CN109107558A - Catalysis material and preparation method thereof, fabric - Google Patents
Catalysis material and preparation method thereof, fabric Download PDFInfo
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- CN109107558A CN109107558A CN201811040306.4A CN201811040306A CN109107558A CN 109107558 A CN109107558 A CN 109107558A CN 201811040306 A CN201811040306 A CN 201811040306A CN 109107558 A CN109107558 A CN 109107558A
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- 239000000463 material Substances 0.000 title claims abstract description 107
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 90
- 239000004744 fabric Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 188
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 145
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 144
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 83
- 239000002105 nanoparticle Substances 0.000 claims abstract description 66
- 238000000265 homogenisation Methods 0.000 claims abstract description 20
- 238000012545 processing Methods 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000007921 spray Substances 0.000 claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 26
- 239000013078 crystal Substances 0.000 claims description 20
- 238000001694 spray drying Methods 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 7
- 230000036571 hydration Effects 0.000 claims description 7
- 238000006703 hydration reaction Methods 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 23
- 230000001699 photocatalysis Effects 0.000 abstract description 23
- 150000001875 compounds Chemical class 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 14
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 3
- 229920000742 Cotton Polymers 0.000 description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- 238000005507 spraying Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000222122 Candida albicans Species 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 229940095731 candida albicans Drugs 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000035614 depigmentation Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 241000233866 Fungi Species 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
-
- 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
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- 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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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
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- B01D2255/20707—Titanium
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- D06M2101/02—Natural fibres, other than mineral fibres
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Abstract
The present invention relates to a kind of catalysis materials and preparation method thereof, fabric.The preparation method of the catalysis material includes: offer graphene oxide solution；Thermal reduction processing is carried out to graphene oxide solution, obtains graphene solution, the concentration of the graphene in graphene solution is 10mg/mL~20mg/mL, and the oxygen content of graphene is 5w%~10w%；Hydrated titanium dioxide is added into graphene solution, and carries out homogenization, obtains mixed liquor；Mixed liquor is spray-dried using spray dryer, obtains catalysis material.Obtained catalysis material is combined by graphene and titanium dioxide nano-particle, and there are gaps between graphene and titanium dioxide nano-particle.Pass through the compound catalysis material of the available graphene of the preparation method and titanium dioxide nano-particle, to effectively improve the photocatalysis effect of titanium dioxide nano-particle, and then when catalysis material is applied to fabric, can be with the polluted gas in efficient degradation environment.
Description
Technical field
The present invention relates to catalyst fields, more particularly to catalysis material and preparation method thereof, fabric.
Background technique
In the world can be many as having for catalysis material, including titanium dioxide, zinc oxide, tin oxide, zirconium dioxide, sulphur
The semiconductor of many oxides such as cadmium, sulfide.Wherein, titanium dioxide because its oxidability it is strong, chemical property stablize it is nontoxic,
As nano photocatalyst catalytic material most hot in the world, it is widely used in the industries such as sewage treatment, gas purification.But two
The forbidden bandwidth of titanium oxide is larger, and the only absorption biggish photon of energy can just be such that valence-band electrons migrate to conduction band, so electronics
It can just be excited under ultraviolet light.In addition, the light induced electron of titanium dioxide and hole are easily compound, its photocatalysis effect is limited
Performance.
Summary of the invention
Based on this, it is necessary to aiming at the problem that optically catalytic TiO 2 effect, provide a kind of catalysis material and its preparation
Method, fabric；By the compound catalysis material of the available graphene of the preparation method and titanium dioxide nano-particle, thus
It can efficiently be dropped when effectively improving the photocatalysis effect of titanium dioxide nano-particle, and then the catalysis material being applied to fabric
Solve the polluted gas in environment.
A kind of preparation method of catalysis material, comprising the following steps:
Graphene oxide solution is provided；
Thermal reduction processing is carried out to the graphene oxide solution, obtains graphene solution, in the graphene solution
The concentration of graphene is 10mg/mL~20mg/mL, and the oxygen content of graphene is 5w%~10w%；
Hydrated titanium dioxide is added into the graphene solution, and carries out homogenization, obtains mixed liquor；
The mixed liquor is spray-dried using spray dryer, obtains catalysis material, the catalysis material
It is combined by graphene and titanium dioxide nano-particle, there is sky between the graphene and the titanium dioxide nano-particle
Gap.
The temperature of the thermal reduction processing is 300 DEG C~400 DEG C in one of the embodiments,.
The pressure of the homogenization is 120MPa~180MPa, flow 50mL/min in one of the embodiments,
~80mL/min.
The mass ratio of graphene and hydrated titanium dioxide is 1:3~6 in the mixed liquor in one of the embodiments:
1。
The intake air temperature of the spray drying is 170 DEG C~190 DEG C in one of the embodiments, air outlet temperature
It is 100 DEG C~110 DEG C.
The graphene oxide solution is prepared by Hummers method in one of the embodiments,.
The preparation method of catalysis material of the present invention has the advantages that
The light that graphene and titanium dioxide nano-particle are combined may be implemented using the method for spray drying in the present invention
Prepared by the scale and serialization of catalysis material, and obtained catalysis material size is uniform, graphene and nano titania
Particle is firmly combined, stability is good.
The concentration of graphene is high in mixed liquor of the present invention, be uniformly dispersed, stability is good, and in the preparation of graphene dispersing solution
It is compound that chemical reagent, the obtained graphenes and titanium dioxide nano-particle such as surfactant, reducing agent are not used in the process
Catalysis material is nontoxic, highly-safe, is widely used.
The present invention replaces the calcination processing after spray drying using thermal reduction processing, and graphene oxide is first carried out also original place
Reason, the controllable obtained graphene surface that restores retains part oxygen-containing group, further convenient for catalysis material and other materials
It is compound.Simultaneously, it is thus also avoided that the crystal transfer of titanium dioxide nano-particle, rutile-type and anatase during calcination processing
The mixed crystal type titanium dioxide nano-particle of type can produce synergistic effect, hinders the compound of light induced electron and electron hole, provides
The photocatalysis effect of catalysis material.
A kind of catalysis material obtained such as above-mentioned preparation method, the catalysis material are received by graphene and titanium dioxide
Rice corpuscles is combined, and there are gaps between the graphene and the titanium dioxide nano-particle.
The crystal form of the titanium dioxide nano-particle includes Detitanium-ore-type and rutile-type in one of the embodiments,.
In catalysis material of the invention, the specific surface area of graphene is high, electron transmission is had excellent performance, and can be effectively reduced
The band gap width of titanium dioxide nano-particle forms energy level difference with titanium dioxide nano-particle, receives to widen titanium dioxide
The optical response range of rice corpuscles.In turn, titanium dioxide nano-particle can be enable to be excited under natural light irradiation, generates photoproduction electricity
Son, and the recombination rate in light induced electron and hole is effectively reduced, the photocatalysis effect of titanium dioxide nano-particle significantly improves.
The graphene surface of catalysis material of the invention retains part oxygen-containing group, convenient for catalysis material and other materials
Material is further compound.Meanwhile the crystal form of the titanium dioxide nano-particle in catalysis material of the present invention include rutile-type with it is sharp
Titanium ore type, the titanium dioxide nano-particle of mixed crystal type can produce synergistic effect, hinder the compound of light induced electron and electron hole,
The photocatalysis effect of photochemical catalyst is provided.
Dirt in catalysis material of the invention, there are gap between graphene and titanium dioxide nano-particle, in air
Dye object molecule (VOC etc.) can from gap enter and come into full contact with titanium dioxide nano-particle, and be broken down into carbon dioxide with
Water, then shed from gap, light-catalysed efficiency significantly improves.Meanwhile catalysis material itself is lossless, and has operation letter
Singly, the advantages that low energy consumption, without secondary pollution.
A kind of fabric, load has above-mentioned catalysis material on the fabric.
The mass ratio of the fabric and photochemical catalyst is 1:(0.1~0.2 in one of the embodiments).
Fabric of the invention can be by organic pollutants such as formaldehyde, toluene, polycyclic aromatic hydrocarbons in air under illumination condition
High efficiency photocatalysis degradation is carried out, it is easy to use without other conditions such as ultraviolet lights.Therefore, fabric can be widely applied in automobile,
Between new clothes room, pet, a variety of living scenes such as wardrobe, toilet, can be carried around, can also standing type sprawl or hang use.
Fabric of the invention can also be killed, inhibit staphylococcus aureus, Escherichia coli, mould, Candida albicans etc. more
Thin, fungi is planted, the purpose of purification air is finally reached.
Specific embodiment
Catalysis material provided by the invention and preparation method thereof, fabric will be described further below.
The preparation method of catalysis material provided by the invention the following steps are included:
S1 provides graphene oxide solution；
S2 carries out thermal reduction processing to the graphene oxide solution, obtains graphene solution, in the graphene solution
The concentration of graphene be 10mg/mL~20mg/mL, the oxygen content of graphene is 5w%~10w%；
Hydrated titanium dioxide is added into the graphene solution, and carries out homogenization by S3, obtains mixed liquor；
The mixed liquor is spray-dried using spray dryer, obtains catalysis material, the photocatalysis material by S4
Material is combined by graphene and titanium dioxide nano-particle, is existed between the graphene and the titanium dioxide nano-particle
Gap.
In step S1, the graphene oxide solution is prepared by Hummers method.When the preparation process of Hummers method
Effect property is relatively preferably and also relatively safer in preparation process, and can be formed and be stablized in water, the mono-layer oxidized stone of sundown
Black alkene suspension.
In step S2, graphene oxide is after thermal reduction is handled, and oxygen-containing functional group depigmentation is reduced, the graphene made
Forbidden bandwidth reduce, can express apparent semiconductor behavior.
Specifically, the temperature of the thermal reduction processing is 300 DEG C~400 DEG C.In the temperature range, graphene oxide
On C-OH the basic depigmentation of OH group, C-O-C group major part depigmentation, the oxygen content 5w% of the graphene made~
10w%, the graphene that can make show semiconductor behavior and graphene are made to have preferable dispersibility, improve
The concentration of graphene in graphene solution.Moreover, in this step, the high toxicity reducing agent such as hydrazine hydrate etc is not used,
Safety is higher.
In step S3, by homogenization, graphene and the hydrated titanium dioxide of addition can be made uniformly to be scattered in molten
Mixed liquor is formed in liquid.Specifically, the pressure of the homogenization be 120MPa~180MPa, flow be 50mL/min~
80mL/min。
Wherein, hydrated titanium dioxide has the function of preventing graphene from reuniting, and the dispersity of mixed liquor can be made more stable.
Specifically, the mass ratio of graphene and hydrated titanium dioxide is 1:3~6:1 in the mixed liquor.Spray drying and
Available graphene and the preferable compound catalysis material of hydrated titanium dioxide after calcining.
In step S4, hydrated titanium dioxide (TiO (OH) after spray drying2) generate titanium dioxide nano-particle be mixed crystal
Type, there is higher photocatalysis performance compared to the titanium dioxide nano-particle of pure Detitanium-ore-type.Moreover, in catalytic process
In, the mixed crystal type of rutile-type and Detitanium-ore-type is equivalent to two kinds of semiconductors couplings, can produce synergistic effect, hinders photoproduction electricity
Son is compound with electron hole.
Specifically, the intake air temperature of the spray drying is 170 DEG C~190 DEG C, air outlet temperature is 100 DEG C~110
DEG C, speed 5mL/min~10mL/min of spray drying.Temperature into and out of air port needs conducive to after mixed liquor spray atomization
Water effective volatilization in droplet, temperature is too low to be unfavorable for its volatilization, too high also to have negative effect.In view of technique is convenient
Property, it is preferred that the intake air temperature of the spray drying is 170 DEG C, and air outlet temperature is 105 DEG C, and the speed of spray drying is
5mL/min。
The light that graphene and titanium dioxide nano-particle are combined may be implemented using the method for spray drying in the present invention
Prepared by the scale and serialization of catalysis material, and obtained catalysis material size is uniform, graphene and nano titania
Particle is firmly combined, stability is good.
The concentration of graphene is high in mixed liquor of the present invention, be uniformly dispersed, stability is good, and in the preparation of graphene dispersing solution
It is compound that chemical reagent, the obtained graphenes and titanium dioxide nano-particle such as surfactant, reducing agent are not used in the process
Catalysis material is nontoxic, highly-safe, is widely used.
The present invention replaces the calcination processing after spray drying using thermal reduction processing, and graphene oxide is first carried out also original place
Reason, the controllable obtained graphene surface that restores retains part oxygen-containing group, further convenient for catalysis material and other materials
It is compound.Simultaneously, it is thus also avoided that the crystal transfer of titanium dioxide nano-particle, rutile-type and anatase during calcination processing
The mixed crystal type titanium dioxide nano-particle of type can produce synergistic effect, hinders the compound of light induced electron and electron hole, provides
The photocatalysis effect of catalysis material.
The present invention also provides a kind of catalysis materials obtained such as above-mentioned preparation method, and the catalysis material is by graphene
It is combined with titanium dioxide nano-particle, there are gaps between the graphene and the titanium dioxide nano-particle.
It should be noted that catalysis material of the invention is spherical in shape, outer layer is graphene, but there is no with two for graphene
Titanium oxide nanoparticles constitute core-shell structure, and graphene is also entrained between titanium dioxide nano-particle, by nano titania
Particle separates and forms gap.It is appreciated that the outer layer being made of graphene is also and Non-smooth surface, complete shell, in graphene
There is also gaps between the outer layer of composition, enter inside catalysis material convenient for the contaminant molecule in air and receive with titanium dioxide
Rice corpuscles contact.
Specifically, the crystal form of the titanium dioxide nano-particle includes Detitanium-ore-type and rutile-type.In catalytic process,
The mixed crystal type of rutile-type and Detitanium-ore-type is equivalent to two kinds of semiconductors couplings, can produce synergistic effect, hinders light induced electron
It is compound with electron hole, the photocatalysis effect of photochemical catalyst is provided.
In catalysis material of the invention, the specific surface area of graphene is high, electron transmission is had excellent performance, and can be effectively reduced
The band gap width of titanium dioxide nano-particle forms energy level difference with titanium dioxide nano-particle, receives to widen titanium dioxide
The optical response range of rice corpuscles.In turn, titanium dioxide nano-particle can be enable to be excited under natural light irradiation, generates photoproduction electricity
Son, and the recombination rate in light induced electron and hole is effectively reduced, the photocatalysis effect of titanium dioxide nano-particle significantly improves.
The graphene surface of catalysis material of the invention retains part oxygen-containing group, convenient for catalysis material and other materials
Material is further compound.Meanwhile the crystal form of the titanium dioxide nano-particle in catalysis material of the present invention include rutile-type with it is sharp
Titanium ore type, the titanium dioxide nano-particle of mixed crystal type can produce synergistic effect, hinder the compound of light induced electron and electron hole,
The photocatalysis effect of photochemical catalyst is provided.
Dirt in catalysis material of the invention, there are gap between graphene and titanium dioxide nano-particle, in air
Dye object molecule (VOC etc.) can from gap enter and come into full contact with titanium dioxide nano-particle, and be broken down into carbon dioxide with
Water, then shed from gap, light-catalysed efficiency significantly improves.Meanwhile catalysis material itself is lossless, and has operation letter
Singly, the advantages that low energy consumption, without secondary pollution.
The present invention also provides a kind of fabric, load has above-mentioned catalysis material on the fabric.
Specifically, the mass ratio of the fabric and photochemical catalyst is 1:(0.1~0.2).Both it can guarantee the flexibility of fabric,
It again can be with the organic pollutant in efficient degradation air.
Wherein, the graphene surface of catalysis material also contains part oxygen-containing group, can form hydrogen bond with fabric surface, increase
Strong interaction keeps catalysis material load secured.
Fabric of the invention can be by organic pollutants such as formaldehyde, toluene, polycyclic aromatic hydrocarbons in air under illumination condition
High efficiency photocatalysis degradation is carried out, it is easy to use without other conditions such as ultraviolet lights.Therefore, fabric can be widely applied in automobile,
Between new clothes room, pet, a variety of living scenes such as wardrobe, toilet, can be carried around, can also standing type sprawl or hang use.
Fabric of the invention can also be killed, inhibit staphylococcus aureus, Escherichia coli, mould, Candida albicans etc. more
Thin, fungi is planted, the purpose of purification air is finally reached.
Hereinafter, will be done further by following specific embodiments to described catalysis material and preparation method thereof, fabric
Explanation.
Embodiment 1:
Graphene oxide solution is prepared using Hummers method, then graphene oxide solution is carried out at 300 DEG C
Thermal reduction processing, obtains graphene solution.Wherein, the concentration of the graphene in graphene solution is 10mg/mL, and graphene contains
Oxygen amount is 5w%.
The condition of homogenization is set are as follows: pressure 120MPa, flow 50mL/min.Hydration two is added into graphene solution
The mass ratio of titanium oxide, graphene and hydrated titanium dioxide is 1:3, and carries out homogenization, obtains finely dispersed mixed liquor.
The intake air temperature that spray dryer is arranged is 170 DEG C, and air outlet temperature is 100 DEG C, the speed of spray drying
5mL/min.Mixed liquor is spray-dried using spray dryer, obtains catalysis material.Obtained catalysis material
It is combined by graphene and titanium dioxide nano-particle, there are gap between graphene and titanium dioxide nano-particle, and two
The crystal form of titanium oxide nanoparticles includes Detitanium-ore-type and rutile-type.
Embodiment 2:
Graphene oxide solution is prepared using Hummers method, then graphene oxide solution is carried out at 320 DEG C
Thermal reduction processing, obtains graphene solution.Wherein, the concentration of the graphene in graphene solution is 13mg/mL, and graphene contains
Oxygen amount is 7w%.
The condition of homogenization is set are as follows: pressure 130MPa, flow 65mL/min.Hydration two is added into graphene solution
The mass ratio of titanium oxide, graphene and hydrated titanium dioxide is 1:1, and carries out homogenization, obtains finely dispersed mixed liquor.
The intake air temperature that spray dryer is arranged is 175 DEG C, and air outlet temperature is 100 DEG C, the speed of spray drying
6mL/min.Mixed liquor is spray-dried using spray dryer, obtains catalysis material.Obtained catalysis material
It is combined by graphene and titanium dioxide nano-particle, there are gap between graphene and titanium dioxide nano-particle, and two
The crystal form of titanium oxide nanoparticles includes Detitanium-ore-type and rutile-type.
Embodiment 3:
Graphene oxide solution is prepared using Hummers method, then graphene oxide solution is carried out at 350 DEG C
Thermal reduction processing, obtains graphene solution.Wherein, the concentration of the graphene in graphene solution is 15mg/mL, and graphene contains
Oxygen amount is 10w%.
The condition of homogenization is set are as follows: pressure 150MPa, flow 60mL/min.Hydration two is added into graphene solution
The mass ratio of titanium oxide, graphene and hydrated titanium dioxide is 2:1, and carries out homogenization, obtains finely dispersed mixed liquor.
The intake air temperature that spray dryer is arranged is 170 DEG C, and air outlet temperature is 105 DEG C, the speed of spray drying
5mL/min.Mixed liquor is spray-dried using spray dryer, obtains catalysis material.Obtained catalysis material
It is combined by graphene and titanium dioxide nano-particle, there are gap between graphene and titanium dioxide nano-particle, and two
The crystal form of titanium oxide nanoparticles includes Detitanium-ore-type and rutile-type.
Embodiment 4:
Graphene oxide solution is prepared using Hummers method, then graphene oxide solution is carried out at 350 DEG C
Thermal reduction processing, obtains graphene solution.Wherein, the concentration of the graphene in graphene solution is 16mg/mL, and graphene contains
Oxygen amount is 8w%.
The condition of homogenization is set are as follows: pressure 160MPa, flow 60mL/min.Hydration two is added into graphene solution
The mass ratio of titanium oxide, graphene and hydrated titanium dioxide is 3:1, and carries out homogenization, obtains finely dispersed mixed liquor.
The intake air temperature that spray dryer is arranged is 185 DEG C, and air outlet temperature is 110 DEG C, the speed of spray drying
8mL/min.Mixed liquor is spray-dried using spray dryer, obtains catalysis material.Obtained catalysis material
It is combined by graphene and titanium dioxide nano-particle, there are gap between graphene and titanium dioxide nano-particle, and two
The crystal form of titanium oxide nanoparticles includes Detitanium-ore-type and rutile-type.
Embodiment 5:
Graphene oxide solution is prepared using Hummers method, then graphene oxide solution is carried out at 380 DEG C
Thermal reduction processing, obtains graphene solution.Wherein, the concentration of the graphene in graphene solution is 18mg/mL, and graphene contains
Oxygen amount is 6w%.
The condition of homogenization is set are as follows: pressure 170MPa, flow 70mL/min.Hydration two is added into graphene solution
The mass ratio of titanium oxide, graphene and hydrated titanium dioxide is 5:1, and carries out homogenization, obtains finely dispersed mixed liquor.
The intake air temperature that spray dryer is arranged is 180 DEG C, and air outlet temperature is 105 DEG C, the speed of spray drying
6mL/min.Mixed liquor is spray-dried using spray dryer, obtains catalysis material.Obtained catalysis material
It is combined by graphene and titanium dioxide nano-particle, there are gap between graphene and titanium dioxide nano-particle, and two
The crystal form of titanium oxide nanoparticles includes Detitanium-ore-type and rutile-type.
Embodiment 6:
Graphene oxide solution is prepared using Hummers method, then graphene oxide solution is carried out at 400 DEG C
Thermal reduction processing, obtains graphene solution.Wherein, the concentration of the graphene in graphene solution is 20mg/mL, and graphene contains
Oxygen amount is 5w%.
The condition of homogenization is set are as follows: pressure 180MPa, flow 80mL/min.Hydration two is added into graphene solution
The mass ratio of titanium oxide, graphene and hydrated titanium dioxide is 6:1, and carries out homogenization, obtains finely dispersed mixed liquor.
The intake air temperature that spray dryer is arranged is 190 DEG C, and air outlet temperature is 110 DEG C, the speed of spray drying
10mL/min.Mixed liquor is spray-dried using spray dryer, obtains catalysis material.Obtained catalysis material
It is combined by graphene and titanium dioxide nano-particle, there are gap between graphene and titanium dioxide nano-particle, and two
The crystal form of titanium oxide nanoparticles includes Detitanium-ore-type and rutile-type.
The forbidden bandwidth for the catalysis material that 1~embodiment of embodiment 6 obtains is decreased to 2.55eV or so, not only exists
The ultraviolet region of 200nm~400nm wavelength has very strong absorbability, and has reached 490nm to the absorption threshold value of visible light
Left and right.Therefore, the photocatalysis effect of obtained catalysis material is remarkably improved.
Embodiment 7:
The catalysis material that embodiment 1 is obtained passes through in the method load and cotton fabric of spraying, cotton fabric and photocatalysis
The mass ratio of material is 1:0.15.
Embodiment 8:
The catalysis material that embodiment 2 is obtained passes through in the method load and cotton fabric of spraying, cotton fabric and photocatalysis
The mass ratio of material is 1:0.15.
Embodiment 9:
The catalysis material that embodiment 3 is obtained passes through in the method load and cotton fabric of spraying, cotton fabric and photocatalysis
The mass ratio of material is 1:0.15.
Embodiment 10:
The catalysis material that embodiment 3 is obtained passes through in the method load and cotton fabric of spraying, cotton fabric and photocatalysis
The mass ratio of material is 1:0.1.
Embodiment 11:
The catalysis material that embodiment 3 is obtained passes through in the method load and cotton fabric of spraying, cotton fabric and photocatalysis
The mass ratio of material is 1:0.2.
Embodiment 12:
The catalysis material that embodiment 4 is obtained passes through in the method load and cotton fabric of spraying, cotton fabric and photocatalysis
The mass ratio of material is 1:0.15.
Embodiment 13:
The catalysis material that embodiment 5 is obtained passes through in the method load and cotton fabric of spraying, cotton fabric and photocatalysis
The mass ratio of material is 1:0.15.
Embodiment 14:
The catalysis material that embodiment 6 is obtained passes through in the method load and cotton fabric of spraying, cotton fabric and photocatalysis
The mass ratio of material is 1:0.15.
The cotton fabric of 7~embodiment of embodiment 14 is subjected to formaldehyde removal test, test result is as shown in table 1.
Table 1
The cotton fabric of 7~embodiment of embodiment 14 is subjected to TVOC removal test, test result is as shown in table 2.
Table 2
By Tables 1 and 2 it is found that catalysis material is high to the removal rate of air pollutants, excellent catalytic effect.
The cotton fabric of 7~embodiment of embodiment 14 is subjected to antibacterial tests, wherein inhibit the test result of Escherichia coli such as
Shown in table 3, inhibit the test result of Candida albicans as shown in table 4, inhibits test result such as 5 institute of table of staphylococcus aureus
Show.
Table 3
Table 4
Table 5
By 3~table of table 5 it is found that catalysis material also has preferable anti-microbial property.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of catalysis material, which comprises the following steps:
Graphene oxide solution is provided；
Thermal reduction processing is carried out to the graphene oxide solution, obtains graphene solution, the graphite in the graphene solution
The concentration of alkene is 10mg/mL~20mg/mL, and the oxygen content of graphene is 5w%~10w%；
Hydrated titanium dioxide is added into the graphene solution, and carries out homogenization, obtains mixed liquor；
The mixed liquor is spray-dried using spray dryer, obtains catalysis material, the catalysis material is by stone
Black alkene and titanium dioxide nano-particle are combined, and there are gaps between the graphene and the titanium dioxide nano-particle.
2. catalysis material according to claim 1, which is characterized in that it is described thermal reduction processing temperature be 300 DEG C~
400℃。
3. catalysis material according to claim 1, which is characterized in that the pressure of the homogenization be 120MPa~
180MPa, flow are 50mL/min~80mL/min.
4. catalysis material according to claim 1, which is characterized in that graphene and hydration titanium dioxide in the mixed liquor
The mass ratio of titanium is 1:3~6:1.
5. catalysis material according to claim 1, which is characterized in that the intake air temperature of the spray drying is 170
DEG C~190 DEG C, air outlet temperature is 100 DEG C~110 DEG C.
6. catalysis material according to claim 1, which is characterized in that the graphene oxide solution is by Hummers method
It is prepared.
7. a kind of catalysis material that the preparation method as described in any one of claim 1~6 obtains, which is characterized in that the light
Catalysis material is combined by graphene and titanium dioxide nano-particle, the graphene and the titanium dioxide nano-particle it
Between there are gaps.
8. catalysis material according to claim 7, which is characterized in that the crystal form of the titanium dioxide nano-particle includes
Detitanium-ore-type and rutile-type.
9. a kind of fabric, which is characterized in that load has the catalysis material described as claimed in claim 7 or 8 on the fabric.
10. fabric according to claim 9, which is characterized in that the mass ratio of the fabric and photochemical catalyst is 1:(0.1
~0.2).
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| CN115976829A (en) * | 2023-01-09 | 2023-04-18 | 浙江烯纺新材料科技有限公司 | Azo modified graphene, antibacterial and deodorant textile and preparation method thereof |
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