soak absorption, just started due to sio soaking2Gel piece density is less than colloidal sol density, and blob of viscose all floats over colloidal sol top, waits to soak
After the completion of bubble absorption, all blob of viscoses sink to colloidal sol bottom.
5. solvent heat deposition: the wo that absorption is obtained3-tio2/sio2Plural gel takes out to be put in 200ml autoclave,
And add the absolute ethyl alcohol of 100ml volume, the addition of absolute ethyl alcohol so that submergence gel piece can be crossed for minimum addition, then
Solvent heat deposition 30min at 150 DEG C, blob of viscose is changed into white from transparent.
6. modified: blob of viscose to be taken out from autoclave, puts in beaker, be then added thereto to 100ml hexamethyl two silicon
Oxygen alkane, the trim,ethylchlorosilane of 5ml is modified.Modification completes in 24h.
7. constant pressure and dry process is carried out to modified wet gel, slow heat up (0.3～5 DEG C/min), to 100 DEG C, is incubated
2h；It is warming up to 150 DEG C again, be incubated 2h, obtain sio2-wo3-tio2Composite aerogel.
After measured, the wo of the method preparation3-tio2/sio2Its specific surface area of composite aerogel is 542m2/ g, pore volume is
1.39cm3/ g, average pore diameter is 10.16nm.Under darkroom, absorption 1h is 70.69% to rhodamine b adsorption rate, in illumination 3h
To rhodamine b degradation rate such as Fig. 4-a.
Embodiment 8
1. silicic acid, ti (so are prepared respectively4)2The aqueous solution and tungstic acid.
Prepare silicic acid: after taking 10ml waterglass to mix with 60ml deionized water, through ion exchange obtain ph=2～
3 silicic acid.
Prepare ti (so4)2Solution: weigh ti (so of certain mass4)2, it is added in deionized water, stirs, be made into
Concentration is ti (so of 1.0mol/l4)2Solution.
Prepare wolframic acid: take 3.3g na2wo4It is added thereto to 20ml deionized water, then by 20ml na2wo4Solution is carried out
Ion exchange, obtains the wolframic acid for 1.5～3 for the ph value.
Step is 2. with step in embodiment 1 2..
3. prepare wo3-tio2Colloidal sol, the wolframic acid of 4ml is added to ti (so that 50ml concentration is 1.0mol/l4)2Solution stirs
Mix 30min, form wo3-tio2Colloidal sol.
Step 4., 5., 6., 7. with embodiment 7 step 4., 5., 6., 7..
After measured, the wo of the method preparation3-tio2/sio2Its specific surface area of composite aerogel is 570m2/ g, pore volume is
1.29cm3/ g, average pore diameter is 9.20nm.Under darkroom, absorption 1h is 70.69% to rhodamine b adsorption rate, in illumination 3h
To rhodamine b degradation rate such as Fig. 4-b.
Embodiment 9
1. silicic acid, ti (so are prepared respectively4)2The aqueous solution and tungstic acid.
Prepare silicic acid: after taking 10ml waterglass to mix with 60ml deionized water, through ion exchange obtain ph=2～
3 silicic acid.
Prepare ti (so4)2Solution: weigh ti (so of certain mass4)2, it is added in deionized water, stirs, be made into
Concentration is ti (so of 1.5mol/l4)2Solution.
Prepare wolframic acid: take 3.3g na2wo4It is added thereto to 20ml deionized water, then by 20ml na2wo4Solution is carried out
Ion exchange, obtains the wolframic acid for 1.5～3 for the ph value.
Step is 2. with step in embodiment 1 2..
3. prepare wo3-tio2Colloidal sol, the wolframic acid of 6ml is added to ti (so that 50ml concentration is 1.5mol/l4)2Solution stirs
Mix 30min, form wo3-tio2Colloidal sol.
Step 4., 5., 6., 7. with embodiment 7 step 4., 5., 6., 7..
After measured, the wo of the method preparation3-tio2/sio2Its specific surface area of composite aerogel is 384m2/ g, pore volume is
1.35cm3/ g, average pore diameter is 14.02nm.Under darkroom, absorption 1h is 87.05% to rhodamine b adsorption rate, in illumination 3h
To rhodamine b degradation rate such as Fig. 4-c.
Embodiment 10
1. silicic acid, ti (so are prepared respectively4)2The aqueous solution and tungstic acid.
Prepare silicic acid: after taking 10ml waterglass to mix with 60ml deionized water, through ion exchange obtain ph=2～
3 silicic acid.
Prepare ti (so4)2Solution: weigh ti (so of certain mass4)2, it is added in deionized water, stirs, be made into
Concentration is ti (so of 2.0mol/l4)2Solution.
Prepare wolframic acid: take 3.3g na2wo4It is added thereto to 20ml deionized water, then by 20ml na2wo4Solution is carried out
Ion exchange, obtains the wolframic acid for 1.5～3 for the ph value.
Step is 2. with step in embodiment 1 2..
3. prepare wo3-tio2Colloidal sol, the wolframic acid of 8ml is added to ti (so that 50ml concentration is 2mol/l4)2Solution stirs
30min, forms wo3-tio2Colloidal sol.
Step 4., 5., 6., 7. with embodiment 7 step 4., 5., 6., 7..
After measured, the wo of the method preparation3-tio2/sio2Its specific surface area of composite aerogel is 267m2/ g, pore volume is
1.05cm3/ g, average pore diameter is 15.78nm.Under darkroom, absorption 1h is 83.65% to rhodamine b adsorption rate, in illumination 3h
To rhodamine b degradation rate such as Fig. 4-d.
Embodiment 11
1. prepare ti (so respectively4)2And fecl3Solution.
12g ti (so4)2It is added in 50ml deionization, obtain ti (so that 50ml concentration is 1mol/l4)2Solution.
Weigh a certain amount of fecl3, it is added in a certain amount of deionized water, be made into the fecl that concentration is 0.5mol/l3Molten
Liquid.
2. prepare fe2o3-tio2Precursor liquid, 5ml concentration is the fecl of 0.5mol/l3Solution is added to 50ml concentration
Ti (so of 1mol/l4)2In solution, agitated uniformly after, obtain fe2o3-tio2Precursor liquid.
3. silicic acid and sio are prepared2Gel: after taking 10ml waterglass to mix with 60ml deionized water, hand over through ion
Get the silicic acid of ph=2～3 in return, adjust so as to gelling between ph to 6～7, after gelling, room temperature is aged 2h.
④fe2o3-tio2/sio2Prepared by plural gel: the sio that 3. step is obtained2Gel is added to what 2. step obtained
fe2o3-tio2In colloidal sol, under room temperature, soak absorption 24h.
5. solvent heat deposition: by the fe of step 4. middle acquisition2o3-tio2/sio2It is poly- that plural gel blob of viscose is added to liner
In the 200ml hydrothermal reaction kettle of tetrafluoroethene (tpfe), add 100ml ethanol, solvent thermal reaction 3h at 120 DEG C, blob of viscose is by saturating
Bright become white.
6. surface modification: add the trim,ethylchlorosilane of 100ml n-hexane and 20ml in the blob of viscose after solvent thermal reaction
(tmcs) carry out surface modification, modification completes in 24h.
Step is 7. with embodiment 1 step 7..
After measured, the fe of the method preparation2o3-tio2/sio2Its specific surface area of composite aerogel is 306.2m2/ g, pore volume
Amass as 0.97cm3/ g, average pore diameter is 11.7nm.
Embodiment 12
1. prepare tio respectively2Colloidal sol and lanthanum acetate solution
tio2Colloidal sol is prepared: the butyl titanate of measured amounts, is added in 40ml ethanol solution, adds 10ml second
Acid, magnetic agitation 2.5h, compound concentration is the tio of 1mol/l2Colloidal sol.
Lanthanum acetate solution is prepared: weighs a certain amount of lanthanum acetate (la (ac)3·nh2O), be added to by 20ml acetic acid and
In the acetic acid aqueous solution that 10ml water is made into, stir, compound concentration is the lanthanum acetate solution of 0.1mol/l.
2. prepare la2o3-tio2Colloidal sol, the lanthanum acetate solution that 5ml concentration is 0.1mol/l is added to 50ml concentration and is
The tio of 1mol/l2In colloidal sol, agitated uniformly after, obtain la2o3-tio2Complex sol.
3. silicic acid and sio are prepared2Gel: after taking 10ml waterglass to mix with 60ml deionized water, hand over through ion
Get the silicic acid of ph=2～3 in return, adjust so as to gelling between ph to 6～7, after gelling, room temperature is aged 2h.
④la2o3-tio2/sio2Prepared by plural gel: the sio that 3. step is obtained2Gel is added to step 2. middle acquisition
La2o3-tio2In colloidal sol, under room temperature, soak absorption 24h.
5. solvent heat deposition: by the la of step 4. middle acquisition2o3-tio2/sio2It is poly- that plural gel blob of viscose is added to liner
In the 200ml hydrothermal reaction kettle of tetrafluoroethene (tpfe), add 100ml ethanol, solvent thermal reaction 3h at 120 DEG C, blob of viscose is by saturating
Bright become white.
Step 6., 7. with embodiment 1 step 6., 7..
After measured, the la-tio of the method preparation2/sio2Its specific surface area of composite aerogel is 286.6m2/ g, pore volume
For 0.93cm3/ g, average pore diameter is 10.8nm.
Comparative example 1
1. silicic acid, ticl are prepared respectively4The aqueous solution and tungstic acid.
Prepare silicic acid: after taking 10ml waterglass to mix with 60ml deionized water, through ion exchange obtain ph=2～
3 silicic acid.
Prepare ticl4Solution: be slowly added dropwise 250ml ticl in 500g ice4Solution, then stirs 30min, is loaded into
In Brown Glass Brown glass bottles and jars only, its concentration is 3mol/l.
Prepare wolframic acid: take 3.3g na2wo4It is added thereto to 20ml deionized water, then by 20ml na2wo4Solution is carried out
Ion exchange, obtains the wolframic acid for 1.5～3 for the ph value.
2. prepare sio2Sol-gel and preparation sio2Aeroge sample.
Take the silicic acid of 50ml, adjust ph value for 6 so as to being gelled is sio with 1.0mnaoh2Gel, then use ethanol/just oneself
Alkane/trim,ethylchlorosilane is to sio2Gel carries out solvent replacement-surface modification treatment, often carries out after the completion of modification at 150 DEG C
Press dry dry, obtain sio2Aeroge, concrete modifying process and dry run participate in patent cn100574863c (tio2-sio2Compound
Aeroge and preparation method thereof).
3. prepare wo3-tio2Colloidal sol, the wolframic acid of 7.2ml is added to the ticl that 60ml concentration is 3mol/l4In solution, go out
Existing white precipitate, after stirring after a while, precipitation disappears, and forms faint yellow colloidal sol, is subsequently further continued for stirring 30min；Then
It is added thereto to 30ml concentrated ammonia liquor, promote hydrolysis.
4. prepare wo3-tio2/sio2Composite aerogel: by sio2Aeroge is heat-treated 2h so as to be changed at 550 DEG C
Hydrophily, is then added to wo3-tio2Carry out in complex sol soaking absorption, after the completion of waiting to soak absorption, all blob of viscoses sink to
Colloidal sol bottom.
5. soak the wo after absorption3-tio2/sio2Composite aerogel carries out constant pressure and dry process, and slowly heat up 5 DEG C/min
To 100 DEG C, it is incubated 2h；It is warming up to 150 DEG C again, be incubated 2h, obtain wo3-tio2/sio2Composite aerogel.
After measured, the wo of the method preparation3-tio2/sio2Its specific surface area of composite aerogel is 263.5m2/ g, pore volume
For 0.26cm3/ g, average pore diameter is 6.84nm.Under darkroom, absorption 1h is 26.12% to rhodamine b adsorption rate.
The specific surface area of sample, permeability parameter and absorption/photocatalysis performance table corresponding to table 1 embodiment 1～embodiment 10
Claims (5)
1. a kind of sio of loaded optic catalyst2The preparation method of aerogel composite it is characterised in that: include subordinate's technique step
Rapid:
1. photochemical catalyst/sio2The step of plural gel preparation:
By sio2Immersing hydrogels, in photocatalyst sol or solution, obtain photochemical catalyst/sio2Plural gel；Gained light is urged
Agent/sio2Plural gel carries out depositing ripening using alkyl organic solvent,
Described alkyl organic solvent is HMDO, alcohols or alkanes solvent, wherein, described alcohols solvent be ethanol or
Isopropanol；Described alkanes solvent is hexane or heptane；Described photochemical catalyst is wo3-tio2、bi2o3-tio2、co-tio2、fe2o3-
tio2、v2o5-tio2、m-tio2, wherein, m is rare earth metal,
Described deposition ripening can be carried out one of as follows:
I-1. by gained photochemical catalyst/sio2Plural gel is placed in alkyl organic solvent, and it is heavy to be aged under 50～100 DEG C of water-baths
Long-pending, until photochemical catalyst/sio2Plural gel is changed into white from Transparent color；Then, continue to be aged 0 under the water-bath of room temperature～95 DEG C
～24h；
I-2. by gained photochemical catalyst/sio2Plural gel is placed in alkyl organic solvent, carries out solvent in 100～200 DEG C heat sink
Long-pending reaction, until photochemical catalyst/sio2Plural gel is changed into white from Transparent color；Then, continue under the water-bath of room temperature～95 DEG C
Ageing 0～24h；
2. the step being modified after deposition ageing:
Specifically can carry out one of as follows:
Ii-1. to the photochemical catalyst/sio after deposition ageing2In plural gel blob of viscose liquid add with blob of viscose volume ratio be 0.05～
1.0 trim,ethylchlorosilane is modified, and every 24h suctions out the water separating out；Suspended in modifying agent according to water yield and blob of viscose
Situation judges whether to continue to supplement trim,ethylchlorosilane, if the water volume that is less than in blob of viscose of water yield and blob of viscose do not float on completely and change
Property separate out the water surface on, then continue to add into the trim,ethylchlorosilane modification 24～72h being 0.05～1.0 with blob of viscose volume ratio,
Till not having elutriation to go out；
Ii-2. to the photochemical catalyst/sio after deposition ageing2HMDO or alkanes solvent is added in plural gel blob of viscose
With the mixed solution of trim,ethylchlorosilane, wherein, the addition of HMDO or alkanes solvent can be complete for blob of viscose
Being submerged in solution is minimum, and the additional proportion of trim,ethylchlorosilane is vtmcs: vBlob of viscose=0.05:1～1:1, soaks 24h
Suction out the modified water separating out afterwards；Judge whether to continue to supplement trimethyl according to the situation that water yield and blob of viscose suspend in modifying agent
Chlorosilane, if less than the water volume in blob of viscose and blob of viscose does not float on the water surface of modified precipitation water yield completely, continues to add
The trim,ethylchlorosilane being equivalent to 0.2～1 times of blob of viscose volume is modified, repeats above step till no longer having elutriation to go out；
3. the modified step being dried:
Constant pressure and dry process is carried out to modified wet gel, is warming up to 100 DEG C with 0.3～5 DEG C/min, be incubated 2h；Heat up again
To 150 DEG C, it is incubated 2h, obtains the sio of loaded optic catalyst2Composite aerogel.
2. method according to claim 1 it is characterised in that: by sio2Gel adds to photocatalyst sol or solution,
Until floating on the sio of photocatalyst sol or solution surface2Gel all submerges below photocatalyst sol or liquid level of solution, obtains
To photochemical catalyst/sio2Plural gel.
3. method according to claim 1 it is characterised in that: described photocatalyst sol or solution are made as follows
Standby: from the presoma generating corresponding catalyst can be hydrolyzed accordingly, to be dissolved in ethanol, water or ethanol water, obtain corresponding
Photocatalyst sol or solution.
4. by the sio of the loaded optic catalyst of claims 1 to 3 any one methods described preparation2Aerogel composite, it is special
Levy and be: the sio of described loaded optic catalyst2Composite aerogel is in meso-hole structure, bore dia 8～20nm, and specific surface area is 200
～700m2/ g, pore volume is 0.5～2.0cm3/g.
5. material according to claim 4 it is characterised in that: described photochemical catalyst be wo3-tio2、bi2o3-tio2、co-
tio2、fe2o3-tio2、v2o5-tio2、m-tio2,
Wherein, m is rare earth metal.
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| CN108246319A (en) * | 2016-12-28 | 2018-07-06 | 天津摩根坤德高新科技发展有限公司 | A kind of preparation method of photocatalytic aerogel material |
| CN109987634A (en) * | 2017-12-30 | 2019-07-09 | 卢斌 | A kind of WO3The preparation method of aeroge |
| CN109894074A (en) * | 2018-11-15 | 2019-06-18 | 齐鲁工业大学 | A kind of ZnO/SiO2Aerogel composite and preparation method thereof |
| CN110170319A (en) * | 2019-05-21 | 2019-08-27 | 华东理工大学 | Bigger serface SiO2The preparation of the tungsten oxide of substrate/titanium catalysis material |
| CN110605121A (en) * | 2019-09-25 | 2019-12-24 | 滨州学院 | Preparation method of bismuth oxide/ferroferric oxide/graphene three-component composite material |
| CN111072036B (en) * | 2019-12-30 | 2021-07-13 | 石家庄铁道大学 | Preparation method of silicon dioxide aerogel loaded with zinc sulfide |
| CN111589382B (en) * | 2020-05-14 | 2022-05-10 | 大连工业大学 | Ptn-MxWO3/SiO2Composite aerogel and preparation method thereof |
| CN111589383B (en) * | 2020-05-14 | 2022-05-10 | 大连工业大学 | TiO 22-MxWO3-SiO2Composite aerogel and preparation method thereof |
| CN113694965B (en) * | 2021-09-03 | 2022-08-05 | 河海大学 | Flower-shaped composite photocatalytic material with stem and preparation method and application thereof |
| CN115364904A (en) * | 2022-07-07 | 2022-11-22 | 福建省蓝光节能科技有限公司 | Photocatalyst for volatile organic pollutants and use method thereof |
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