CN114985001A - Polyacrylonitrile non-woven fabric based photocatalytic material and preparation method and application thereof - Google Patents
Polyacrylonitrile non-woven fabric based photocatalytic material and preparation method and application thereof Download PDFInfo
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- CN114985001A CN114985001A CN202210502741.4A CN202210502741A CN114985001A CN 114985001 A CN114985001 A CN 114985001A CN 202210502741 A CN202210502741 A CN 202210502741A CN 114985001 A CN114985001 A CN 114985001A
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- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 136
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 134
- 239000000463 material Substances 0.000 title claims abstract description 60
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 58
- 230000008961 swelling Effects 0.000 claims abstract description 37
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000011068 loading method Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 37
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 15
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 108010061338 ranpirnase Proteins 0.000 abstract description 32
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
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- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 64
- 239000004408 titanium dioxide Substances 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
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- 238000012360 testing method Methods 0.000 description 9
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- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
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- 239000010936 titanium Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
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- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
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- 125000002560 nitrile group Chemical group 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
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- CUHVTYCUTYWQOR-UHFFFAOYSA-N formaldehyde Chemical compound O=C.O=C CUHVTYCUTYWQOR-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 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
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- 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
- B01D53/007—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 by irradiation
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- 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
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- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention provides a polyacrylonitrile non-woven fabric based photocatalytic material and a preparation method and application thereof. The preparation method of the polyacrylonitrile non-woven fabric based photocatalytic material comprises the following steps: s1 preparation of TiO-containing 2 The swelling solution of (4); s2, drying the polyacrylonitrile non-woven fabric after sequentially passing the swelling solution, the coagulating bath and the water solution to obtain TiO 2 Load(s)Onto the polyacrylonitrile nonwoven fabric; s3, loading TiO obtained in step S2 2 The polyacrylonitrile non-woven fabric is subjected to pre-oxidation treatment to obtain the polyacrylonitrile non-woven fabric-based photocatalytic material. TiO 2 2 Can be uniformly loaded on PAN non-woven fabric, and TiO can be regulated and controlled by adjusting the speed of polyacrylonitrile non-woven fabric passing through swelling liquid 2 The amount of load of (a); the pre-oxidized PAN non-woven fabric has adsorption effect on volatile organic pollutants and can be mixed with TiO 2 And the efficiency of catalytic degradation of volatile organic compounds is improved by the synergistic effect.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a polyacrylonitrile non-woven fabric based photocatalytic material and a preparation method and application thereof.
Background
The photocatalysis technology can convert harmful VOCs into harmless CO at normal temperature and normal pressure 2 And H 2 O, and has the advantages of low cost, simple operation, wide application range, less secondary pollution and the like. Therefore, the photocatalytic technology is considered to be an atmospheric environment purification technology with great potential for treating low-concentration VOCs. TiO 2 2 Commonly used as photocatalysts, but TiO 2 Since the size is too small (nano-scale), the recycling rate is not high, and the light utilization rate is low because the forbidden band width is too small (3.2eV), the recycling rate is improved if the light can be loaded on a substrate material. At present, metal mesh is used as a substrate material to load TiO 2 As a catalytic material, the metal mesh substrate material is relatively expensive. If a non-metallic base material is used, TiO 2 There is some degree of damage to the substrate material during the photocatalytic process. Therefore, the research and development of the novel efficient, light aging resistant and reusable photocatalytic material for VOS treatment has very important practical significance.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to provide a method for preparing a Polyacrylonitrile (PAN) nonwoven fabric-based photocatalytic material, TiO 2 Can be uniformly loadedLoaded on PAN non-woven fabric, TiO can be regulated and controlled by adjusting the speed of polyacrylonitrile non-woven fabric passing through swelling liquid 2 The amount of load of (a); the pre-oxidation treatment slows down the aging rate of the PAN non-woven fabric and prolongs the service life of the composite material; the pre-oxidized PAN non-woven fabric has adsorption effect on volatile organic pollutants and can be mixed with TiO 2 And the efficiency of catalytic degradation of volatile organic compounds is improved by the synergistic effect.
In one aspect of the present invention, the present invention provides a method for preparing a polyacrylonitrile non-woven fabric based photocatalytic material, which is characterized by comprising:
s1 preparation of TiO-containing 2 The swelling solution of (4);
s2, drying the polyacrylonitrile non-woven fabric after sequentially passing the swelling solution, the coagulating bath and the water solution to obtain TiO 2 Loading the polyacrylonitrile non-woven fabric;
s3, loading TiO obtained in step S2 2 The polyacrylonitrile non-woven fabric is subjected to pre-oxidation treatment to obtain the polyacrylonitrile non-woven fabric-based photocatalytic material.
Further, the preparation method of the swelling solution comprises the following steps:
mixing nano-scale TiO 2 Dispersing in a mixed solution of dimethyl sulfoxide and absolute ethyl alcohol, and performing ultrasonic dispersion uniformly to obtain the swelling solution.
Further, the time of ultrasonic dispersion is 10-20 min.
Further, in the swelling solution, TiO 2 The content is 0.01-0.1 g/L; the volume ratio of the dimethyl sulfoxide to the absolute ethyl alcohol is 80-90: 20 to 10.
Further, in step S2, the moving speed of the polyacrylonitrile nonwoven fabric through the swelling solution is 0.1-1 m/min;
and/or the speed of the polyacrylonitrile non-woven fabric passing through the coagulating bath and the aqueous solution is 1-5m/min respectively;
and/or the coagulation bath is deionized water.
Further, in step S2, the drying process includes: and (3) placing the polyacrylonitrile non-woven fabric which sequentially passes through the swelling solution, the coagulating bath and the aqueous solution in a vacuum oven, and drying for 24 hours at the temperature of 60 ℃.
Further, in step S3, the pre-oxidation conditions include: heating to 220-250 ℃ at a heating rate of 7-8 ℃/min, and keeping the temperature for 150 min.
Further, the TiO supported material obtained in the step S2 and having a size of 2-4 cm × 6-8 cm 2 The polyacrylonitrile non-woven fabric is put into an oven for pre-oxidation.
In another aspect of the invention, the invention provides a polyacrylonitrile non-woven fabric based photocatalytic material, which is prepared by the preparation method.
In another aspect of the present invention, the present invention provides a use of the above-mentioned polyacrylonitrile non-woven fabric based photocatalytic material for the treatment of volatile organic gases.
Compared with the prior art, the invention can at least obtain the following beneficial effects:
polyacrylonitrile (PAN) nonwoven fabric containing titanium dioxide (TiO) 2 ) The swelling solution can dissolve nano TiO 2 Uniformly loading the mixture on PAN non-woven fabric; TiO can be regulated and controlled by adjusting the speed of polyacrylonitrile non-woven fabric passing through swelling liquid 2 The amount of load of (a); the sunlight and the photocatalyst can generate etching damage effect on the substrate material, and the pre-oxidation treatment can slow down the aging rate of the PAN non-woven fabric and prolong the service life of the composite material; the pre-oxidized PAN non-woven fabric has adsorption effect on volatile organic pollutants and can be mixed with TiO 2 And the efficiency of catalytic degradation of volatile organic compounds is improved by the synergistic effect. The method has the advantages of simple process, environmental friendliness, low production cost, continuous preparation and uniform sample.
The polyacrylonitrile non-woven fabric-based photocatalytic material prepared by the preparation method is low in price.
Drawings
FIG. 1 is a schematic view of a process flow for preparing the polyacrylonitrile nonwoven fabric-based photocatalytic material of example 1;
FIG. 2 shows SEM and EDX test results of the polyacrylonitrile nonwoven fabric-based photocatalytic material, the SEM image of PAN nonwoven fabric, and TiO-supported photocatalyst material in example 1 2 SEM image of PAN nonwoven fabric of (1);
fig. 3 shows FTIR test results of the materials of example 1 and XPS test results of the polyacrylonitrile nonwoven fabric-based photocatalytic material;
FIG. 4 is a graph of fiber break strength versus time of light, TGA and DTG test results for each of the materials of example 1;
FIG. 5 shows a photocatalytic reactor according to example 3;
in fig. 6, a and b represent the photocatalytic removal efficiency of the polyacrylonitrile nonwoven fabric based photocatalytic material for toluene and formaldehyde in example 1, respectively.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In one aspect of the present invention, the present invention provides a method for preparing a polyacrylonitrile non-woven fabric based photocatalytic material, which is characterized by comprising:
s1 preparation of TiO-containing 2 The swelling solution of (4).
In some embodiments of the present invention, the method for preparing the swelling solution comprises: mixing nano-scale TiO 2 Dispersing in a mixed solution of dimethyl sulfoxide and absolute ethyl alcohol, and performing ultrasonic dispersion uniformly to obtain the swelling solution; the ultrasonic dispersion time is 10-20 min.
In some embodiments of the invention, the swelling solution is TiO 2 The content is 0.01-0.1 g/L; the volume ratio of the dimethyl sulfoxide to the absolute ethyl alcohol is 80-90: 20 to 10.
S2, passing the polyacrylonitrile non-woven fabric through the swelling solution, the coagulating bath and the water solution in sequenceDrying the mixture to obtain TiO 2 And loading the polyacrylonitrile non-woven fabric.
In some embodiments of the invention, Polyacrylonitrile (PAN) nonwoven is a precursor of carbon fiber, is resistant to high temperature, can be pre-oxidized at 220 degrees, and has stronger thermal stability than other nonwoven fibers; and the PAN non-woven fabric has low cost and is suitable for large-scale application.
In some embodiments of the present invention, in step S2, the moving speed of the polyacrylonitrile nonwoven fabric through the swelling solution is 0.1-1m/min (for example, 0.1m/min, 0.3m/min, 0.5m/min, 0.7m/min, 0.9m/min, 1m/min, etc.). Thus, TiO can be made 2 Uniformly loaded on the polyacrylonitrile non-woven fabric.
In some embodiments of the invention, the coagulation bath is deionized water.
In some embodiments of the invention, the polyacrylonitrile nonwoven fabric passes through the coagulation bath and the aqueous solution at a rate of 1-5m/min (e.g., may be 1m/min, 2m/min, 3m/min, 4m/min, or 5m/min, etc.), respectively.
In some embodiments of the present invention, in step S2, the drying process includes: and (3) placing the polyacrylonitrile non-woven fabric which sequentially passes through the swelling solution, the coagulating bath and the water solution in a vacuum oven, and drying at the temperature of 60 ℃ for 24 hours.
S3, loading TiO obtained in step S2 2 The polyacrylonitrile non-woven fabric is subjected to pre-oxidation treatment to obtain the polyacrylonitrile non-woven fabric-based photocatalytic material.
In some embodiments of the invention, in step S3, the pre-oxidation conditions include: heating to 220-250 deg.C (for example, 220 deg.C, 230 deg.C, 240 deg.C or 250 deg.C) at a heating rate of 7-8 deg.C/min, and holding for 100-150min (for example, 100min, 110min, 120min, 130min, 140min or 150 min).
In some embodiments of the present invention, the TiO-loaded material obtained in step S2 with a size of 2-4 cm × 6-8 cm 2 Putting the polyacrylonitrile non-woven fabric into an oven for pre-oxidation。
The dimension of 2-4 cm × 6-8 cm refers to the width × length dimension.
The inventor finds that Polyacrylonitrile (PAN) non-woven fabric has the characteristics of low cost, large specific surface area, excellent adsorption performance and the like, and is suitable for being used as TiO 2 But TiO, a base material of 2 There is some degree of damage to the substrate material during the photocatalytic process. And the pre-oxidation treatment can slow down the aging rate of the PAN non-woven fabric and prolong the service life of the composite material.
In the present invention, the polyacrylonitrile nonwoven fabric contains titanium dioxide (TiO) 2 ) The swelling solution can dissolve nano TiO 2 Uniformly loading the mixture on PAN non-woven fabric; TiO can be regulated and controlled by adjusting the speed of polyacrylonitrile non-woven fabric passing through swelling liquid 2 The amount of load of (a); the sunlight and the photocatalyst can generate etching damage effect on the substrate material, and the pre-oxidation treatment can slow down the aging rate of the PAN non-woven fabric and prolong the service life of the composite material; the pre-oxidized PAN non-woven fabric has adsorption effect on volatile organic pollutants and can be mixed with TiO 2 And the efficiency of catalytic degradation of volatile organic compounds is improved by the synergistic effect. The method of the invention can be used for continuous preparation, and the obtained samples are relatively uniform.
In some embodiments of the present invention, the preparation method of the polyacrylonitrile non-woven fabric based photocatalytic material comprises the following steps:
(1) containing TiO 2 Preparation of the swelling solution
Weighing a certain amount of nano-grade TiO 2 (P25), dispersing in a mixed solution of dimethyl sulfoxide (DMSO) and absolute ethyl alcohol (EtOH), and uniformly dispersing by ultrasonic to prepare a swelling solution.
(2)TiO 2 Loaded on PAN non-woven fabric
Passing the PAN non-woven fabric into the swelling solution prepared in the step (1) at a certain speed, taking out the PAN non-woven fabric, passing the PAN non-woven fabric through a coagulating bath and a deionized water solution at a certain speed, and then drying the PAN non-woven fabric in a vacuum oven at 60 ℃ for 24 hours to obtain the supported TiO 2 The PAN nonwoven fabric of (1).
(3) Supported TiO 2 PAN non-woven fabric pre-oxidation
Taking the loaded TiO prepared in the step (2) with a certain size 2 The PAN non-woven fabric is put into an oven, heated to a certain temperature at a certain speed, kept warm for a certain time, cooled to room temperature and taken out to obtain the polyacrylonitrile non-woven fabric-based photocatalytic material with metallic luster.
In another aspect of the invention, the invention provides a polyacrylonitrile non-woven fabric based photocatalytic material, which is prepared by the preparation method.
In another aspect of the present invention, the present invention provides a use of the polyacrylonitrile non-woven fabric based photocatalytic material described above for the treatment of volatile organic gases.
It can be understood that the polyacrylonitrile non-woven fabric based photocatalytic material is used as a photocatalyst to treat volatile organic gases; volatile organic gases include toluene, formaldehyde, and the like.
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Examples
Example 1
The preparation method of the polyacrylonitrile non-woven fabric based photocatalytic material comprises the following steps:
0.1g of commercial nanoscale TiO was weighed 2 (P25), 1000mL of a mixed solution of dimethyl sulfoxide (DMSO) and absolute ethanol (EtOH) (the volume ratio of DMSO to EtOH is 9:1), and ultrasonic dispersion is carried out for 20min to prepare a swelling solution. Unwinding PAN non-woven fabric from a reel, passing through swelling liquid containing P25 at the speed of 1m/min, then passing through coagulating bath and deionized water solution at the speed of 5m/min, taking out, placing in a vacuum oven at 60 ℃ and drying for 24h to obtain the supported TiO 2 PAN nonwoven (labeled TiO) 2 @ PAN nonwoven). Will support TiO 2 The PAN non-woven fabric is put into an oven, heated to 220 ℃ at the speed of 8 ℃/min and insulated for 150min, cooled to room temperature and taken out to obtain the polyacrylonitrile non-woven fabric based photocatalytic material (marked as preoxidized TiO) 2 @ PAN non-woven fabric), the preparation process flow is shown in figure 1 (wherein, the figure shows1 is a schematic diagram, and in the actual operation process, the PAN non-woven fabric passes through a swelling solution, a coagulating bath and a water washing bath in different containers, and the passing rates can be different from each other).
The results of SEM and EDX tests of the polyacrylonitrile nonwoven fabric-based photocatalytic material of the embodiment are shown in FIG. 2 (wherein, a 'in FIG. 2 are SEM pictures of PAN nonwoven fabric, and b, b' are TiO nonwoven fabric 2 SEM figure of @ PAN non-woven fabric, c and c' are pre-oxidized TiO 2 SEM image of @ PAN non-woven fabric, d is pre-oxidized TiO 2 EDX image of @ PAN nonwoven). The fiber surface of the untreated PAN nonwoven fabric exhibits smooth ravines (as shown in a and a' in fig. 2), which conform to the fiber surface topography of the polyacrylonitrile nonwoven fabric. TiO 2 2 After loading the nanoparticles, the surface appeared rough (as shown in b, b' in FIG. 2), indicating that TiO 2 The nanoparticles were successfully and uniformly supported on the PAN nonwoven. The rough surface of the fiber was maintained after the pre-oxidation treatment (as shown in c, c' in FIG. 2), indicating that TiO was present after the pre-oxidation treatment 2 The nano particles can be uniformly distributed on the fiber surface of the PAN non-woven fabric. SEM image shows that TiO 2 The nano particles are successfully loaded on the PAN non-woven fabric, and the nano particles can still be uniformly distributed on the surface of the PAN non-woven fabric after the pre-oxidation treatment. In addition, it is also possible to pre-oxidize TiO 2 @ PAN fiber samples were subjected to EDX detection (as shown in FIG. 2 at d, e and f), further demonstrating TiO 2 The nano particles are successfully loaded and uniformly distributed on the pre-oxidized PAN non-woven fabric.
The results of FTIR and XPS tests of the polyacrylonitrile nonwoven fabric-based photocatalytic material of the present example are shown in fig. 3 (wherein a in fig. 3 is PAN nonwoven fabric (labeled as PAN), pre-oxidized PAN nonwoven fabric (labeled as P-PAN), TiO nonwoven fabric, and 2 @ PAN non-woven fabric (labeled TiO in the figure) 2 @ PAN) and pre-oxidized TiO 2 @ PAN non-woven fabric (marked as P-TiO in the figure) 2 @ PAN), b in FIG. 3 is pre-oxidized TiO 2 XPS Spectrum of @ PAN nonwoven Fabric, c in FIG. 3 is Pre-oxidized TiO 2 @ PAN nonwoven Fabric C1s Spectrum, d in FIG. 3 being Pre-oxidized TiO 2 @ PAN nonwoven Fabric Ti 2p Spectrum). As can be seen from a in FIG. 3, TiO pre-oxidized compared to untreated PAN nonwoven fabric 2 The loaded PAN non-woven fabric is 680cm -1 And 1592cm -1 The corresponding characteristic peaks for Ti-O-Ti and C ═ N appear. Description of TiO 2 The nano particles are successfully loaded on the PAN non-woven fabric, and C ≡ N in the PAN fiber is converted into C ≡ N after pre-oxidation treatment. XPS characterization to evaluate pre-oxidized TiO 2 @ PAN nonwoven Fabric surface composition (b, c, d in FIG. 3). XPS measurement spectra show signals for the elements Ti, C, N and O. XPS spectra of Ti 2p confirmed two peaks for Ti 2p1/2 and Ti 2p3/2 at 464.4eV and 458.5eV, further demonstrating that TiO 2 Successfully loaded on PAN non-woven fabrics. The main peak at 284.6eV is assigned to the pre-oxidized TiO 2 @ PAN non-woven fabric contains carbon as an indefinite element and a C-C bond. The peak 286.2eV is derived from nitrile groups and 288.6eV shows that preoxidized TiO 2 Part of nitrile groups in the non-woven fabric fiber of @ PAN are changed into N ═ C-N conjugated structures, and the success of preoxidation is shown. The XPS data sheet further indicates that TiO 2 Successfully supported on the fibers of the PAN nonwoven and the pre-oxidation was successful.
The strength test, TGA and DTG analysis of the polyacrylonitrile nonwoven fabric-based photocatalytic material of the embodiment are shown in fig. 4 (wherein, a and b in fig. 4 are PAN nonwoven fabrics (labeled as PAN), TiO nonwoven fabrics treated by different methods 2 @ PAN nonwoven Fabric (labeled TiO in the figure) 2 @ PAN) and pre-oxidized TiO 2 @ PAN non-woven fabric (marked as P-TiO in the figure) 2 @ PAN) fiber breaking strength versus illumination time; in FIG. 4, c and d are PAN nonwoven fabric (PAN in the figure), pre-oxidized PAN nonwoven fabric (P-PAN in the figure), and TiO, respectively 2 @ PAN nonwoven Fabric (labeled TiO in the figure) 2 @ PAN) and pre-oxidized TiO 2 @ PAN non-woven fabric (marked as P-TiO in the figure) 2 @ PAN) TGA and DTG test results).
A and b in fig. 4 show that the breaking strength of the fiber decreases with the irradiation time. This is due to the fact that C ≡ N in some PAN fibers is photo-converted to C ≡ N. The C ≡ N group with strong polarity is gradually converted into C ≡ N, resulting in gradually weakened intramolecular and intermolecular dipole-dipole forces, and correspondingly reduced cohesive energy and association force of macromolecules. The load required for cohesive energy is reduced and thus the tensile strength is gradually reduced. Wherein, after the breaking strength of the fiber is reduced, the breaking strength is in the order of P-TiO 2 @PAN<P-PAN<TiO 2 @ PAN. According to the absolute value of the slope of the change curve of the breaking strength of the optical fiber along with the illumination time, the breaking strength of the optical fiber can be judged, and the aging rate can be further obtained. k is a radical of 1 、k 2 And k 3 Correspond in turn to TiO 2 @ PAN, P-PAN and P-TiO 2 @ PAN strongly varies slope. Slope absolute value of P-PAN is maximum (| k) 2 0.00308) indicating that it ages the fastest after sun exposure, and P-TiO 2 Absolute value of slope of @ PAN is minimum (| k) 3 0.00158) indicating that it ages the slowest when exposed to sunlight. This is probably because the PAN fibers form a more stable ladder-like structure after pre-oxidation treatment, which improves their physical stability and slows down the aging rate of the fibers. In fig. 4, c and d are TGA and DTG spectra of PAN nonwoven fabrics treated by different treatment methods. P-TiO 2 2 The titania loading on @ PAN was 4.1 wt%. PAN, TiO 2 @ PAN, P-PAN and P-TiO 2 The maximum pyrolysis temperatures of @ PAN are 318.1 deg.C, 319.43 deg.C, 347.58 deg.C and 347.99 deg.C, respectively. After pre-oxidation, the maximum pyrolysis temperature of PAN and P-PAN is respectively increased by 29 ℃, and the thermal stability is improved because the pre-oxidized polyacrylonitrile generates cyclization reaction and a generated ladder-shaped structure, so that the thermal stability is improved.
Example 2
The preparation method of the polyacrylonitrile non-woven fabric based photocatalytic material comprises the following steps:
0.01g of commercial nanoscale TiO was weighed 2 (P25), 1000mL of a mixed solution of dimethyl sulfoxide (DMSO) and absolute ethanol (EtOH) (volume ratio of DMSO to EtOH is 8:2), and ultrasonic dispersion is carried out for 10min to prepare a swelling solution. Unwinding PAN non-woven fabric from a reel, passing through a swelling solution containing P25 at the speed of 0.1m/min, then passing through a coagulating bath and a deionized water solution at the speed of 1m/min, taking out, and placing in a vacuum oven at 60 ℃ for drying for 24h to obtain the supported TiO 2 The PAN nonwoven fabric of (1). Will support TiO 2 The PAN non-woven fabric is put into an oven, heated to 250 ℃ at the speed of 7 ℃/min and insulated for 100min, cooled to room temperature and taken out to obtain the pre-oxidized load TiO with metallic luster 2 The PAN nonwoven fabric-based photocatalytic material of (1) was consistent with example 1 in the structure and performance test.
Example 3
Testing the catalytic performance of the polyacrylonitrile non-woven fabric-based photocatalytic material:
the polyacrylonitrile nonwoven fabric-based photocatalytic material prepared in example 1 was placed in a home-made photocatalytic reactor (see fig. 5, in which the reactor on the right side of the gas removal system in fig. 5 is an enlarged view of the sample chamber, the reaction chamber above the reactor is an enlarged view of the reaction chamber in the reactor, and the pre-oxidized TiO on the left side of the reaction chamber is 2 @ PAN nonwoven fabric is an enlarged view of the polyacrylonitrile nonwoven fabric-based photocatalytic material prepared in example 1 placed in a reaction chamber, respectively), a gas injector and a gas pump inject model gas into a sample chamber, the gas is collected in a gas chromatograph after reacting for a period of time, and the gas components and content after reacting are analyzed by a computer. The specific operation process is as follows: a certain amount of Toluene (Toluene) is injected at one time, the whole system is kept in closed cycle by an air pump, adsorption balance is achieved after adsorption is carried out for a certain time, then ultraviolet light is turned on to irradiate for a certain time, the Toluene concentration is dynamically measured in real time by using a gas infrared instrument in the whole adsorption degradation process, and the degradation effect is shown as a in figure 6. As can be seen from a in fig. 6, the adsorption is balanced for 3.4h, and the degradation rate is 75% after 4.5h of photocatalytic degradation. And (3) injecting Formaldehyde (Formaldehyde) gas into the reactor in the same operation, wherein the adsorption and degradation effects are shown as b in figure 6, no adsorption occurs in the treatment process, and the degradation rate of the toluene is 92% after 4.5h of photocatalytic degradation. The experimental result shows that the polyacrylonitrile non-woven fabric-based photocatalytic material prepared in the example 1 has a good photocatalytic degradation effect on volatile gas pollutants such as toluene and formaldehyde.
The above is not mentioned, is suitable for the prior art.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
While certain specific embodiments of the present invention have been described in detail by way of illustration, it should be understood by those skilled in the art that the foregoing description is for purposes of illustration only and not by way of limitation, and that various modifications, additions and substitutions can be made to the specific embodiments described without departing from the scope of the invention as defined in the accompanying claims. It should be understood by those skilled in the art that any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention shall be included in the scope of the present invention.
Claims (10)
1. A preparation method of a polyacrylonitrile non-woven fabric based photocatalytic material is characterized by comprising the following steps:
s1 preparation of TiO-containing 2 The swelling solution of (4);
s2, drying the polyacrylonitrile non-woven fabric after sequentially passing the swelling solution, the coagulating bath and the water solution to obtain TiO 2 Loading the polyacrylonitrile non-woven fabric;
s3, loading TiO obtained in step S2 2 The polyacrylonitrile non-woven fabric is subjected to pre-oxidation treatment to obtain the polyacrylonitrile non-woven fabric-based photocatalytic material.
2. The method according to claim 1, wherein the swelling solution is prepared by a method comprising:
mixing nano-scale TiO 2 Dispersing in a mixed solution of dimethyl sulfoxide and absolute ethyl alcohol, and performing ultrasonic dispersion uniformly to obtain the swelling solution.
3. The method of claim 2, wherein the time of ultrasonic dispersion is 10-20 min.
4. The method according to claim 2 or 3, wherein TiO is contained in the swelling solution 2 The content is 0.01-0.1 g/L; the volume ratio of the dimethyl sulfoxide to the absolute ethyl alcohol is 80-90: 20 to 10.
5. The production method according to claim 1, wherein in step S2, the moving speed of the polyacrylonitrile nonwoven fabric through the swelling liquid is 0.1 to 1 m/min;
and/or the speed of the polyacrylonitrile non-woven fabric passing through the coagulating bath and the aqueous solution is 1-5m/min respectively;
and/or the coagulating bath is deionized water.
6. The production method according to claim 1, wherein in step S2, the drying process includes: and (3) placing the polyacrylonitrile non-woven fabric which sequentially passes through the swelling solution, the coagulating bath and the water solution in a vacuum oven, and drying at the temperature of 60 ℃ for 24 hours.
7. The method according to claim 1, wherein in step S3, the pre-oxidation conditions include: heating to 220-250 ℃ at a heating rate of 7-8 ℃/min, and keeping the temperature for 150 min.
8. The method according to claim 7, wherein the TiO-supported material obtained in step S2 is 2 to 4cm by 6 to 8cm in size 2 The polyacrylonitrile non-woven fabric is put into an oven for pre-oxidation.
9. A polyacrylonitrile non-woven fabric based photocatalytic material, characterized in that the material is prepared by the preparation method of any one of claims 1 to 8.
10. Use of the photocatalytic material based on polyacrylonitrile nonwoven fabric according to claim 9, characterized in that the photocatalytic material based on polyacrylonitrile nonwoven fabric is used for the treatment of volatile organic gases.
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