CN106563501A - Preparing method for polysiloxane sponge loaded with titanium dioxide photocatalyst - Google Patents
Preparing method for polysiloxane sponge loaded with titanium dioxide photocatalyst Download PDFInfo
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- CN106563501A CN106563501A CN201610957047.6A CN201610957047A CN106563501A CN 106563501 A CN106563501 A CN 106563501A CN 201610957047 A CN201610957047 A CN 201610957047A CN 106563501 A CN106563501 A CN 106563501A
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- sponge
- titanium dioxide
- polysiloxanes
- preparation
- dioxide photocatalyst
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 48
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 47
- -1 polysiloxane Polymers 0.000 title claims abstract description 44
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 229910000077 silane Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 241000209051 Saccharum Species 0.000 claims description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 239000003344 environmental pollutant Substances 0.000 abstract description 8
- 231100000719 pollutant Toxicity 0.000 abstract description 8
- 229920002379 silicone rubber Polymers 0.000 abstract description 5
- 238000006459 hydrosilylation reaction Methods 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 11
- 238000007146 photocatalysis Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 229930006000 Sucrose Natural products 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
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- Hydrology & Water Resources (AREA)
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Abstract
The invention discloses a preparing method for polysiloxane sponge loaded with a titanium dioxide photocatalyst. Bi-component addition-cured silicon rubber sold in the market serves as a carrier to load anatase nano TiO2, and after being modified, the TiO2 sold on the market is evenly mixed with the silicon rubber; after a physical hole making agent is added, the hydrosilylation crosslinking reaction is conducted; then, the physical hole making agent is removed, polysiloxane/TiO2 composite sponge is obtained, and accordingly the polysiloxane sponge is loaded with the nano TiO2. The specific surface area of the prepared sponge is greatly increased, the sponge has good adsorption performance for oily pollutants, the oily pollutants are enriched, accordingly, more TiO2 makes contact with the pollutants, the synergistic effect is generated, and the photocatalytic performance is improved. The load has the beneficial effects that the specific surface area is large, the adsorption performance is good, the photocatalytic performance is good, and practical application and recovery are convenient.
Description
Technical field
The present invention relates to titanium dioxide optical catalyst technical field, and in particular to a kind of loaded titanium dioxide photocatalyst
The preparation method of polysiloxanes sponge.
Background technology
As environmental pollution increasingly obtains the attention of people, people constantly find power consumption less, and process more simply has
The mode of effect is solving environmental pollution.Wherein anatase titanium dioxide TiO2Utilize the active group that the ultraviolet in sunlight is produced can with it
This chemical bond is less than to cut off many bond energys, so as to realizing consuming energy less, processing simple and effective pollution process.
Due to the usual TiO for preparing2Need to be through high-temperature calcination, it is serious to thus result in particle aggregation, and it is not born
Carry, then recycling is difficult, cause in water secondary pollution so as to be allowed to residue in.In conventional organic carrier, due to C-C key keys
Can (346kJmol-1) it is less than TiO2(OOH is 431kJmol to the energy of the active group of generation-1, OH is
402.7kJ·mol-1), thus the heavy damage for matrix can be caused.And polysiloxane backbone is Si-O keys, bond energy
(460kJ·mol-1) it is higher than TiO2The energy of the active group of generation, it is aging not result in matrix, thus is a kind of preferably to carry
Body.
Ding Xiaofeng [CN101724342A；CN101962514A；J Mater Chem,2011,21:6161～6164] with poly-
Silicone cross-linked film forming is loading commercial powder TiO2, a series of automatically cleaning with super-hydrophobic or super parents' function is obtained and gathers
Fluorosilicone/TiO2Nano-composite coating.Zhou Shuxue [Progress in Organic Coatings, 2013,76:563～
570] etc. by fluorinated polysiloxane and anatase titanium dioxide powder TiO2Carry out composite, obtained it is a kind of have good mechanical strength and
The automatically cleaning composite membrane of durability.But due to powder TiO2Reunite more serious, thus affect the performance of its performance, thus result in
Its powder TiO2Large usage quantity just can use to obtain self-cleaning effect.
Jiang Mei [macromolecule journal, 2008,6:594～599], Wang Fang [Journal of Inorganic Materials, 2010,25 (1):37～
40], Peng Ruimai [coatings industry, 2010,40 (8):36～38] it is then etc. come real by the way of collosol and gel and curing of coating
Existing TiO2Uniform with polysiloxanes mixes, but this TiO2For unformed shape, photocatalysis performance is poor.
Application publication number is CN103483607A (a kind of preparation method of titanium dioxide/polysiloxane photocatalytic composite film)
Patent to disclose a kind of polysiloxanes by vinyl-terminated silicone fluid and containing hydrogen silicone oil hydrosilylation and titanium dioxide former
The method that position polymerization prepares photocatalysis composite membrane.TiO in photocatalysis composite membrane obtained by this method2It is for anatase titanium dioxide and more equal
It is even to be scattered in composite membrane, thus with preferable photocatalysis performance.But have more TiO2In film, thus fail fully
Due effect is given play to.
Approach described above is conceived to and prepares composite membrane to load TiO2, but this method can serious restricted T iO2Light urge
Change performance, because made nano-TiO2Size is 10-100nm, and film thickness is then 100-300 μm, has many TiO2It is detained
Due effect cannot have been given play in film.And Xu Huarui [CN 101856609A] is with titanium sponge loading TiO2It is then with sponge
The titanium of shape is carrier and titanium source, is conceived to three dimensions to expand specific surface area, so that more TiO2Light can have been given play to
Catalytic performance.But this method operation is more and more expensive with material, is not suitable for being applied to sewage disposal.And inorganic carrier is to organic
Pollutant do not have good absorbability, it is impossible to produce synergism with photocatalyst.
The content of the invention
The invention provides a kind of preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst, by poly- silica
Alkane makes sponge, and in three-dimensional sponge form carried titanium dioxide is carried out, and sponge specific surface area is obtained and greatly increases, to oiliness pollutant
With preferably absorption and accumulation ability, so that more TiO2Contact with pollutant, produce cooperative effect, improve photocatalysis
Performance.
A kind of preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst, comprises the following steps：
1) titanium dioxide is scattered in ethanol, carries out ultrasonic disperse, be subsequently adding silane coupler and be modified, afterwards
Jing is centrifuged, is dried to obtain modifying titanium dioxide；
2) by basic components, linked, toluene, modifying titanium dioxide mix homogeneously, in adding mould, then again in mould
Add physics perforating agent, mix homogeneously to be placed in 6-24h molding in 50-120 DEG C of environment in tool, obtain equipped with molding composite sponge
Mould；
3) mould that will be equipped with molding composite sponge is placed in water dissolving removal physics perforating agent, obtains carried titanium dioxide
The polysiloxanes sponge of photocatalyst.
It is following as the preferred technical solution of the present invention：
Step 1) in, the condition of described ultrasonic disperse：300～500W of ultrasonic power, 5～20min of ultrasonic time, enters one
Step is preferred, ultrasonic power 400W, ultrasonic time 10min.
Described silane coupler is octyl group trimethoxy silane (OTMS)；
Described modified condition is：Modification temperature is 40～60 DEG C, 5～7h of modification time, and further preferably, be modified temperature
Spend for 50 DEG C, modification time 6h；
Described silane coupler is 0.3～1.5 with the mass ratio of titanium dioxide：10, further preferred 1：10；
Described ethanol is 100～300 with the mass ratio of titanium dioxide：1, the consumption of ethanol is with being capable of fully dispersed dioxy
Change titanium to be defined, more preferably 200：1.
Modifying process TiO2Said by taking octyl group trimethoxy silane (OTMS) as an example by Degussa P25, silane coupler
It is bright.
Modified purpose is to improve the compatibility of P25 and polysiloxanes.There is hydroxyl in P25 surfaces, cause P25 particle tables
Face presents hydrophilic oleophobic property, and polysiloxanes are oily matter, and both have certain repulsion between interface.When with physics system
When hole agent carries out the synthesis of composite sponge for template, the repulsion between P25 and polysiloxanes can cause more TiO2Particle departs from
Polysiloxanes, so as to cause the situation of load effect difference.And surface is carried out to P25 with hydrophobic silane coupling agent and is modified, when
OTMS is grafted on P25 surfaces, then can increase its surface lipophile, increases its compatibility with polysiloxanes, good so as to realize
Good load effect.But the consumption of OTMS also can not be excessive, will otherwise cause TiO2The compatibility with polysiloxanes is good, makes
Be more present in polysiloxanes sponge body so as to be exposed to sponge hole wall ratio reduce.It is modified to certain journey simultaneously
After degree, there is one layer of OTMS molecular layer in P25 particle surfaces, produce steric effect, cause follow-up OTMS molecules to participate in P25
It is modified.With experimental results, OTMS amount of modifier is advisable with 3%～15%.I.e. described silane coupler and titanium dioxide
The mass ratio of titanium is 0.3～1.5：10.
Step 2) in, described basic components, linked, toluene, the mass ratio of modifying titanium dioxide are 20～40：1
～5：66：0.33～0.99, more preferably 30：3：66：0.33～0.99, the consumption of toluene is unsuitable less, otherwise by nothing
Method ensures that mixed liquor is wrapped up with the abundant moistening of physics perforating agent.Simultaneously the consumption of toluene is also unsuitable excessive, will otherwise cause silicon
The crosslinking degree of oil is reduced, and affects the mechanical property of composite sponge, also results in the TiO in composite sponge2Particle skewness.
Described basic components, linked are bi-component addition silicone rubber component A and B component, are added with commercially available bi-component
Molding silicone rubber is carrier loaded dichloride in anatase type TiO2。
Described physics perforating agent is one or two in Saccharum Sinensis Roxb., continuous sugar, further preferably, described physics perforating agent
For two kinds in Saccharum Sinensis Roxb., continuous sugar, mass ratio is 1：1.
The quality of described physics perforating agent is 6-20 with both mass ratios of basic components and linked：1, enter one
Step is preferred, is 18：1.
Commercially available Saccharum Sinensis Roxb. is added with continuous sugar and is mixed homogeneously in mould.Such as Fructose perforating agent incomplete mixing, it will cause sponge
Internal void skewness so that its mechanical property is poor.The consumption and ratio of two kinds of sugar can be used to adjust the hole of composite sponge
Gap rate and specific surface area.In order to obtain higher porosity and specific surface area, so that more TiO2It is exposed to sponge hole wall table
Face, Saccharum Sinensis Roxb. is with continuous sugared mass ratio with 1:1 is advisable.If the consumption of sugar is less, porosity is relatively low, and specific surface area is relatively low；
If sugar consumption it is larger, sponge hole wall will be caused relatively thin, poor mechanical property so that its without actual application value.Sand
Sugar is with continuous sugared gross mass with the 6-20 of silicone rubber gross mass：It is advisable between 1 times.Using white sugar be with continuous sugar it is commercially available,
Wherein white sugar particle diameter is more than 500 μm, and white soft sugar particle diameter is less than 500 μm.
10-14h molding in 60-80 DEG C of environment is placed in, 12h molding in 70 DEG C of environment is more preferably placed in.
Polysiloxanes/TiO2The preparation principle of composite sponge is：By basic components, linked, TiO2, solvent and physics
After perforating agent mix homogeneously, the volatilization and the hydrosilylation of silicone oil using solvent makes uniformly to be surrounded on physics perforating agent
The silicone oil crosslinking curing molding on surface, constructs out 3 D stereo cross-linked structure, the TiO in mixing and silicone oil2Then it is tied to solid
On sponge after change, subsequently the dissolving of physics perforating agent is removed, you can obtain polysiloxanes/TiO2Composite sponge.
Described basic components contain vinyl-terminated silicone fluid and containing hydrogen silicone oil, and described linked contains end-vinyl silicon
Oil and Karstedt catalyst, described basic components can specifically adopt Dow corning Sylgard 184A products, described
Linked can specifically adopt Dow corning Sylgard 184B products.
Step 3) in, the mould that will be equipped with molding composite sponge is immersed in the water the sugared particle of removal, so as to load dioxy is obtained
Change the polysiloxanes sponge of titanium photocatalyst.
The preparation method of composite sponge adopts physics drilling method.There is hydrosilylation with linked and hand in basic components
Connection solidification, be modified TiO2Retain on composite sponge, physics perforating agent is removed afterwards, obtain composite sponge.
The polysiloxanes sponge of described loaded titanium dioxide photocatalyst has the perforate being mutually communicated between Kong Yukong
Structure, and with certain mechanical property.
Further preferably, the preparation method of the polysiloxanes sponge of a kind of loaded titanium dioxide photocatalyst, including it is following
Step：
1) titanium dioxide is scattered in ethanol, carries out ultrasonic disperse, be subsequently adding silane coupler and be modified, afterwards
Jing is centrifuged, is dried to obtain modifying titanium dioxide；
The condition of described ultrasonic disperse：Ultrasonic power 400W, ultrasonic time 10min.
Described silane coupler is octyl group trimethoxy silane (OTMS)；
Described modified condition is：Modification temperature is 50 DEG C, modification time 6h；
Described silane coupler is 1 with the mass ratio of titanium dioxide：10；
Described ethanol is 200 with the mass ratio of titanium dioxide：1；
2) by basic components, linked, toluene, modifying titanium dioxide mix homogeneously, in adding mould, then again in mould
Add physics perforating agent, mix homogeneously to be placed in 12h in 70 DEG C of environment in tool, obtain the mould equipped with molding composite sponge；
Described basic components, linked, toluene, the mass ratio of modifying titanium dioxide are 30：3：66：0.99；
Described physics perforating agent is two kinds in Saccharum Sinensis Roxb., continuous sugar, and mass ratio is 1：1；
The quality of described physics perforating agent is 18 with both mass ratios of basic components and linked：1；
3) mould that will be equipped with molding composite sponge is placed in water dissolving removal physics perforating agent, obtains carried titanium dioxide
The polysiloxanes sponge of photocatalyst.
Under the preparation method, under the polysiloxanes sponge daylight of the loaded titanium dioxide photocatalyst for obtaining dyestuff drop is carried out
During solution experiment, the 1st time sunlight degradation is 97%, and the 5th sunlight degradation is 96%, and photocatalysis efficiency is very high.
Compared with prior art, the invention has the advantages that：
1. polysiloxanes photocatalyst sponge porosity of the present invention is high, connectivity cans be compared to that surface area is big, be exposed to sea
The photocatalyst granular quantity in continuous body surface face is more, and polysiloxanes sponge has stronger adsorption to pollutant.
2. due to stronger absorption property, after the pollutant of sponge absorption are supported photocatalyst for degrading, can be after
Pollutant in continuous absorption water, so as to realize a process adsorbed-degrade-adsorb again-degrade again, both collaborations are made
With making the great actual application value of the system.
3. the present invention adopts relatively low cost of material, process is simple and density is less, the water surface can be rested on, so as to reality
Using and reclaim very convenient, suitable industrialized production.
Description of the drawings
Fig. 1 is the modified TiO of OTMS in embodiment 12Schematic diagram；
Fig. 2 is the SEM photograph of the gained composite sponge of embodiment 1, and amplification is 500 times；
Fig. 3 is the optical photograph of the gained composite sponge of embodiment 1；
Fig. 4 is the compression stress strain curve of the gained composite sponge of embodiment 1.
Specific embodiment
Embodiment：
10g titanium dioxide (commercially available Degussa P25) ultrasonic disperse is taken in 2000g ethanol, ultrasonic power 400W, when ultrasonic
Between 10min, be added in double-deck reactor after ultrasound, add 1gOTMS afterwards, 50 DEG C of water-baths after 6h, are centrifuged, are dried to obtain and change
Property P25.
The preparation method of embodiment 1-5 is by basic components (Dow corning Sylgard 184A), the linked (U.S.
DOW CORNING Sylgard 184B), toluene, after modified P25 mix homogeneously, in adding mould, be added thereto to white sugar and white continuous
Sugar stirs.12h in 70 DEG C of environment is placed on, be subsequently drawn off and be dissolved in water removing perforating agent sugar particle, obtains final product
The polysiloxanes sponge sample of the loaded titanium dioxide photocatalyst of embodiment 1-5.
The preparation method of embodiment 6 (as a comparison case) is by basic components (Dow corning Sylgard 184A), hands over
Teflon mould is added after joint group point (Dow corning Sylgard 184B), toluene, modified P25 powder mix homogeneously
In, make toluene therein volatilize naturally 24h under the conditions of 25 DEG C of room temperature, obtain final product afterwards the sample of embodiment 6 (polysiloxanes/
TiO2Composite membrane), it is embodied as shown in table 1 below：
Table 1
Fig. 1 is the modified TiO of OTMS in embodiment 12Schematic diagram；Fig. 2 is the SEM photograph of the gained composite sponge of embodiment 1,
Amplification is 500 times；Fig. 3 is the optical photograph of the gained composite sponge of embodiment 1；Fig. 4 is the gained composite sponge of embodiment 1
Compression stress strain curve.
By the composite sponge obtained by embodiment 1-3, by SEM photograph it can be seen that：With the increasing of modified P25 consumptions
Greatly, its number of particles for being exposed to composite sponge bore wall also increases therewith, so as to its photocatalysis performance increases.
By embodiment 2,4 and 5 gained composite sponges, by SEM photograph it can be seen that：With the increasing of sugared particle template consumption
Greatly, what its hole wall became is thinner, so that more TiO2Bore wall is exposed to, so that its photocatalysis performance increases.
It is as follows that embodiment 1-6 gained sample carries out dyestuff degradation experiment data.Experiment is carried out in the sunlight, and experiment condition is
Fine day, daylight is sufficient, and the sunshine-duration starts for 10 points of morning, terminates after 48h, carries out dye liquor test.Dyestuff is rhodamine B, dense
Spend for 20ppm, volume is 50mL.The quality of composite sponge is 1g.Its degradation effect is as shown in table 2.
Table 2
| Sample | 1st sunlight degradation | The 5th sunlight degradation |
| Blank dye liquor | 0.2% | 0.21% |
| Blank sponge | 0.4% | 0.4% |
| Embodiment 1 | 66% | 63% |
| Embodiment 2 | 83% | 81% |
| Embodiment 3 | 97% | 96% |
| Embodiment 4 | 64% | 64% |
| Embodiment 5 | 71% | 70% |
| Embodiment 6 (as a comparison case) | 19% | 18% |
Claims (10)
1. the preparation method of the polysiloxanes sponge of a kind of loaded titanium dioxide photocatalyst, it is characterised in that including following step
Suddenly：
1) titanium dioxide is scattered in ethanol, carries out ultrasonic disperse, be subsequently adding silane coupler and be modified, after Jing from
The heart, it is dried to obtain modifying titanium dioxide；
2) by basic components, linked, toluene, modifying titanium dioxide mix homogeneously, in adding mould, then again in a mold
Add physics perforating agent, mix homogeneously to be placed in 6-24h molding in 50-120 DEG C of environment, obtain the mould equipped with molding composite sponge
Tool；
3) mould that will be equipped with molding composite sponge is placed in water dissolving removal physics perforating agent, obtains carried titanium dioxide light and urges
The polysiloxanes sponge of agent.
2. the preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst according to claim 1, its feature
It is, step 1) in, the condition of described ultrasonic disperse：300～500W of ultrasonic power, 5～20min of ultrasonic time.
3. the preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst according to claim 1, its feature
It is, step 1) in, described silane coupler is octyl group trimethoxy silane.
4. the preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst according to claim 1, its feature
It is, step 1) in, described modified condition is：Modification temperature is 40～60 DEG C, 5～7h of modification time.
5. the preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst according to claim 1, its feature
It is, step 1) in, described silane coupler and the mass ratio of titanium dioxide is 0.3～1.5：10；
Described ethanol is 100～300 with the mass ratio of titanium dioxide：1.
6. the preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst according to claim 1, its feature
It is, step 2) in, described basic components, linked, toluene, the mass ratio of modifying titanium dioxide are 20～40：1～5：
66：0.33～0.99.
7. the preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst according to claim 1, its feature
It is, step 2) in, described physics perforating agent is one or two in Saccharum Sinensis Roxb., continuous sugar.
8. the preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst according to claim 1, its feature
It is, step 2) in, the described quality of physics perforating agent and both mass ratios of basic components and linked is 6-20：
1。
9. the preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst according to claim 1, its feature
It is, step 2) in, it is placed in 10-14h molding in 60-80 DEG C of environment.
10. the preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst according to claim 1, its feature
It is, step 3) in, the polysiloxanes sponge of described loaded titanium dioxide photocatalyst has between Kong Yukong and is mutually communicated
Open-celled structure.
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