CN110918130A - cellulose/SiO2Composite aerogel photocatalytic material and preparation method thereof - Google Patents
cellulose/SiO2Composite aerogel photocatalytic material and preparation method thereof Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 68
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 59
- 229920002678 cellulose Polymers 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 57
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 23
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 23
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011941 photocatalyst Substances 0.000 claims abstract description 6
- 239000000499 gel Substances 0.000 claims description 48
- 239000007787 solid Substances 0.000 claims description 46
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 17
- 239000000017 hydrogel Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000010893 paper waste Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 16
- 230000002209 hydrophobic effect Effects 0.000 abstract description 5
- 239000003921 oil Substances 0.000 description 45
- 238000001179 sorption measurement Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011358 absorbing material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
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- 229920000742 Cotton Polymers 0.000 description 1
- FHNINJWBTRXEBC-UHFFFAOYSA-N Sudan III Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 FHNINJWBTRXEBC-UHFFFAOYSA-N 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
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- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000011957 budget and coverage analysis Methods 0.000 description 1
- 239000003653 coastal water Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003305 oil spill Substances 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940099373 sudan iii Drugs 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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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
- 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
- C02F1/30—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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- 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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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
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Abstract
The invention discloses a cellulose/SiO2Composite aerogel photocatalytic material and preparation method thereof, and composite aerogel photocatalytic material loaded TiO2The invention provides a photocatalyst, and provides an oil absorption material which is green and environment-friendly, hydrophobic and oleophilic, absorbs oil and can degrade oil stains.
Description
Technical Field
The invention relates to the technical field of sea surface oil spill treatment, in particular to cellulose/SiO2A composite aerogel photocatalytic material and a preparation method thereof.
Background
With the rapid increase in the use and transportation of petroleum and chemical solvents, accidents of petroleum leakage and chemical leakage often occur around the world. Such accidents can severely contaminate coastal waters and our living environment and can also result in significant loss of valuable resources. The method is characterized in that the method comprises the following steps of treating large-scale spilled oil on the sea surface, intercepting the spilled oil by an oil containment boom, and then pumping the spilled oil by an oil skimmer, wherein a small amount of oil stains are remained on the sea surface finally, so that the common recovery and cleaning method for thin oil layers and small-area oil layers on the sea surface is an adsorption method. Natural materials such as zeolite, bentonite, wool fibers, etc. have been used for adsorption degreasing due to their porous structure and high specific surface area. However, these adsorption materials have limited practical applications due to their large density, low absorption rate, poor oil-water selectivity, and the like.
Therefore, development of novel environmentally friendly materials having super hydrophobicity and super lipophilicity is urgently needed to improve the process of cleaning and recovering oil stains. Aiming at the problems, the invention takes the waste paper cellulose and the methyltrimethoxysilane as raw materials to prepare the cellulose/SiO with excellent performance2The composite aerogel photocatalytic material has small aerogel density (the lowest density is 0.107 g/cm)3) The thermal stability is improved, and the oil absorption material is convenient to recycle and store; after being hydrolyzed, the methyl trimethoxy silane and the waste paper cellulose form a three-dimensional network structure, so that the mechanical property of the paper is improved, and the absorption and desorption of the oil absorption material are facilitated to be repeatedly utilized; -Si-CH3The oil-absorbing material is grafted to cellulose to ensure that the oil-absorbing material has good hydrophobicity and lipophilicity (the static hydrophobic contact angle can reach 148.5 degrees), the oil-water selectivity of the oil-absorbing material is improved, the oil adsorption capacity can reach 12 times of the self weight, the reutilization property after adsorption and desorption is good, and 90% of the oil-absorbing capacity is still realized after 10 times. The aerogel material is environment-friendly, has good performance, has good application potential in the aspect of adsorbing floating oil on the water surface, and is a resource utilization of waste paper. TiO 22The addition of the composite material endows the material with photocatalytic performance, and can degrade oil stains while absorbing the oil stains.
The invention provides a hydrophobic and oleophilic oil absorption material which can degrade oil stains while absorbing oil, and relates to cellulose/SiO2A composite aerogel photocatalytic material and a preparation method thereof.
Disclosure of Invention
In order to make up for the above disadvantages, the invention provides a cellulose/SiO2A composite aerogel photocatalytic material and a preparation method thereof.
The scheme of the invention is as follows:
cellulose/SiO2Composite aerogel photocatalytic material loaded with TiO2A photocatalyst.
As a preferred technical scheme, the TiO2The photocatalyst is TiO2Particulate or rare earth doped TiO2。
As a preferred technical scheme, the TiO2The addition amount of the composite aerogel photocatalytic material is 0.1-0.6% of the mass of the composite aerogel photocatalytic material.
The invention also provides a method for preparing the cellulose/SiO2A method of compounding an aerogel photocatalytic material, comprising the steps of:
step 1 hydrogel formation
Adding cellulose into a mixed solvent of dimethyl sulfoxide and ethanol at 30 ℃, and stirring until the cellulose is uniformly dispersed to obtain cellulose hydrogel;
Adding methyltrimethoxysilane, oxalic acid and deionized water into the cellulose hydrogel at 30 ℃, stirring for 30-60 min, hydrolyzing to obtain a solution A, and adding a certain amount of TiO into the solution A2Adding ammonia water diluted by dissolved dimethyl sulfoxide into the solution B, stirring for 15-45 min, and performing polycondensation to obtain a solution C; heating the solution C to 40-50 ℃ for heat preservation to obtain solid gel;
step 3 solid gel aging
Washing the solid gel obtained in the step 2 with ethanol for 3 times within 24 hours, and then soaking the solid gel in distilled water for 24 hours to finish the aging of the solid gel;
step 4 aerogel formation
Freezing the aged solid gel obtained in the step 3 at-20 ℃ for 6h, and then putting the frozen gel into a freeze dryer for drying; after the drying is finished, the supported TiO is obtained2cellulose/SiO2A composite aerogel photocatalytic material.
According to a preferable technical scheme, the mass ratio of the dimethyl sulfoxide to the ethanol in the mixed solvent of the dimethyl sulfoxide and the ethanol is (1-9): 1.
As a preferable technical scheme, the mass ratio of the methyltrimethoxysilane, the oxalic acid and the deionized water is 6.8: (0.45-1): (7.2-9.2).
In a preferred embodiment, the hydrolysis time of step 2 is 30min, and the polycondensation time of step 2 is 30 min.
According to a preferable technical scheme, the mass ratio of the methyltrimethoxysilane to the ammonia water is 1: (0.5 to 1.1).
As a preferable technical scheme, the cellulose is waste paper cellulose.
As a preferable technical scheme, the heat preservation temperature of the step 2 is 45 ℃.
Due to the adoption of the technical scheme, the cellulose/SiO2The composite aerogel photocatalytic material and the preparation method thereof comprise the following steps:
step 1 hydrogel formation
Adding cellulose into a mixed solvent of dimethyl sulfoxide and ethanol at 30 ℃, and stirring until the cellulose is uniformly dispersed to obtain cellulose hydrogel;
Adding methyltrimethoxysilane, oxalic acid and deionized water into the cellulose hydrogel at 30 ℃, stirring for 30-60 min, hydrolyzing to obtain a solution A, and adding a certain amount of TiO into the solution A2Adding ammonia water diluted by dissolved dimethyl sulfoxide into the solution B, stirring for 15-45 min, and performing polycondensation to obtain a solution C; heating the solution C to 40-50 ℃ for heat preservation to obtain solid gel;
step 3 solid gel aging
Washing the solid gel obtained in the step 2 with ethanol for 3 times within 24 hours, and then soaking the solid gel in distilled water for 24 hours to finish the aging of the solid gel;
step 4 aerogel formation
Freezing the aged solid gel obtained in the step 3 at-20 ℃ for 6h, and then putting the frozen gel into a freeze dryer for drying; after the drying is finished, the supported TiO is obtained2cellulose/SiO2A composite aerogel photocatalytic material.
The oil absorption material which is hydrophobic and oleophilic and can degrade oil stains while absorbing oil can be obtained.
Drawings
FIG. 1 Supported TiO2cellulose/SiO2The contact angle of the composite aerogel photocatalytic material;
FIG. 2 Supported TiO2cellulose/SiO2The oil absorption rate of the composite aerogel photocatalytic material is increased;
FIG. 3 cellulose/SiO2The adsorption capacity of the composite aerogel photocatalytic material to different oils changes along with time;
FIG. 4 cellulose/SiO2The composite aerogel photocatalytic material has cyclic use performance;
FIG. 5 shows the effect of the loading of the catalyst on the photocatalytic performance of the composite aerogel photocatalytic material.
Detailed Description
The invention is further illustrated below with reference to examples. The examples are intended to illustrate the invention, but not to limit the scope of the invention.
The first embodiment is as follows:
(1) formation of hydrogel: adding waste paper cellulose into dimethyl sulfoxide and ethanol at the temperature of 30 ℃, wherein the weight ratio of the waste paper cellulose to the dimethyl sulfoxide to the ethanol is 1: 1, stirring the mixed solvent until cellulose is uniformly dispersed to obtain waste paper cellulose hydrogel;
(2) formation of solid gel: at the temperature of 30 ℃, methyltrimethoxysilane, oxalic acid and deionized water are mixed according to the weight ratio of 6.8: 0.45: 7.2, stirring for 35min, hydrolyzing to obtain solution A, and adding TiO with the mass fraction of 0.3% in the solution A to obtain the composite aerogel photocatalytic material2Granulating to obtain a solution B, adding ammonia water diluted by dissolved dimethyl sulfoxide into the solution B, stirring for 30min, and performing polycondensation to obtain a solution C; heating the solution C to 45 ℃ for heat preservation to obtain solid gel;
(3) aging of solid gel: washing the solid gel with ethanol for 3 times within 24h, and then soaking the solid gel in distilled water for 24h to finish the aging of the solid gel;
(4) forming the aerogel: freezing the aged solid gel at-20 ℃ for 6h, and then putting the solid gel into a freeze dryer for drying; after the drying is finished, the supported TiO is obtained2cellulose/SiO2A composite aerogel photocatalytic material.
The mass ratio of the methyltrimethoxysilane to the ammonia water is 1: 0.5.
example two:
(1) formation of hydrogel: adding waste paper cellulose into dimethyl sulfoxide, ethanol 9: 1, stirring the mixed solvent until cellulose is uniformly dispersed to obtain waste paper cellulose hydrogel;
(2) formation of solid gel: at the temperature of 30 ℃, methyltrimethoxysilane, oxalic acid and deionized water are mixed according to the weight ratio of 6.8: 1: 9.2, stirring for 45min to obtain a solution A, and adding TiO doped with rare earth metal with the mass fraction of 0.5 percent of the composite aerogel photocatalytic material into the solution A2Adding ammonia water diluted by dissolved dimethyl sulfoxide into the solution B, stirring for 40min, and performing polycondensation to obtain a solution C; heating the solution C to 50 ℃ for heat preservation to obtain solid gel;
(3) aging of solid gel: washing the solid gel with ethanol for 3 times within 24h, and then soaking the solid gel in distilled water for 24h to finish the aging of the solid gel;
(4) forming the aerogel: freezing the aged solid gel at-20 ℃ for 6h, and then putting the solid gel into a freeze dryer for drying; after the drying is finished, the supported TiO is obtained2cellulose/SiO2A composite aerogel photocatalytic material.
The mass ratio of the methyltrimethoxysilane to the ammonia water is 1: 1.1.
example three:
(1) formation of hydrogel: at 30 ℃, add cellulose to dimethylsulfoxide, ethanol 5: 1, stirring the mixed solvent until cellulose is uniformly dispersed to obtain waste paper cellulose hydrogel;
(2) formation of solid gel: at the temperature of 30 ℃, methyl trimethoxySilane, oxalic acid and deionized water are mixed according to the weight ratio of 6.8: 0.7: 8 is added into the cellulose hydrogel and stirred for 37min for hydrolysis to obtain a solution A, and the TiO doped with the rare earth metal with the mass fraction of 0.6 percent of the composite aerogel photocatalytic material is added into the solution A2Adding ammonia water diluted by dissolved dimethyl sulfoxide into the solution B, stirring for 48min, and performing polycondensation to obtain a solution C; heating the solution C to 47 ℃ for heat preservation to obtain solid gel;
(3) aging of solid gel: washing the solid gel with ethanol for 3 times within 24h, and then soaking the solid gel in distilled water for 24h to finish the aging of the solid gel;
(4) forming the aerogel: freezing the aged solid gel at-20 ℃ for 6h, and then putting the solid gel into a freeze dryer for drying; after the drying is finished, the supported TiO is obtained2cellulose/SiO2A composite aerogel photocatalytic material.
The mass ratio of the methyltrimethoxysilane to the ammonia water is 1: 0.7.
as shown in FIG. 1, the hydrophobic angle of the composite aerogel photocatalytic material provided by the invention is about 148.5 degrees, and the composite aerogel photocatalytic material is close to a super-hydrophobic state, namely cellulose/SiO2Hydrophobic predominantly surface-grafted-OSi-CH3Plays an important role.
As shown in FIG. 2, the supported TiO2cellulose/SiO2The oil absorption rate and the oil absorption of the composite aerogel photocatalytic material are key factors for treating floating oil on water surface. Fig. 2 shows the change of the composite aerogel photocatalytic material in the adsorption of oil stains on water surface with time. A small piece of composite aerogel photocatalytic material is placed on the water surface of which pump oil (Sudan III dyeing) is dripped, oil stains are rapidly gathered around the composite aerogel photocatalytic material and are adsorbed, after 60 s, the color of the oil is lightened, a lot of floating oil is adsorbed, all coloring oil after 120s is adsorbed into the composite aerogel photocatalytic material, and the oil absorption speed is high. With pure SiO2Compared with the aerogel used for absorbing oil stains, the fragile aerogel framework can not bear the capillary force and is seriously broken. cellulose/SiO2The composite aerogel photocatalytic material can quickly and easily absorb oil stains from water without usingDestroying the integrity of the material. SEM analysis shows that the composite aerogel photocatalytic material has a large number of macropores, mesopores and micropores inside, and forms a fiber network structure with different pore diameters. The pores of different grades provide a diffusion channel (macropore) and an oil storage space (mesopore and micropore) for absorbing oil stains, and SiO on the surface of the cellulose2The hydrophobicity and the mechanical property of the cellulose aerogel are improved, so that the oil can be absorbed quickly, and the destructiveness of the composite aerogel photocatalytic material is reduced.
As shown in FIG. 3, cellulose/SiO2The absorption capacity of the composite aerogel photocatalytic material to various oils reaches saturation basically in about 50 s, and the change with time is small later, which shows that the absorption rate of the composite aerogel photocatalytic material to various oil stains is high, the oil absorption saturation time is improved by about 10 seconds compared with the oil absorption saturation time of the existing BCAs/SAs material, and the composite aerogel photocatalytic material has the advantages in the aspect of treating floating oil on the water surface.
As shown in fig. 4, the adsorption capacity of the composite aerogel photocatalytic material to various oils and organic solvents is 11 to 12.67 times of the weight of the composite aerogel photocatalytic material, which is about 1.5 times higher than that of the existing aerogel, at least 3 to 6 times higher than that of the traditional activated carbon, and 1 to 2 times higher than that of the "cotton candy-like" macroporous aerogel. The organic matter is mainly stored in the three-level pores of the composite aerogel photocatalytic material, the composite aerogel photocatalytic material mainly adopts physical adsorption as main chemical adsorption as auxiliary chemical adsorption, and the difference of the absorption capacity of the oil to be researched is related to the difference of the density and the functional group of organic liquid.
As shown in fig. 5, the TiO supported on the composite aerogel photocatalytic material2When the content of the composite material reaches 0.5%, the degradation efficiency of the composite material to crude oil reaches the maximum value. This is because increasing the amount of catalyst increases the photocatalytically active component and thus increases the TiO content2The degradation activity of (3). However, a high amount of catalyst not only causes agglomeration due to the presence of hydroxyl groups, resulting in an increase in the particle size thereof and a decrease in the specific surface area thereof, thereby preventing sunlight from contacting the catalyst.
The foregoing shows and describes the general principles of the present invention, its essential features, and its advantages. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. cellulose/SiO2The composite aerogel photocatalytic material is characterized in that: the composite aerogel photocatalytic material loaded TiO2A photocatalyst.
2. A cellulose/SiO as claimed in claim 12The composite aerogel photocatalytic material is characterized in that: the TiO is2The photocatalyst is TiO2Particulate or rare earth metal doped TiO2。
3. A cellulose/SiO as claimed in claim 22The composite aerogel photocatalytic material is characterized in that: the TiO is2The addition amount of the photocatalyst is 0.1-0.6% of the mass of the composite aerogel photocatalytic material.
4. A process for preparing a cellulose/SiO solid as claimed in any of claims 1 to 32The method for preparing the composite aerogel photocatalytic material is characterized by comprising the following steps of:
step 1 hydrogel formation
Adding cellulose into a mixed solvent of dimethyl sulfoxide and ethanol at 30 ℃, and stirring until the cellulose is uniformly dispersed to obtain cellulose hydrogel;
step 2 solid gel formation
Adding methyltrimethoxysilane, oxalic acid and deionized water into the cellulose hydrogel at 30 ℃, stirring for 30-60 min, hydrolyzing to obtain a solution A, and adding a certain amount of TiO into the solution A2Obtaining a solution B, adding ammonia water diluted by dissolved dimethyl sulfoxide into the solution BStirring for 15-45 min to perform polycondensation to obtain a solution C; heating the solution C to 40-50 ℃ for heat preservation to obtain solid gel;
step 3 solid gel aging
Washing the solid gel obtained in the step 2 with ethanol for 3 times within 24 hours, and then soaking the solid gel in distilled water for 24 hours to finish the aging of the solid gel;
step 4 aerogel formation
Freezing the aged solid gel obtained in the step 3 at-20 ℃ for 6h, and then putting the frozen gel into a freeze dryer for drying; after the drying is finished, the supported TiO is obtained2cellulose/SiO2A composite aerogel photocatalytic material.
5. A cellulose/SiO as claimed in claim 42The preparation method of the composite aerogel photocatalytic material is characterized by comprising the following steps of: the mass ratio of the dimethyl sulfoxide to the ethanol in the mixed solvent of the dimethyl sulfoxide and the ethanol is (1-9) to 1.
6. A cellulose/SiO as claimed in claim 42The preparation method of the composite aerogel photocatalytic material is characterized by comprising the following steps of: the mass ratio of the methyltrimethoxysilane to the oxalic acid to the deionized water is 6.8: (0.45-1): (7.2-9.2).
7. A cellulose/SiO as claimed in claim 42The preparation method of the composite aerogel photocatalytic material is characterized by comprising the following steps of: the hydrolysis time of the step 2 is 30min, and the polycondensation time of the step 2 is 30 min.
8. A cellulose/SiO as claimed in claim 42The preparation method of the composite aerogel photocatalytic material is characterized by comprising the following steps of: the mass ratio of the methyltrimethoxysilane to the ammonia water is 1: (0.5 to 1.1).
9. A cellulose/SiO as claimed in claim 42Preparation method of composite aerogel photocatalytic materialCharacterized in that: the cellulose is waste paper cellulose.
10. A cellulose/SiO as claimed in claim 42The preparation method of the composite aerogel photocatalytic material is characterized by comprising the following steps of: the heat preservation temperature of the step 2 is 45 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111481871A (en) * | 2020-04-21 | 2020-08-04 | 范数学 | Plastic garbage degradation treatment agent and preparation method thereof |
| CN115364904A (en) * | 2022-07-07 | 2022-11-22 | 福建省蓝光节能科技有限公司 | Photocatalyst for volatile organic pollutants and use method thereof |
| CN115463689A (en) * | 2022-09-14 | 2022-12-13 | 北方民族大学 | Method for catalyzing Suzuki-Miyaura coupling reaction by cellulose aerogel supported catalyst |
-
2019
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111481871A (en) * | 2020-04-21 | 2020-08-04 | 范数学 | Plastic garbage degradation treatment agent and preparation method thereof |
| CN115364904A (en) * | 2022-07-07 | 2022-11-22 | 福建省蓝光节能科技有限公司 | Photocatalyst for volatile organic pollutants and use method thereof |
| CN115463689A (en) * | 2022-09-14 | 2022-12-13 | 北方民族大学 | Method for catalyzing Suzuki-Miyaura coupling reaction by cellulose aerogel supported catalyst |
| CN115463689B (en) * | 2022-09-14 | 2023-11-03 | 北方民族大学 | Method for catalyzing Suzuki-Miyaura coupling reaction by using cellulose aerogel supported catalyst |
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