CN106563501B - A kind of preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst - Google Patents
A kind of preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst Download PDFInfo
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- CN106563501B CN106563501B CN201610957047.6A CN201610957047A CN106563501B CN 106563501 B CN106563501 B CN 106563501B CN 201610957047 A CN201610957047 A CN 201610957047A CN 106563501 B CN106563501 B CN 106563501B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 45
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 43
- -1 polysiloxanes Polymers 0.000 title claims abstract description 39
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical group CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 claims description 14
- 235000000346 sugar Nutrition 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 235000021552 granulated sugar Nutrition 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229920002545 silicone oil Polymers 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 4
- 241000628997 Flos Species 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003344 environmental pollutant Substances 0.000 abstract description 7
- 231100000719 pollutant Toxicity 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000007259 addition reaction Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- 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
- 230000008859 change Effects 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000008569 process Effects 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
- 238000004140 cleaning Methods 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
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000012545 processing Methods 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
- 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
- 230000006378 damage Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005265 energy consumption 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
- 238000011068 loading method Methods 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
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 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
- 239000004576 sand Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000004945 silicone rubber Substances 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
- 238000001179 sorption measurement Methods 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
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- 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
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- 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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Abstract
It is with commercially available bi-component addition type silicon rubber for carrier loaded dichloride in anatase type TiO the invention discloses a kind of preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst2, to commercially available TiO2Be uniformly mixed after being modified with silicon rubber, be added physics perforating agent after carry out Si―H addition reaction cross-linking reaction, after physics perforating agent is removed, obtain polysiloxanes/TiO2Composite sponge, to realize that polysiloxanes sponge loads nano-TiO2.The present invention is made sponge specific surface area and greatly increases, and there is preferable absorption property to be allowed to be enriched with oiliness pollutant, to make more TiO2It is contacted with pollutant, generates synergistic effect, improve photocatalysis performance.This load has many advantages, such as that large specific surface area, adsorptivity are preferable, photocatalysis performance is good, practical application and recycling are more convenient.
Description
Technical field
The present invention relates to titanium dioxide optical catalyst technical fields, and in particular to a kind of loaded titanium dioxide photocatalyst
The preparation method of polysiloxanes sponge.
Background technique
As environmental pollution increasingly obtains the attention of people, people constantly find energy consumption less, and processing more simply has
The mode of effect solves environmental pollution.Wherein anatase titanium dioxide TiO2It can using the active group that the ultraviolet light in sunlight generates with it
To cut off the chemical bond that many bond energys are lower than this, consumes energy less to realize, handles simple and effective pollution processing.
Due to the TiO usually prepared2High-temperature calcination need to be passed through, thus cause particle aggregation serious, and do not bear to it
It carries, then recycling and reusing is difficult, and secondary pollution is caused in water to be allowed to remain on.In conventional organic carrier, due to C-C key key
It can (346kJmol-1) it is lower than TiO2Energy (the OOH 431kJmol of the active group of generation-1, OH is
402.7kJ·mol-1), thus will cause the serious destruction for matrix.And polysiloxane backbone is Si-O key, bond energy
(460kJ·mol-1) it is higher than TiO2The energy of the active group of generation not will cause matrix aging, thus be a kind of ideal load
Body.
Ding Xiaofeng [CN101724342A；CN101962514A；J Mater Chem, 2011,21:6161~6164] with poly-
Silicone cross-linked film forming is to load commercial powder TiO2, it is poly- that a series of automatically cleaning with super-hydrophobic or super parents' function is made
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 performance that is more serious, thus influencing its performance, thus causes
Its powder TiO2Dosage is desirable compared with great talent to derive from clean effect.
Jiang Mei [macromolecule journal, 2008,6:594~599], Wang Fang [Journal of Inorganic Materials, 2010,25 (1): 37~
40], [coatings industry, 2010,40 (8): being then 36~38] etc. by the way of collosol and gel and curing of coating come real to Peng Ruimai
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 disclose it is a kind of former by the polysiloxanes of vinyl-terminated silicone fluid and containing hydrogen silicone oil hydrosilylation and titanium dioxide
The method that position polymerization prepares photocatalysis composite membrane.TiO in photocatalysis composite membrane obtained by this method2For anatase titanium dioxide, and more
It is even to be scattered in composite membrane, thus there is preferable photocatalysis performance.But there is more TiO2In film, thus fail sufficiently
Play due effect.
Approach described above, which is conceived to, prepares composite membrane to load TiO2, but this method can serious restricted T iO2Light urge
Change performance, because of made nano-TiO2Size is 10-100nm, and film thickness is then 100-300 μm, can be there are many TiO2It is detained
In due effect can not be played 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-dimensional space to expand specific surface area, to make more TiO2Light can be played
Catalytic performance.But this method process is more and more expensive with material, is not suitable for being applied to sewage treatment.And inorganic carrier is to organic
Pollutant does not have good adsorption capacity, cannot generate synergistic effect with photochemical catalyst.
Summary of the invention
The present invention provides a kind of preparation methods of the polysiloxanes sponge of loaded titanium dioxide photocatalyst, by poly- silicon oxygen
Alkane is made into sponge, and carried titanium dioxide is carried out in the form of three-dimensional sponge, and sponge specific surface area is made and greatly increases, to oiliness pollutant
With preferable absorption and accumulation ability, to make more TiO2It is contacted with pollutant, generates synergistic effect, improve photocatalysis
Performance.
A kind of preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst, comprising the following steps:
1) it disperses titanium dioxide in ethyl alcohol, carries out ultrasonic disperse, silane coupling agent is then added and is modified, later
It is centrifuged, is dried to obtain modifying titanium dioxide；
2) basic components, cross-linking component, toluene, modifying titanium dioxide are uniformly mixed, are added in mold, then again in mould
Physics perforating agent is added in tool, is uniformly mixed, is placed in 6-24h in 50-120 DEG C of environment and forms, obtain equipped with molding composite sponge
Mold；
3) mold equipped with molding composite sponge is placed in water dissolution removal physics perforating agent, obtains carried titanium dioxide
The polysiloxanes sponge of photochemical catalyst.
It is used as the preferred technical solution of the present invention below:
In step 1), the condition of the ultrasonic disperse: 300~500W of ultrasonic power, 5~20min of ultrasonic time, into one
Step is preferred, ultrasonic power 400W, ultrasonic time 10min.
The silane coupling agent is octyl trimethoxy silane (OTMS)；
The condition of the modification are as follows: modification temperature is 40~60 DEG C, 5~7h of modification time, further preferably, modified temperature
Degree is 50 DEG C, modification time 6h；
The mass ratio of the silane coupling agent and titanium dioxide is 0.3~1.5:10, further preferred 1:10；
The mass ratio of the ethyl alcohol and titanium dioxide is 100~300:1, and the dosage of ethyl alcohol is with being capable of fully dispersed dioxy
Change subject to titanium, further preferably 200:1.
Modifying process TiO2It is said by taking octyl trimethoxy silane (OTMS) as an example by Degussa P25, silane coupling agent
It is bright.
Modified purpose is the compatibility in order to improve P25 and polysiloxanes.There are hydroxyls on the surface P25, lead to P25 particle table
Face shows hydrophilic and oleophobic property, and polysiloxanes is oily matter, and there are certain repulsions between the two interface.When with physics system
When hole agent is the synthesis that template carries out composite sponge, the repulsion between P25 and polysiloxanes will lead to more TiO2Particle is detached from
Polysiloxanes, 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 the surface P25, then can increase its surface lipophilicity, increase its compatibility with polysiloxanes, to realize good
Good load effect.But the dosage of OTMS also can not be excessive, otherwise will lead to TiO2It is good with the compatibility of polysiloxanes, make
It is to be more present in polysiloxanes cavernous body, so that it is exposed to the reduction of the ratio of sponge hole wall.It is modified to certain journey simultaneously
After degree, there are one layer of OTMS molecular layers for P25 particle surface, generate steric effect, cause subsequent OTMS molecule that can not participate in P25
It is modified.With experimental results, OTMS amount of modifier is advisable with 3%~15%.That is the silane coupling agent and titanium dioxide
The mass ratio of titanium is 0.3~1.5:10.
In step 2), the basic components, cross-linking component, toluene, modifying titanium dioxide mass ratio be 20~40:1
~5:66:0.33~0.99, further preferably 30:3:66:0.33~0.99, the dosage of toluene is unsuitable less, otherwise by nothing
Method guarantees that the abundant wetting of mixed liquor and physics perforating agent is wrapped up.Simultaneously otherwise the dosage of toluene also excessively should not will lead to silicon
The crosslinking degree of oil reduces, and influences the mechanical property of composite sponge, also results in the TiO in composite sponge2Particle distribution is uneven.
The basic components, cross-linking component are bi-component addition silicon rubber component A and B component, are added with commercially available bi-component
Molding silicone rubber is carrier loaded dichloride in anatase type TiO2。
The physics perforating agent is one or both of granulated sugar, continuous sugar, further preferably, the physics perforating agent
For two kinds in granulated sugar, continuous sugar, mass ratio 1:1.
The quality and basic components of the physics perforating agent and the two mass ratio of cross-linking component are 6-20:1, into one
Step is 18:1 preferably.
Commercially available granulated sugar is added in mold with continuous sugar and is uniformly mixed.Such as fructose perforating agent incomplete mixing, it will lead to sponge
Internal void is unevenly distributed, so that its mechanical property is poor.Two kinds of sugared dosages and ratio 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, to make more TiO2It is exposed to sponge hole wall table
The mass ratio in face, granulated sugar and continuous sugar is advisable with 1:1.If the dosage of sugar is smaller, porosity is lower, and specific surface area is lower；
If the dosage of sugar is larger, it is relatively thin to will lead to sponge hole wall, poor mechanical property, so that its made is without practical application value.Sand
The gross mass of sugar and continuous sugar is to be advisable between 6-20:1 times of silicon rubber gross mass.The white granulated sugar of use with continuous sugar be it is commercially available,
Wherein white granulated sugar partial size is greater than 500 μm, and white soft sugar partial size is less than 500 μm.
It is placed in 10-14h in 60-80 DEG C of environment to form, is further preferably placed in 12h in 70 DEG C of environment and forms.
Polysiloxanes/TiO2The preparation principle of composite sponge are as follows: by basic components, cross-linking component, TiO2, solvent and physics
After perforating agent is uniformly mixed, using the volatilization of solvent and the hydrosilylation of silicone oil, make uniformly to be surrounded on physics perforating agent
The silicone oil crosslinking curing on surface forms, and constructs out 3 D stereo cross-linked structure, mixing and the TiO in silicone oil2It is then tied to solid
On sponge after change, then physics perforating agent is dissolved and is removed, polysiloxanes/TiO can be obtained2Composite sponge.
The basic components contain vinyl-terminated silicone fluid and containing hydrogen silicone oil, and the cross-linking component contains end-vinyl silicon
Oil and Karstedt catalyst, the basic components can specifically use Dow corning Sylgard 184A product, described
Cross-linking component can specifically use Dow corning Sylgard 184B product.
In step 3), the mold equipped with molding composite sponge is immersed in the water the sugared particle of removal, so that load dioxy be made
Change the polysiloxanes sponge of titanium photochemical catalyst.
The preparation method of composite sponge uses physics drilling method.Basic components and cross-linking component occur hydrosilylation and hand over
Connection solidification, modified TiO2It retains on composite sponge, removes physics perforating agent later, obtain composite sponge.
The polysiloxanes sponge of the loaded titanium dioxide photocatalyst has the aperture being mutually communicated between Kong Yukong
Structure, and there is 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) it disperses titanium dioxide in ethyl alcohol, carries out ultrasonic disperse, silane coupling agent is then added and is modified, later
It is centrifuged, is dried to obtain modifying titanium dioxide；
The condition of the ultrasonic disperse: ultrasonic power 400W, ultrasonic time 10min.
The silane coupling agent is octyl trimethoxy silane (OTMS)；
The condition of the modification are as follows: modification temperature is 50 DEG C, modification time 6h；
The mass ratio of the silane coupling agent and titanium dioxide is 1:10；
The mass ratio of the ethyl alcohol and titanium dioxide is 200:1；
2) basic components, cross-linking component, toluene, modifying titanium dioxide are uniformly mixed, are added in mold, then again in mould
Physics perforating agent is added in tool, is uniformly mixed, is placed in 12h in 70 DEG C of environment, obtains the mold equipped with molding composite sponge；
The basic components, cross-linking component, toluene, modifying titanium dioxide mass ratio be 30:3:66:0.99；
Two kinds during the physics perforating agent is granulated sugar, silk floss is sugared, mass ratio 1:1；
The quality and basic components of the physics perforating agent and the two mass ratio of cross-linking component are 18:1；
3) mold equipped with molding composite sponge is placed in water dissolution removal physics perforating agent, obtains carried titanium dioxide
The polysiloxanes sponge of photochemical catalyst.
Under the preparation method, dyestuff drop is carried out under the polysiloxanes sponge daylight of obtained loaded titanium dioxide photocatalyst
When solution experiment, the 1st 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 following advantages:
1. polysiloxanes photochemical catalyst sponge porosity of the present invention is high, the good large specific surface area of connectivity, is exposed to sea
The photocatalyst granular quantity in continuous body surface face is more, and polysiloxanes sponge has stronger suction-operated to pollutant.
2., can be after after the pollutant of sponge absorption is supported photocatalyst for degrading due to having stronger absorption property
Pollutant in continuous absorption water, thus an absorption-degradation-is adsorbed again-process degraded again of realization, the collaboration of the two is made
With making the great practical application value of the system.
3. the present invention uses lower cost of material, simple process and density smaller, the water surface can be rested on, thus practical
Using and recycling it is very convenient, be suitable for industrialized production.
Detailed description of the invention
Fig. 1 is the modified TiO of OTMS in embodiment 12Schematic diagram；
Fig. 2 is the SEM photograph of 1 gained composite sponge of embodiment, and amplification factor is 500 times；
Fig. 3 is the optical photograph of 1 gained composite sponge of embodiment；
Fig. 4 is the compression stress strain curve of 1 gained composite sponge of embodiment.
Specific embodiment
Embodiment:
Take 10g titanium dioxide (commercially available Degussa P25) ultrasonic disperse in 2000g ethyl alcohol, ultrasonic power 400W, when ultrasonic
Between 10min, be added into the double-deck reaction kettle after ultrasound, be added 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 cross-linking component (U.S.
DOW CORNING Sylgard 184B), toluene, modified P25 after mixing, be added in mold, white granulated sugar and white silk floss be added thereto
Sugar stirs evenly.Place it in 12h in 70 DEG C of environment, be then drawn off and be dissolved in water remove perforating agent sugar particle to get
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 in connection component (Dow corning Sylgard 184B), toluene, modified P25 powder after mixing
In, so that toluene therein is volatilized naturally for 24 hours under the conditions of 25 DEG C of room temperature, later up to 6 sample of embodiment (polysiloxanes/
TiO2Composite membrane), specific implementation is 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 1 gained composite sponge of embodiment,
Amplification factor is 500 times；Fig. 3 is the optical photograph of 1 gained composite sponge of embodiment；Fig. 4 is 1 gained composite sponge of embodiment
Compression stress strain curve.
By the obtained composite sponge of embodiment 1-3, by SEM photograph it can be seen that with the increasing for being modified P25 dosage
Greatly, the number of particles for being exposed to composite sponge bore wall also increases with it, so that its photocatalytic can increase.
By embodiment 2,4 and 5 gained composite sponges, by SEM photograph it can be seen that with sugared particle template dosage increasing
Greatly, what hole wall became is thinner, to make more TiO2It is exposed to bore wall, so that its photocatalytic be made to can increase.
It is as follows that sample obtained by embodiment 1-6 carries out dyestuff degradation experiment data.Experiment carries out in the sunlight, and experiment condition is
Fine day, daylight is sufficient, and the sunshine-duration is to start 10 points of morning, is terminated after 48h, carries out dye liquor test.Dyestuff is rhodamine B, dense
Degree is 20ppm, volume 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 (5)
1. a kind of preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst, which is characterized in that including following step
It is rapid:
1) disperse titanium dioxide in ethyl alcohol, carry out ultrasonic disperse, then be added silane coupling agent be modified, after through from
The heart is dried to obtain modifying titanium dioxide, and the silane coupling agent is octyl trimethoxy silane, and modification temperature is 40~60
DEG C, 5~7h of modification time, the mass ratio of the silane coupling agent and titanium dioxide is 0.3~1.5:10；
2) basic components, cross-linking component, toluene, modifying titanium dioxide are uniformly mixed, are added in mold, then again in a mold
Physics perforating agent is added, is uniformly mixed, is placed in 6-24h in 50-120 DEG C of environment and forms, obtain the mould equipped with molding composite sponge
Tool, the basic components, cross-linking component, toluene, modifying titanium dioxide mass ratio be 20~40:1~5:66:0.33~
0.99；The basic components contain vinyl-terminated silicone fluid and containing hydrogen silicone oil, and the cross-linking component contains vinyl-terminated silicone fluid
With Karstedt catalyst；Two kinds during the physics perforating agent is granulated sugar, silk floss is sugared, mass ratio 1:1；Granulated sugar and continuous sugar
Gross mass is 6-20 times of silicon rubber gross mass；
3) mold equipped with molding composite sponge is placed in water dissolution removal physics perforating agent, obtains loaded modified titanium dioxide
The polysiloxanes sponge of photochemical catalyst, modifying titanium dioxide are embedded on sponge hole wall in polysiloxanes cavernous body with exposed.
2. the preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst according to claim 1, feature
It is, in step 1), the condition of the 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, feature
It is, in step 1), the mass ratio of the ethyl alcohol and titanium dioxide is 100~300:1.
4. the preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst according to claim 1, feature
It is, in step 2), is placed in 10-14h in 60-80 DEG C of environment and forms.
5. the preparation method of the polysiloxanes sponge of loaded titanium dioxide photocatalyst according to claim 1, feature
It is, in step 3), the polysiloxanes sponge of the loaded titanium dioxide photocatalyst has to be mutually communicated between Kong Yukong
Open-celled structure.
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