CN109622047A - A kind of preparation method of fabric/poly- nitrogen/polypyrrole/halogenation oxygen bismuth catalysis material - Google Patents
A kind of preparation method of fabric/poly- nitrogen/polypyrrole/halogenation oxygen bismuth catalysis material Download PDFInfo
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- CN109622047A CN109622047A CN201811632285.5A CN201811632285A CN109622047A CN 109622047 A CN109622047 A CN 109622047A CN 201811632285 A CN201811632285 A CN 201811632285A CN 109622047 A CN109622047 A CN 109622047A
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- Prior art keywords
- fabric
- nitrogen
- poly
- polypyrrole
- oxygen bismuth
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000004744 fabric Substances 0.000 title claims abstract description 84
- 239000000463 material Substances 0.000 title claims abstract description 56
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 50
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 30
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 28
- 230000026030 halogenation Effects 0.000 title claims abstract description 25
- 238000005658 halogenation reaction Methods 0.000 title claims abstract description 25
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical compound [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 28
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 32
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 229920000742 Cotton Polymers 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- LOZAIRWAADCOHQ-UHFFFAOYSA-N triphosphazene Chemical compound PNP=NP LOZAIRWAADCOHQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 3
- 229920004934 Dacron® Polymers 0.000 claims description 2
- 229920000271 Kevlar® Polymers 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 claims description 2
- 229920000297 Rayon Polymers 0.000 claims description 2
- 229920002334 Spandex Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000004761 kevlar Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000004759 spandex Substances 0.000 claims description 2
- 210000002268 wool Anatomy 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 238000005406 washing Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 15
- 239000002041 carbon nanotube Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- -1 30min is stirred Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 2
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000002028 Biomass Substances 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
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of fabric/poly- nitrogen/polypyrrole/halogenation oxygen bismuth catalysis material preparation methods.This method comprises: fabric/poly- nitrogen material preparation, fabric/poly- nitrogen/polypyrrole material preparation, fabric/poly- nitrogen/polypyrrole/halogenation oxygen bismuth catalysis material preparation.This method effectively widens photoresponse region to near-infrared, the utilization rate of solar energy is substantially improved, catalysis material can be repeated several times recycling.
Description
Technical field
The invention belongs to composite photocatalyst material field, in particular to a kind of fabric/poly- nitrogen/polypyrrole/halogenation oxygen bismuth is urged
Change the preparation method of material.
Background technique
With the quickening of China's industrialization and urbanization process, by organic pollutant, Polymer wastes, biomass pollution and
Caused environmental pollution has become a serious social concern.Even if the organic dirt of certain low concentrations may also generate high poison
Property, to constitute a serious threat to the ecosystem and human health.Traditional pollutant process technology, such as physical absorption, chemistry
The methods of precipitating cannot completely remove these organic dirts, and may generate many other nocuousness in the actual operation process
By-product causes secondary pollution.Therefore, it is necessary to a kind of effective " green " technologies by noxious pollutant be converted into innocuous substance and
It not will cause secondary pollution.In order to solve these problems, a lot of research work person attempts to solve the problems, such as this with scientific method, with
Realize the sustainable development of human society.In recent years, Photocatalitic Technique of Semiconductor is unanimously considered to solve environmental problem
Effectively, the solution of green and most prospect.This technology has huge economic and social benefit in field of environmental improvement,
It is even more especially to yield unusually brilliant results in the fields such as sewage treatment, air cleaning and antibacterial of keeping a public place clean.However, current most of photochemical catalysts
Be primarily present following problems: (primarily responsive to ultraviolet light) too low to solar energy utilization ratio, quantum efficiency be low and recycling difficulty etc..
Therefore, the catalysis material designing and developing a kind of efficient catalytic and easily recycling is of great significance.
The common photochemical catalysts such as halogenation oxygen bismuth, zinc oxide, tungstic acid, band gap is generally wider, and anti-light corrosivity is preferable,
But its response region is mainly at ultra-violet (UV) band (account for solar energy 5% or so).Therefore, the photoresponse model of photochemical catalyst is widened
It encloses, improves the utilization rate to sunlight, be the important research direction of current photocatalysis technology.Currently used method has noble metal
Doping, semiconductors coupling and ion doping etc..Studies have shown that these methods successfully optical response range can be extended to it is visible
Light area, but wavelength can be widened successfully to rarely having near infrared region to and heard of (visible light account for solar energy 45%).
It in order to effectively load to catalysis material on fabric, and does not influence its catalytic efficiency as far as possible, there is researcher
Once by the way of padding by photocatalyst to fabric, research shows that loaded using this method, binding strength compared with
It is good, but it only also is covered on fiber surface since catalyst is most of, the catalyst into fibrous inside is less and keeps its water-fast
It is poor to wash fastness；And cause fabric corrosion more serious since the pick-up of padding method is higher.Also there is researcher using colloidal sol-
The method of gel loads to catalyst on fabric, the advantage is that simple process and can effectively improve fabric self-cleaning effect
(by controlling surface roughness), but generally carry out load using the method and high temperature is needed to bake, fabric can be caused so directly
Damage, also results in catalyst agglomeration, influences photocatalysis effect.Simultaneously as catalyst forms chemical bond in conjunction with fabric
Active force is faint, repeatedly easily falls off after washing, substantially reduces its photocatalysis efficiency.Compare patent
CN201611095874.5, CN201611095891.9, the catalyst that these patents use all are under visible light, to light source benefit
With rate, and it is weaker with the active force of fiber, its repeat performance is influenced, secondary pollution is caused, seriously constrains technology
Industrial applications, this patent overcomes existing patent insufficient, using high performance catalyst under near infrared light, and passes through covalent bond side
Formula and fiber combine, and durability is good, and repeat performance is good.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of fabric/poly- nitrogen/polypyrrole/halogenation oxygen bismuth catalysis materials
Preparation method, to overcome the defect that photochemical catalyst is low to solar energy utilization ratio in the prior art and catalytic efficiency is low.
A kind of fabric of the invention/poly- nitrogen/polypyrrole/halogenation oxygen bismuth catalysis material preparation method, comprising:
(1) in a solvent by triphosphazene dispersion, stirring is immersed fabric (5cm*5cm), and melamine is added and continues to stir
Mix, light irradiation is washed, dry, obtain fabric/poly- nitrogen material, wherein the ratio of triphosphazene and solvent be 1.50~
The molar ratio of 3.00mmol:150~200mL, triphosphazene and melamine is 1.5~3:0.75~1.5；
(2) pyrrole monomer is dissolved in solvent, fabric/poly- nitrogen material makes it adsorb pyrrole monomer, drop in investment step (1)
Add ferric trichloride/hydrochloric acid solution, takes out fabric, obtain fabric/poly- nitrogen/polypyrrole material, wherein the body of pyrrole monomer and solvent
Product than being 0.8~1.6:120~200, the molar ratio of pyrrole monomer and ferric trichloride be 0.011~0.023:0.031~
0.062；
(3) fabric in step (2)/poly- nitrogen/polypyrrole material is immersed in halogenation oxygen bismuth suspension, stir process is washed
It washs, it is dry, obtain fabric/poly- nitrogen/polypyrrole/halogenation oxygen bismuth catalysis material.
Solvent is acetonitrile in the step (1).
Fabric is cotton fabric, dacron, kevlar fabric, acrylic fabric, viscose fabric, carbon cloth, glass in the step (1)
It is glass fabric, spandex fabric, nylon fabric, silk fabric, one or several kinds of in wool fabric.
Stirring and continuation mixing time are 30~60min in the step (1).
The technological parameter that light irradiates in the step (1) are as follows: use high-pressure sodium lamp, power is 100~200W, irradiation time
For 12~for 24 hours.
Washing is washed for several times with acetonitrile in the step (1).
Drying is dry 8~12h at 60~80 DEG C in the step (1).
Solvent is 0.8~1.2mol/L hydrochloric acid in the step (2).
The time of absorption pyrrole monomer and halogenation oxygen bismuth is 1~2h in the step (2).
Ferric trichloride/hydrochloric acid solution is added dropwise in the step (2) to be carried out at 0-5 DEG C of temperature.
Ferric trichloride/concentration of hydrochloric acid solution is 100~200g/L in the step (2).
Halogenation oxygen bismuth suspension concentration is 0.01~0.02g/L in the step (3).
Treatment temperature is 70~90 DEG C in the step (3), and the processing time is 1~2h.
Washing is to be washed with deionized for several times in the step (3).
Drying is dry 4~6h at 60~80 DEG C in the step (3).
The present invention provide the fabric of the preparation method preparation of fabric/poly- nitrogen/polypyrrole/halogenation oxygen bismuth catalysis material a kind of/
Poly- nitrogen/polypyrrole/halogenation oxygen bismuth catalysis material.
The present invention also provides a kind of knitting for fabric/poly- nitrogen/polypyrrole/halogenation oxygen bismuth catalysis material preparation method preparation
The application of object/poly- nitrogen/polypyrrole/halogenation oxygen bismuth catalysis material.
The present invention is first to obtain fabric/poly- nitrogen material, and the pyrroles of halogenation oxygen bismuth is then blended with using chemical oxidization method
Monomer is arranged onto fabric/poly- nitrogen material, and obtaining fabric/poly- nitrogen/polypyrrole/halogenation oxygen bismuth, efficiently repeatable be recycled is catalyzed
Material.
The present invention can widen optical response range to the poly- nitrogen of near-infrared due to introducing, and can be substantially improved to solar energy
Utilization rate (nearly 50%)；Polypyrrole is introduced on the poly- nitrogen with high efficiency photocatalysis activity again, can effectively delay electronics and sky
Cave it is compound to increase more active sites so that catalytic activity further strengthens；Poly- nitrogen is set to pass through chemical bond and fabric again
In conjunction with being greatly improved material and performance be recycled for multiple times, it is often more important that influenced on its catalytic activity smaller.
Beneficial effect
The present invention it is low in cost, easy to operate and can large-scale industrial production, effectively widen photoresponse region to close red
Outside.It is existing flexibility catalysis material to the response of light within 550nm, catalysis material prepared by the present invention 600-2000nm all
There is different degrees of absorption to light, the utilization rate of solar energy is substantially improved, composite catalyzing material catalytic performance is excellent, using chemistry
Mode loads, and greatly improves closed matereial cycle rate, and number is recycled on the influence of the catalytic activity of photochemical catalyst itself
It is smaller, it can be widely applied to organic pollutant degradation field and prepare the simple organics such as methane by restoring carbon dioxide,
It has broad application prospects and market prospects.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
(1) 1.5mmol triphosphazene is dispersed in 150mL acetonitrile, stirs 30min, immersed cotton fabric (5cm*5cm),
Then it is gradually added 0.75mmol melamine and stirs 30min, then irradiate 12h at the high-pressure sodium lamp of 150W (ultraviolet lamp)
Afterwards, the dry 8h for several times and at 60 DEG C is washed with acetonitrile, obtains cotton fabric/poly- nitrogen material；
(2) then the pyrrole monomer of 0.8mL is dissolved in 120mL hydrochloric acid (0.8mol/L), investment cotton fabric/poly- nitrogen material makes
Its adsorb pyrrole monomer 1h, so that mixeding liquid temperature is maintained at 0 DEG C or so under ice bath, be then slowly added dropwise 50mL ferric trichloride/
Hydrochloric acid solution (100g/L), it is black by leucismus to can be observed fabric, finally for several times and dry at 60 DEG C by deionized water washing
4h obtains the efficiently repeatable recycling catalysis material of cotton fabric/poly- nitrogen/polypyrrole.
(3) fabric in step (2)/poly- nitrogen/polypyrrole material is immersed in the aqueous solution that 50mL contains 0.01g/L BiOBr
In, 1.5h is handled at 80 DEG C under magnetic stirring, finally passes through deionized water washing for several times and the dry 4h at 60 DEG C, obtains
Cotton fabric/poly- nitrogen/polyaniline/BiOX is efficiently repeatable to be recycled catalysis material.
Embodiment 2
(1) 2.25mmol triphosphazene is dispersed in 175mL acetonitrile, stirs 30min, immersed cotton fabric (5cm*5cm),
Then it is gradually added 0.75mmol melamine and stirs 45min, then irradiate 18h at the high-pressure sodium lamp of 150W (ultraviolet lamp)
Afterwards, the dry 10h for several times and at 70 DEG C is washed with acetonitrile, obtains cotton fabric/poly- nitrogen material；
(2) then the pyrrole monomer of 1.2mL is dissolved in 160mL hydrochloric acid (1mol/L), investment cotton fabric/poly- nitrogen material makes it
Pyrrole monomer 1.5h is adsorbed, so that mixeding liquid temperature is maintained at 2.5 DEG C or so under ice bath, 50mL tri-chlorination is then slowly added dropwise
Iron/hydrochloric acid solution (150g/L), it is black by leucismus to can be observed fabric, finally does for several times and at 70 DEG C by deionized water washing
Dry 5h obtains the efficiently repeatable recycling catalysis material of cotton fabric/poly- nitrogen/polypyrrole.
(3) fabric in step (2)/poly- nitrogen/polypyrrole material is immersed in 50mL and contains the water-soluble of 0.015g/L BiOCl
In liquid, 1.5h is handled at 80 DEG C under magnetic stirring, finally passes through deionized water washing for several times and the dry 4h at 60 DEG C, obtains
Catalysis material is recycled to cotton fabric/poly- nitrogen/polyaniline/BiOX is efficiently repeatable.
Embodiment 3
(1) 3mmol triphosphazene is dispersed in 200mL acetonitrile, stirs 30min, immersed cotton fabric (5cm*5cm), connect
Be gradually added 1.5mmol melamine and stir 60min, then the high-pressure sodium lamp of 150W (ultraviolet lamp) irradiation for 24 hours after, use
12h is dried in acetonitrile washing for several times and at 80 DEG C, obtains cotton fabric/poly- nitrogen material；
(2) then the pyrrole monomer of 1.6mL is dissolved in 200mL hydrochloric acid (1.2mol/L), investment cotton fabric/poly- nitrogen material makes
Its adsorb pyrrole monomer 2h, so that mixeding liquid temperature is maintained at 5 DEG C or so under ice bath, be then slowly added dropwise 50mL ferric trichloride/
Hydrochloric acid solution (200g/L), it is black by leucismus to can be observed fabric, finally for several times and dry at 80 DEG C by deionized water washing
6h obtains the efficiently repeatable recycling catalysis material of cotton fabric/poly- nitrogen/polypyrrole.
(3) fabric in step (2)/poly- nitrogen/polypyrrole material is immersed in the aqueous solution that 50mL contains 0.02g/L BiOI
In, 2h is handled at 90 DEG C under magnetic stirring, finally passes through deionized water washing for several times and the dry 4h at 60 DEG C, obtains cotton
Fabric/poly- nitrogen/polyaniline/BiOX is efficiently repeatable to be recycled catalysis material.
It is 50mg/L RB-19 dye liquor that 50mg RB-19 dyestuff addition deionized water, which is settled to 1L compound concentration, using reality
Apply the efficiently repeatable recycling catalysis material of cotton fabric prepared by example 1~3/poly- nitrogen/polypyrrole/halogenation oxygen bismuth and comparison
For catalysis material to dyestuff degradation 2h under near infrared light, degradation rate is as follows in example 1-2:
| Embodiment number | Degradation rate (the 1st time) | Degradation rate (after circulation 30 times) |
| Embodiment 1 | 96.22% | 93.49% |
| Embodiment 2 | 95.88% | 93.43% |
| Embodiment 3 | 95.89% | 93.62% |
| Comparative example 1 | 40.24% | 18.25% |
| Comparative example 2 | 39.91% | 17.97% |
Comparative example 1
(1) 200mg CNTs is added to the 30%FeCl of 40mL2In solution, pH=3 is adjusted, 40mL is then added
H2O2, room temperature ultrasound 2h, room temperature magnetic agitation 8h add water 500mL, filter washing to neutrality, filter.It is dried in vacuo at 60 DEG C
Product a is obtained for 24 hours；Under logical condition of nitrogen gas, under the conditions of drying nitrogen, disperse 3g product a in dry three-necked flask
In 200mL DMF, ice-water bath is cooling, 0 DEG C of addition NaH 522mg, continues to stir 30min.Then it is gradually warmed up to 90 DEG C, dropwise
3mL1- perfluoro-hexyl iodide is added, ultrasonic reaction is for 24 hours.Add a small amount of water quenching reaction, successively DMF, second alcohol and water centrifuge washing.?
To black particle product b in vacuum drying oven 50 DEG C of dry 96h；2g product b is dispersed in 50mL water, 438mg is added
NaOH, ultrasonic disperse 1h, 2g Cyanuric Chloride are dispersed in 50mL water, are added in three-necked flask, 0~5 DEG C is stirred to react 48h.According to
It is secondary to use water and ethyl alcohol centrifuge washing.25 DEG C of vacuum drying 96h, obtain product c；Under logical condition of nitrogen gas, in dry three-necked flask
1.5g product c, triethylamine 2.4mL, DMF 150mL is added.Ice-water bath is cooling, and acryloyl chloride 1mL is added dropwise at 0 DEG C and (is dissolved in
10mL DMF), ultrasonic reaction is for 24 hours.Successively use second alcohol and water centrifuge washing.Obtained black solid product d, room temperature in vacuo dry
It is dry；Product d 1g is added in three-necked flask, 0.3mL DBU (0.5mol) is dissolved in by dimethylphosphite 415mg, DMF 150mL
It in 20mL DMF, is added dropwise in above-mentioned three-necked flask, 25 DEG C of ultrasonic reaction 48h.Successively use second alcohol and water centrifuge washing
The drying of (300mL × 3 time) room temperature in vacuo, obtains multifunctional carbon nanotube e.
(2) by FeVO4, disodium ethylene diamine tetraacetate (stabilizer), mass ratio be 1:3 triblock polyether P123 and three it is embedding
Response type carbon nanotube is added to concentration and is in the mixture (template) and above-mentioned steps (1) of section copolymer F127
In the buffer of 0.025mol/L sodium dihydrogen phosphate and 0.05mol/L dibastic sodium phosphate composition, 30min is stirred, suspension is formed；Its
Middle FeVO4Concentration be 0.01mol/L, the concentration of stabilizer is 0.01mol/L, the concentration of template is 0.05mol/L.
It (3) is 5 with the pH value that the sodium hydrate aqueous solution of concentration 0.5mol/L adjusts above-mentioned suspension, at 80 DEG C of heating,
Flow back 6h, and filtering obtains reaction product；Wherein FeVO4Mass ratio with carbon nanotube is 1:5.
(4) by fiber impregnation to contain the compound FeVO of 0.05g/L carbon nanotube4Disperse with 0.025g/L polyethylene glycol 2000
In liquid, 60 DEG C of reaction 2h are dried, and washing, repeated impregnations are dried water-washing process 3 times, and fiber/carbon nanotube/FeVO is made4It is three-dimensional
Recyclable efficient catalytic material.
Comparative example 2
(1) 200mg CNTs is added to the 30%FeCl of 40mL2In solution, pH=3 is adjusted, 40mL is then added
H2O2, room temperature ultrasound 2h, room temperature magnetic agitation 8h add water 500mL, filter washing to neutrality, filter.It is dried in vacuo at 60 DEG C
Product a is obtained for 24 hours；Under logical condition of nitrogen gas, under the conditions of drying nitrogen, disperse 3g product a in dry three-necked flask
In 200mL DMF, ice-water bath is cooling, 0 DEG C of addition NaH 522mg, continues to stir 30min.Then it is gradually warmed up to 90 DEG C, dropwise
3mL 1- perfluoro-hexyl iodide is added, ultrasonic reaction is for 24 hours.Add a small amount of water quenching reaction, successively DMF, second alcohol and water centrifuge washing.?
To black particle product b in vacuum drying oven 50 DEG C of dry 96h；2g product b is dispersed in 50mL water, 438mg is added
NaOH, ultrasonic disperse 1h, 2g Cyanuric Chloride are dispersed in 50mL water, are added in three-necked flask, 0~5 DEG C is stirred to react 48h.According to
It is secondary to use water and ethyl alcohol centrifuge washing.25 DEG C of vacuum drying 96h, obtain product c；Under logical condition of nitrogen gas, in dry three-necked flask
1.5g product c, triethylamine 2.4mL, DMF 150mL is added.Ice-water bath is cooling, and acryloyl chloride 1mL is added dropwise at 0 DEG C and (is dissolved in
10mL DMF), ultrasonic reaction is for 24 hours.Successively use second alcohol and water centrifuge washing.Obtained black solid product d, room temperature in vacuo dry
It is dry；Product d 1g is added in three-necked flask, 0.3mL DBU (0.5mol) is dissolved in by dimethylphosphite 415mg, DMF 150mL
It in 20mL DMF, is added dropwise in above-mentioned three-necked flask, 25 DEG C of ultrasonic reaction 48h.Successively use second alcohol and water centrifuge washing
The drying of (300mL × 3 time) room temperature in vacuo, obtains multifunctional carbon nanotube e.
(2) by TiO2, disodium ethylene diamine tetraacetate (stabilizer), mass ratio be 1:3 triblock polyether P123 and three it is embedding
Response type carbon nanotube is added to concentration and is in the mixture (template) and above-mentioned steps (1) of section copolymer F127
In the buffer of 0.025mol/L sodium dihydrogen phosphate and 0.05mol/L dibastic sodium phosphate composition, 30min is stirred, suspension is formed；Its
Middle TiO2Concentration be 0.01mol/L, the concentration of stabilizer is 0.01mol/L, the concentration of template is 0.05mol/L.
It (3) is 5 with the pH value that the sodium hydrate aqueous solution of concentration 0.5mol/L adjusts above-mentioned suspension, at 80 DEG C of heating,
Flow back 6h, and filtering obtains reaction product；Wherein TiO2Mass ratio with carbon nanotube is 1:5.
(4) by fiber impregnation to contain 0.05g/L carbon nanotube composite Ti O2Disperse with 0.025g/L polyethylene glycol 2000
In liquid, 60 DEG C of reaction 2h are dried, and washing, repeated impregnations are dried water-washing process 3 times, and fiber/carbon nanotube/TiO is made2It is three-dimensional
Recyclable efficient catalytic material.
Claims (10)
1. a kind of fabric/poly- nitrogen/polypyrrole/halogenation oxygen bismuth catalysis material preparation method, comprising:
(1) in a solvent by triphosphazene dispersion, fabric is immersed in stirring, and melamine is added and continues to stir, and light irradiation is washed
Wash, it is dry, obtain fabric/poly- nitrogen material, wherein the ratio of triphosphazene and solvent be 1.50~3.00mmol:150~
The molar ratio of 200mL, triphosphazene and melamine is 1.5~3:0.75~1.5；
(2) pyrrole monomer is dissolved in solvent, fabric/poly- nitrogen material makes it adsorb pyrrole monomer in investment step (1), is added dropwise three
Iron chloride/hydrochloric acid solution takes out fabric, obtains fabric/poly- nitrogen/polypyrrole material, wherein the volume ratio of pyrrole monomer and solvent
For 0.8~1.6:120~200, the molar ratio of pyrrole monomer and ferric trichloride is 0.011~0.023:0.031~0.062；
(3) fabric in step (2)/poly- nitrogen/polypyrrole material is immersed in halogenation oxygen bismuth suspension, stir process, is washed, done
It is dry, obtain fabric/poly- nitrogen/polypyrrole/halogenation oxygen bismuth catalysis material.
2. the method according to claim 1, wherein solvent is acetonitrile in the step (1).
3. the method according to claim 1, wherein in the step (1) fabric be cotton fabric, dacron,
Kevlar fabric, acrylic fabric, viscose fabric, carbon cloth, glass fabric, spandex fabric, nylon fabric, silk fabric, wool
It is one or several kinds of in fabric.
4. the method according to claim 1, wherein stirring and continuation mixing time are 30 in the step (1)
~60min.
5. the method according to claim 1, wherein the technological parameter that light irradiates in the step (1) are as follows: use
High-pressure sodium lamp, power be 100~200W, irradiation time be 12~for 24 hours.
6. the method according to claim 1, wherein solvent is 0.8~1.2mol/L salt in the step (2)
Acid；The time for adsorbing pyrrole monomer is 1~2h.
7. the method according to claim 1, wherein ferric trichloride/hydrochloric acid solution is added dropwise in the step (2) is
It is carried out at 0-5 DEG C of temperature；Ferric trichloride/concentration of hydrochloric acid solution is 100~200g/L.
8. the method according to claim 1, wherein halogenation oxygen bismuth suspension concentration is in the step (3)
0.01~0.02g/L；Treatment temperature is 70~90 DEG C, and the processing time is 1~2h.
9. a kind of fabric/poly- nitrogen/polypyrrole/halogenation oxygen bismuth catalysis material of method preparation as described in claim 1.
10. a kind of fabric/poly- nitrogen/polypyrrole/halogenation oxygen bismuth catalysis material application of method preparation as described in claim 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109663601A (en) * | 2019-01-04 | 2019-04-23 | 三峡大学 | Load the application in the preparation method and its removal microcystic aeruginosa of nano material BiOBr/ fabric |
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| CN103657719A (en) * | 2013-12-18 | 2014-03-26 | 江苏大学 | Graphitic carbon nitride/polypyrrole composite photocatalytic material and preparation method thereof |
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| CN109663601A (en) * | 2019-01-04 | 2019-04-23 | 三峡大学 | Load the application in the preparation method and its removal microcystic aeruginosa of nano material BiOBr/ fabric |
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