CN115364904A - Photocatalyst for volatile organic pollutants and use method thereof - Google Patents
Photocatalyst for volatile organic pollutants and use method thereof Download PDFInfo
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- CN115364904A CN115364904A CN202210794669.7A CN202210794669A CN115364904A CN 115364904 A CN115364904 A CN 115364904A CN 202210794669 A CN202210794669 A CN 202210794669A CN 115364904 A CN115364904 A CN 115364904A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 105
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 53
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 52
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000017 hydrogel Substances 0.000 claims abstract description 41
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 40
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 40
- 239000006260 foam Substances 0.000 claims abstract description 39
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 29
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 29
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 29
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 29
- 230000015556 catabolic process Effects 0.000 claims abstract description 12
- 238000006731 degradation reaction Methods 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000012855 volatile organic compound Substances 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229920000428 triblock copolymer Polymers 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 6
- 238000007906 compression Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 229920001400 block copolymer Polymers 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- YYJNCOSWWOMZHX-UHFFFAOYSA-N triethoxy-(4-triethoxysilylphenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=C([Si](OCC)(OCC)OCC)C=C1 YYJNCOSWWOMZHX-UHFFFAOYSA-N 0.000 claims description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001282 organosilanes Chemical class 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000021615 conjugation Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011490 mineral wool Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229910003556 H2 SO4 Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000004065 wastewater treatment 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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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
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/804—UV light
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a photocatalyst for volatile organic pollutants and a using method thereof, and relates to the field of photocatalysis, and the technical scheme comprises TiO2, organic SiO2 and polymethyl methacrylate, wherein the organic SiO2 and the polymethyl methacrylate form hydrogel foam, then TiO2 is deposited in situ in formed hydrogel foam mesopores, the prepared PMMA/silicon dioxide hydrogel foam doped with TiO2 is used as the photocatalyst and added into the volatile organic pollutants, and PMMA/silicon dioxide hydrogel foam has high light transmission (more than 90 percent) so that ultraviolet light can penetrate through PMMA, the TiO2 is deposited in situ in micropores of the hydrogel foam and forms heterojunction with silicon dioxide, and the photocatalytic efficiency is higher; in addition, the PMMA/silicon dioxide hydrogel foam is of a porous structure, and the complex pore channels are beneficial to increasing the interception of volatile organic gas, so that the contact time with the nano TiO2 is realized, and the degradation efficiency of the volatile gas is increased.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a photocatalyst for volatile organic pollutants and a using method thereof.
Background
The photocatalysis principle is based on the oxidation-reduction capability of the photocatalyst under the condition of illumination, so that the aims of purifying pollutants, synthesizing and converting substances and the like can be fulfilled. In general, a photocatalytic oxidation reaction uses a semiconductor as a catalyst and light as energy to degrade organic substances into carbon dioxide and water.
Through retrieval, the invention patent with the Chinese patent number of CN104326524A discloses a method for degrading phenol through photocatalysis, and belongs to the field of wastewater treatment methods. The method for degrading phenol by photocatalysis comprises the following steps: filling rock wool loaded with a TiO2 photocatalyst in a reactor with an ultraviolet lamp tube fixed in the middle, introducing phenol-containing wastewater from the bottom of the reactor at a certain flow rate, irradiating by using the ultraviolet lamp, simultaneously adding a small amount of hydrogen peroxide and introducing air, and discharging water from the top of the reactor, namely the wastewater after phenol degradation. The method for degrading phenol by photocatalysis adopts rock wool loaded with TiO2 photocatalyst as photocatalyst, has better treatment effects of photocatalytic degradation, adsorption and the like on phenol under the conditions of ultraviolet lamp irradiation, ventilation and hydrogen peroxide addition, and basically and completely degrades phenol after 120min treatment.
However, in the above-mentioned photocatalytic treatment method, the rock wool loaded with the TiO2 photocatalyst absorbs the ultraviolet light, and then purifies the phenol-containing industrial wastewater to oxidize the organic substances therein, but in the actual use process, the TiO2 photocatalyst requires a large amount of light energy, and it is difficult to effectively purify the wastewater, and the purification efficiency is low, so that there is a need for a photocatalyst for volatile organic pollutants and a method for using the same.
Disclosure of Invention
The invention aims to solve the defects that TiO2 as a photocatalyst in the prior art needs a large amount of light energy, waste water is difficult to purify effectively, and the purification efficiency is low, and provides the photocatalyst for volatile organic pollutants and a using method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a photocatalyst for volatile organic pollutants and a using method thereof comprise TiO2, organic SiO2 and polymethyl methacrylate, wherein the organic SiO2 and the polymethyl methacrylate form hydrogel foam, and then the TiO2 is deposited in situ in the formed hydrogel foam mesopores;
the photocatalyst is prepared by the following steps:
the method comprises the following steps: respectively preheating the prepared organic silicon dioxide nano particles and polymethyl methacrylate at the preheating temperature of 80 ℃;
step two: mixing the preheated SiO2 hydrogel and the polymethyl methacrylate, and then putting the mixture into an internal mixer for reaction, wherein the reaction time is 30min, the reaction temperature is 220 ℃, and the rotor speed is 60rpm;
step three: compressing and molding the reacted substances in the internal mixer at the high temperature of 160 ℃, wherein the thickness of the compressed sheet is 3mm, and the compression time is 50min;
step four: putting the generated sheet into an autoclave, and filling sufficient carbon dioxide into the autoclave for saturation for 12h;
step five: rapidly opening the high-pressure kettle to enable the air pressure in the high-pressure kettle to be suddenly reduced, and shaping the generated foam through cold water to form PMMA/silicon dioxide hydrogel foam doped with TiO 2;
step six: the hydrogel foam was ultrasonically dispersed in a solvent and the TiO2 precursor was added.
In the process, the PMMA/silicon dioxide hydrogel foam has high light transmittance (more than 90 percent) so that ultraviolet light can penetrate through the PMMA, tiO2 is deposited in situ in micropores of the hydrogel foam and forms a heterojunction with silicon dioxide, and the photocatalytic efficiency is higher;
the PMMA/silicon dioxide hydrogel foam is of a porous structure, and the complex pore channels are beneficial to increasing the interception of volatile organic gas, so that the contact time with the nano TiO2 is realized, and the degradation efficiency of the volatile gas is increased.
The above technical solution further comprises:
further, in the second photocatalyst preparation step, the reaction time was 30min, the reaction temperature was 220 ℃, and the rotor speed was 60rpm.
Further, the dosage of the organic SiO2 hydrogel and the polymethyl methacrylate is 1.
Further, the hydrogel foam, solvent and TiO2 precursor were used in an amount of 0.1.
Further, the preparation of the organic SiO2 comprises the following steps:
the first step is as follows: dissolving a F127PEO-PPO-PEO triblock copolymer in a mixture of distilled water and H2SO 4;
a second step of stirring the mixture for 2 hours, adding 1.02g of 1, 4-bis (triethoxysilyl) benzene, stirring the mixture for 2.5 hours at 40 ℃, and then aging for 24 hours at 100 ℃ to obtain a precipitate;
thirdly, the block copolymer template is extracted 4 times for 12 hours with a mixed solvent containing ethanol and 37wt% HCl under magnetic stirring at 70 ℃, and then the flask is filtered and washed with distilled water and acetone under suction and dried at 100 ℃ for 1d to obtain organic SiO2;
in the process, the organic SiO2 contains benzene rings, so that pi-pi conjugation exists between the organic SiO2 and benzene-containing ring substances in the volatile organic compounds, selective adsorption of the benzene-containing ring substances in the volatile organic compounds is realized, and the benzene-containing ring substances in the volatile organic compounds can be better degraded.
Further, 0.5g of F127PEO-PPO-PEO triblock copolymer, 22.38g of distilled water, 0.12g of H2SO4, 60g of ethanol, 2g of 37wt% HCl, F127: organosilane: H2O: acid = 1:63-65:29260-33440:25.6-61.3.
Further, in the fourth step of the photocatalyst preparation, the inside atmosphere of the autoclave was 100 ℃ and 16MPa.
A method of using a photocatalyst for volatile organic contaminants, comprising the steps of:
the method comprises the following steps: preparing a photocatalyst of the volatile organic compound, and placing the prepared photocatalyst into a degradation container;
step two: conveying the volatile organic compounds into a degradation container through a pipeline;
step three: placing an ultraviolet lamp tube in the degradation container for irradiation, and simultaneously introducing external air into the degradation container at a constant speed;
step four: and after the photocatalytic degradation is finished, discharging the wastewater.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the prepared PMMA/silicon dioxide hydrogel foam doped with TiO2 is used as a photocatalyst and added into volatile organic pollutants, and the PMMA in the PMMA/silicon dioxide hydrogel foam has high light transmittance (more than 90%), so that ultraviolet light can penetrate through PMMA, tiO2 is deposited in situ in micropores of the hydrogel foam and forms heterojunction with silicon dioxide, and the photocatalytic efficiency is higher; in addition, the PMMA/silicon dioxide hydrogel foam is of a porous structure, and the complex pore channels are beneficial to increasing the interception of volatile organic gas, so that the contact time with the nano TiO2 is realized, and the degradation efficiency of the volatile gas is increased.
2. In the invention, because the organic SiO2 contains benzene rings, pi-pi conjugation exists between the organic SiO2 and benzene-containing ring substances in volatile organic compounds, selective adsorption of the benzene-containing ring substances in the volatile organic compounds is realized, and the benzene-containing ring substances in the volatile organic compounds can be better degraded.
3. In the technical scheme of the invention, PMMA is a polymer with hydrophobicity, and since the volatile organic pollutants have hydrophobicity, PMMA can realize interception and adsorption of the volatile organic pollutants through physical interaction, and realize a better adsorption effect on the volatile organic pollutants in cooperation with organic SiO2, and realize photodegradation of the volatile organic pollutants in cooperation with a TiO 2-silicon dioxide heterojunction structure.
Detailed Description
Example one
S1, dissolving 0.5g of the F127PEO-PPO-PEO triblock copolymer in a mixture of 22.38g of distilled water and 0.12gH2SO4;
s2: after stirring the mixture for 2 hours, 1.02g of 1, 4-bis (triethoxysilyl) benzene was added, the mixture was stirred at 40 ℃ for 2.5 hours, and then aged at 100 ℃ for 24 hours to obtain a precipitate;
s3: the block copolymer template was extracted 4 times for 12 hours with a mixed solvent containing 60g of ethanol and 2g of 37wt% HCl under magnetic stirring at 70 ℃, and then the flask was suction-filtered and washed with distilled water and acetone and dried at 100 ℃ for 1d to obtain organo-SiO 2.
Example two
S1, dissolving 0.5g of the F127PEO-PPO-PEO triblock copolymer in a mixture of 22.38g of distilled water and 0.12g of H2 SO4;
s2: after stirring the mixture for 2 hours, 1.12g of 1, 4-bis (triethoxysilyl) benzene was added, the mixture was stirred at 40 ℃ for 2.5 hours, and then aged at 100 ℃ for 24 hours to obtain a precipitate;
s3: the block copolymer template was extracted 4 times for 12 hours with a mixed solvent containing 60g of ethanol and 2.2g of 37wt% HCl under magnetic stirring at 70 ℃ and then the flask was filtered and washed with distilled water and acetone with suction and dried at 100 ℃ for 1d to obtain organic SiO2.
EXAMPLE III
S1, dissolving 0.5g of the F127PEO-PPO-PEO triblock copolymer in a mixture of 22.38g of distilled water and 0.12gH2SO4;
s2: after stirring the mixture for 2 hours, 0.92g of 1, 4-bis (triethoxysilyl) benzene was added, the mixture was stirred at 40 ℃ for 2.5 hours, and then a precipitate was obtained after aging at 100 ℃ for 24 hours;
s3: the block copolymer template was extracted 4 times for 12 hours with a mixed solvent containing 60g of ethanol and 1.85g of 37wt% HCl under magnetic stirring at 70 ℃ and then the flask was filtered and washed with distilled water and acetone with suction and dried at 100 ℃ for 1d to obtain organic SiO2.
Comparative example 1
S1: adopting commercially available SiO2 as a synthetic raw material of subsequent hydrogel foam;
s2: and carrying out ultrasonic crushing on the obtained SiO2 to obtain SiO2 nano-particles.
Example four
S1: respectively preheating the organic silicon dioxide nano particles and the polymethyl methacrylate prepared in the first embodiment, wherein the preheating temperature is 80 ℃;
s2: mixing the preheated SiO2 hydrogel and the polymethyl methacrylate, and then putting the mixture into an internal mixer for reaction, wherein the reaction time is 30min, the reaction temperature is 220 ℃, and the rotor speed is 60rpm;
s3: compressing and molding the reacted substances in the internal mixer at the high temperature of 160 ℃, wherein the thickness of the compressed sheet is 3mm, and the compression time is 50min;
s4: putting the generated sheet into an autoclave, and filling sufficient carbon dioxide into the autoclave for saturation for 12 hours;
s5: rapidly opening the high-pressure kettle to enable the air pressure in the high-pressure kettle to be suddenly reduced, and shaping the generated foam through cold water to form PMMA/silicon dioxide hydrogel foam doped with TiO 2;
s6: the hydrogel foam is ultrasonically dispersed in a solvent, and then a TiO2 precursor is added to obtain the photocatalyst.
EXAMPLE five
S1: respectively preheating the organic silicon dioxide nano particles and the polymethyl methacrylate prepared in the second embodiment, wherein the preheating temperature is 80 ℃;
s2: mixing the preheated SiO2 hydrogel and the polymethyl methacrylate, and then putting the mixture into an internal mixer for reaction, wherein the reaction time is 30min, the reaction temperature is 220 ℃, and the rotor speed is 60rpm;
s3: compressing and molding the reacted substances in the internal mixer at the high temperature of 160 ℃, wherein the thickness of the compressed sheet is 3mm, and the compression time is 50min;
s4: putting the generated sheet into an autoclave, and filling sufficient carbon dioxide into the autoclave for saturation for 12 hours;
s5: rapidly opening the high-pressure kettle to enable the air pressure in the high-pressure kettle to be suddenly reduced, and shaping the generated foam through cold water to form PMMA/silicon dioxide hydrogel foam doped with TiO 2;
s6: the hydrogel foam is ultrasonically dispersed in a solvent, and then a TiO2 precursor is added to obtain the photocatalyst.
EXAMPLE six
S1: respectively preheating the organic silicon dioxide nano particles and the polymethyl methacrylate prepared in the third embodiment, wherein the preheating temperature is 80 ℃;
s2: mixing the preheated SiO2 hydrogel and the polymethyl methacrylate, and then putting the mixture into an internal mixer for reaction, wherein the reaction time is 30min, the reaction temperature is 220 ℃, and the rotor speed is 60rpm;
s3: compressing and molding the reacted substances in the internal mixer at the high temperature of 160 ℃, wherein the thickness of the compressed sheet is 3mm, and the compression time is 50min;
s4: putting the generated sheet into an autoclave, and filling sufficient carbon dioxide into the autoclave for saturation for 12 hours;
s5: rapidly opening the high-pressure kettle to enable the air pressure in the high-pressure kettle to be suddenly reduced, and shaping the generated foam through cold water to form PMMA/silicon dioxide hydrogel foam doped with TiO 2;
s6: the hydrogel foam is ultrasonically dispersed in a solvent, and then a TiO2 precursor is added to obtain the photocatalyst.
Comparative example No. two
S1: respectively preheating the organic silicon dioxide nano particles and the polymethyl methacrylate prepared in the first comparative example at the preheating temperature of 80 ℃;
s2: mixing the preheated SiO2 hydrogel and polymethyl methacrylate, and then putting the mixture into an internal mixer for reaction, wherein the reaction time is 30min, the reaction temperature is 220 ℃, and the rotor speed is 60rpm;
s3: compressing and molding the reacted substances in the internal mixer at the high temperature of 160 ℃, wherein the thickness of the compressed sheet is 3mm, and the compression time is 50min;
s4: putting the generated sheet into an autoclave, and filling sufficient carbon dioxide into the autoclave for saturation for 12 hours;
s5: rapidly opening the high-pressure kettle to enable the air pressure in the high-pressure kettle to be suddenly reduced, and shaping the generated foam through cold water to form PMMA/silicon dioxide hydrogel foam doped with TiO 2;
s6: the hydrogel foam is ultrasonically dispersed in a solvent, and then a TiO2 precursor is added to obtain the photocatalyst.
Now, the photocatalytic materials prepared in examples 4 to 6 and comparative example 2 were tested for performance, and the values of the concentration in the purification test were formaldehyde (6.38 mg/m 3), benzene (6.41 mg/m 3), toluene (6.36 mg/m 3), and ethylbenzene (6.38 mg/m 3): in a sealed test chamber containing formaldehyde, benzene, toluene and ethylbenzene, the initial concentration is firstly measured, the purification material prepared by the invention is placed, under the environment with the relative humidity of 90%, the natural attenuation rate is removed by using the ultraviolet lamp for irradiation, the concentration of various pollutants after 12h is tested, and the test results are shown in the following table 1:
| item | Formaldehyde concentration after 12h (mg/m 3) | Benzene concentration after 12h (mg/m 3) | Toluene concentration after 12h (mg/m 3) | Ethylbenzene concentration after 12h (mg/m 3) |
| Example 4 | 0.01 | 0.02 | 0.03 | 0.07 |
| Example 5 | 0.02 | 0.01 | 0.08 | 0.15 |
| Example 6 | 0.01 | 0.02 | 0.13 | 0.21 |
| Comparative example 2 | 0.21 | 0.34 | 0.34 | 0.45 |
TABLE 1
As can be seen from table 1 above, the photocatalyst prepared in the fourth embodiment of the present invention effectively absorbs formaldehyde, benzene, toluene, and ethylbenzene, and greatly improves the photocatalytic degradation effect on organic pollutants compared to the fifth and sixth embodiments and the second comparative example;
as can be seen from the data in table 1, in the first example, compared with the second and third examples and the first comparative example, the performance of the generated hydrogel foam is more excellent, meanwhile, the organic SiO2 contains benzene rings, and pi-pi conjugation exists between the organic SiO2 and the benzene-containing cyclic substances in the volatile organic compounds, so that selective adsorption of the benzene-containing cyclic substances in the volatile organic compounds is realized, and the benzene-containing cyclic substances in the volatile organic compounds can be better degraded.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. The photocatalyst for the volatile organic pollutants is characterized by comprising TiO2, organic SiO2 and polymethyl methacrylate, wherein the organic SiO2 and the polymethyl methacrylate form hydrogel foam, and then the TiO2 is deposited in situ in the mesoporous pores of the formed hydrogel foam;
the photocatalyst is prepared by the following steps:
the method comprises the following steps: respectively preheating the prepared organic silicon dioxide nano particles and polymethyl methacrylate at the preheating temperature of 80 ℃;
step two: mixing the preheated SiO2 hydrogel and polymethyl methacrylate, and then putting the mixture into an internal mixer for reaction;
step three: compressing and molding the reacted substances in the internal mixer at the high temperature of 160 ℃, wherein the thickness of the compressed sheet is 3mm, and the compression time is 50min;
step four: putting the generated sheet into an autoclave, and filling sufficient carbon dioxide into the autoclave for saturation for 12 hours;
step five: rapidly opening the high-pressure kettle to enable the air pressure in the high-pressure kettle to be suddenly reduced, and shaping the generated foam through cold water to form PMMA/silicon dioxide hydrogel foam doped with TiO 2;
step six: the hydrogel foam is ultrasonically dispersed in a solvent, and then a TiO2 precursor is added.
2. The photocatalyst for volatile organic pollutants as claimed in claim 1, wherein in the second photocatalyst preparation step, the reaction time is 30min, the reaction temperature is 220 ℃, and the rotor speed is 60rpm.
3. The photocatalyst for volatile organic pollutants as claimed in claim 1, wherein the organic SiO2 hydrogel and the polymethyl methacrylate are used in an amount of 1.
4. A photocatalyst for volatile organic contaminants, as claimed in claim 1, wherein the hydrogel foam, solvent and TiO2 precursor are used in the ratio of 0.1.
5. The photocatalyst for volatile organic pollutants as claimed in claim 1, wherein the preparation of the organic SiO2 comprises the following steps:
the first step is as follows: dissolving a F127PEO-PPO-PEO triblock copolymer in a mixture of distilled water and H2SO 4;
a second step of stirring the mixture for 2 hours, adding 1.02g of 1, 4-bis (triethoxysilyl) benzene, stirring the mixture for 2.5 hours at 40 ℃, and then aging for 24 hours at 100 ℃ to obtain a precipitate;
third, the block copolymer template was extracted 4 times for 12 hours with a mixed solvent containing ethanol and 37wt% HCl under magnetic stirring at 70 ℃, and then the flask was suction-filtered and washed with distilled water and acetone and dried at 100 ℃ for 1d to obtain organo-SiO 2.
6. The photocatalyst for volatile organic pollutants as claimed in claim 5, wherein the amount of F127PEO-PPO-PEO triblock copolymer is 0.5g, the amount of distilled water is 22.38g, the amount of H2SO4 is 0.12g, the amount of ethanol is 60g, the amount of 37wt% HCl is 2g, the ratio of F127: organosilane: H2O: acid = 1:63-65:29260-33440:25.6-61.3.
7. The photocatalyst for volatile organic contaminants of claim 1, wherein the photocatalyst is prepared in the fourth step in which the inside of the autoclave is at an atmosphere of 100 ℃ and 16Mpa.
8. The method of using the photocatalyst for the volatile organic pollutants as claimed in claim 1, comprising the steps of:
the method comprises the following steps: preparing a photocatalyst of the volatile organic compound, and placing the prepared photocatalyst into a degradation container;
step two: conveying the volatile organic compounds into a degradation container through a pipeline;
step three: placing an ultraviolet lamp tube in the degradation container for irradiation, and simultaneously introducing external air into the degradation container at a constant speed;
step four: and after the photocatalytic degradation is finished, discharging the wastewater.
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