CN110064437A - A kind of rule of surface loaded Ag/BiOBr nanometer sheet cellulose based fabric and its preparation and application - Google Patents
A kind of rule of surface loaded Ag/BiOBr nanometer sheet cellulose based fabric and its preparation and application Download PDFInfo
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- CN110064437A CN110064437A CN201910279868.2A CN201910279868A CN110064437A CN 110064437 A CN110064437 A CN 110064437A CN 201910279868 A CN201910279868 A CN 201910279868A CN 110064437 A CN110064437 A CN 110064437A
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- biobr
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- fabric
- cmf
- nanometer sheet
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- 239000004744 fabric Substances 0.000 title claims abstract description 46
- 229920002678 cellulose Polymers 0.000 title claims abstract description 22
- 239000001913 cellulose Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000012986 modification Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 24
- 230000015556 catabolic process Effects 0.000 claims description 22
- 238000006731 degradation reaction Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000007540 photo-reduction reaction Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- 238000006266 etherification reaction Methods 0.000 claims description 6
- 238000005956 quaternization reaction Methods 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 5
- 229940006460 bromide ion Drugs 0.000 claims description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 5
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 238000011109 contamination Methods 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000004332 silver Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 18
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 14
- 229940043267 rhodamine b Drugs 0.000 description 14
- PUIYMUZLKQOUOZ-UHFFFAOYSA-N isoproturon Chemical compound CC(C)C1=CC=C(NC(=O)N(C)C)C=C1 PUIYMUZLKQOUOZ-UHFFFAOYSA-N 0.000 description 11
- 230000005855 radiation Effects 0.000 description 8
- 229910021642 ultra pure water Inorganic materials 0.000 description 7
- 239000012498 ultrapure water Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- -1 antibiotic Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 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
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000009514 concussion Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000039 congener Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009647 facial growth Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The present invention relates to a kind of rule of surface loaded Ag/BiOBr nanometer sheet cellulose based fabric and its preparations and application, using the ion layer assembly BiOBr nanometer sheet cellulose based fabric surface modified in carboxylated, silver ion of the ultraviolet light reduction adsorption on BiOBr micron chip surface, the BiOBr nanometer sheet by silver particles modification is constructed in cellulose based fabric surface, has been obviously improved the ability of Ag/BiOBr nanometer sheet cellulose based fabric Visible Light Induced Photocatalytic organic pollutant.
Description
Technical field
The invention belongs to catalysis material and its preparation and application field, in particular to a kind of rule of surface loaded Ag/
BiOBr nanometer sheet cellulose based fabric and its preparation and application.
Background technique
With the fast development of industry, organic pollutant (dyestuff, antibiotic, chemical pesticide) and pathogenic bacteria in trade effluent
Purified treatment, it has also become people's thorny problem of concern.In recent years, Photocatalitic Technique of Semiconductor is considered as that removal is organic
One effective way of pollutant, but since there are forbidden bandwidths for traditional photochemical catalyst such as titanium dioxide, zinc oxide and cadmium sulfide
The problems such as wide high with photo-generated carrier recombination rate, greatly limit its application in terms of environment and the energy.Meanwhile it actually answering
With in the process, photochemical catalyst is often suspended among waste water in the form of solid particle, photocatalysis after pollutant process is completed
The recycling separation process of agent is time-consuming and laborious, and photochemical catalyst powder in removal process inevitable that part be lost.
Therefore, photocatalyst activity is promoted, suitable load method is selected, there is actual meaning for the effective use of photochemical catalyst.
In terms of the promotion of photocatalyst activity, researcher is mainly modified from heterogeneous photocatalytic system, carbon-based material is constructed
Improve photocatalysis efficiency with modified three directions of metal nanoparticle surface: (1) heterogeneous photocatalytic system be using it is a variety of not
Congener semiconductor light-catalyst constitutes heterojunction structure, and according to the forbidden band structure and electron energy level of semiconductor, multicomponent is partly led
The heterogeneous photocatalytic system of body can be divided into five classes, comprising: energy band great-leap-forward heterojunction structure, energy band alternative expression heterojunction structure, p-n are different
Matter junction structure, homogeneity junction structure and Z-type heterojunction structure；(2) it is usually will have preferable electronics to conduct that carbon-based material is modified
Compound with the carbon material and photochemical catalyst of transfer performance, the light induced electron on semiconductor conduction band can promptly be transferred to carbon substrate
Material, to promote the separation of photo-generate electron-hole, current research concentrates on graphene (Graphene) class and carbon quantum dot
(CQDs) two class carbon-based material；(3) metal nanoparticle surface is modified mainly usual using the fermi level of metal nanoparticle
The feature lower than semiconductor light-catalyst promotes the light induced electron of semiconductor light-catalyst to receive by Schottky contacts toward metal
It is migrated at rice grain.This modification mode generallys use the rare precious metals such as Pt, Pd, Au, Ag and Rh and is deposited on photochemical catalyst
Surface, for the opposite heterogeneous photocatalytic system of building is modified with carbon-based material, metal nanoparticle surface is modified to have method simple
It is single, the obvious feature of raising efficiency.
In terms of the load of photochemical catalyst, multiple technologies are invented, such as thermal sintering method, sol-gel method, magnetron sputtering
Method, chemical vapour deposition technique, liquid phase deposition, electrochemical deposition method etc..The operation of thermal sintering method is relatively easy, it is desirable that carrier has
Certain temperature tolerance.Sol-gel method is suitable for variety carrier material, and cost is relatively low, but regular appearance is poor.Magnetron sputtering method
An effective way is provided for low temperature loaded optic catalyst, is suitable for glass and organic polymer species carrier, this method load
Photocatalyst granular it is smaller and particle diameter distribution is uniform, but need special processing equipment.Chemical vapour deposition technique is also one
The method that photochemical catalyst can be deposited on any carrier by kind in a short time, the photochemical catalyst of method preparation have quite high
Purity, but the high requirements on the equipment.
CN101850263A discloses a kind of BiOBr catalysis material and its preparation method and application of Ag doping, the patent
The BiOBr nanometer sheet of prepared Ag doping is larger, and shape is inhomogenous, and catalytic process needs to be stirred continuously reaction solution, the group of being easy
It is poly-, and the recycling of catalyst with recycle it is more difficult.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of rule of surface loaded Ag/BiOBr nanometer sheet cellulose bases
Fabric and its preparation and application effectively overcome the dispersion and recycling problem of nanocatalyst, have been obviously improved BiOBr and have received
Rice piece catalytic efficiency and recycle performance, the present invention use LBL self-assembly method, in modified cellulose based fabric table
Face growth in situ BiOBr nanometer sheet, efficiently solves the loading problem that light urges agent, meanwhile, in-situ reducing silver ion is received in BiOBr
Rice piece surface, enhances it in the absorption intensity of visible light region, improves the separative efficiency of photo-generated carrier.
A kind of loaded Ag of the invention/BiOBr nanometer sheet cellulose based fabric preparation method, comprising:
(1) cellulosic fabric surface is carried out carboxylated to be modified, obtains carboxymethyl-modification cellulosic fabric CMF；
(2) carboxymethylated cellulosic fabric is carrier, and using ion, absorption method assembles BiOBr on CMF layer by layer specifically:
Under room temperature, CMF is soaked in 10~120s in aqueous bismuth nitrate solution, pulls out and ultrapure water cleans CMF to no Bi2O2 2+It is de-
It falls, then is immersed in 10~120s in bromide ion solution, fall off finally, cleaning CMF with ultrapure water again without bromide ion, in circulation
Operation is stated, washing, drying obtain BiOBr-CMF；
(3) by above-mentioned BiOBr-CMF impregnate silver nitrate solution, then carry out photo-reduction, wash, drying to get loaded Ag/
BiOBr nanometer sheet cellulose based fabric.
The preferred embodiment of above-mentioned preparation method is as follows:
Cellulosic fabric is cotton fabric, viscose fabric, one of linen in the step (1).
It is modified to carry out carboxylated for cellulosic fabric surface in the step (1) specifically: cellulosic fabric is added to hydrogen
In sodium hydroxide solution, quaternization is carried out, monoxone is added after alkalization, is warming up to etherification temperature and is reacted, reaction knot
Room temperature is cooled to after beam, reaction is adjusted between pH=7~8, pulls fabric out and wash, and dries；Wherein monoxone and cellulose
The mass ratio of based fabric is 0.1~1:1.
The mass fraction of the sodium hydroxide solution is 1~10%；The solvent of sodium hydroxide solution is that mass fraction is
70%~90% ethanol water.
The quaternization are as follows: 10~60min of quaternization at 10~30 DEG C；Etherification temperature is reacted: etherification temperature
It is 50~70 DEG C, reaction time 60-300min.
The agents useful for same of pH=7~8 that is adjusted to is hydrochloric acid, sulfuric acid, one of nitric acid.
The drying is 80 DEG C of drying.
Room temperature condition is 20~25 DEG C in the step (2).
The concentration of aqueous bismuth nitrate solution is 0.5~10mmol/L in the step (2)；The concentration of bromide ion solution is 0.5
~10mmol/L.
The bromide ion solution is one of potassium bromide or sodium bromide.
Cycle-index is 10~60 times in the step (2).
Washing is washed in the step (2) for washing, ethyl alcohol；Drying is 80 DEG C of drying.
The concentration of silver nitrate solution is 0.2-3g/L in the step (3).
Photo-reduction in the step (3) are as follows: a length of 235nm of the ultraviolet light wave of use, photo-reduction time are 1~60min.
Washing is washed in the step (3) for washing, ethyl alcohol；Drying is 80 DEG C of drying.
A kind of loaded Ag/BiOBr nanometer sheet cellulose based fabric of the method preparation of the invention.
The present invention provides a kind of loaded Ag/BiOBr nanometer sheet cellulose based fabric organic dirt in light degradation sewage
Contaminate the application in object.
It is described that light degradation is carried out as light source using sunlight or xenon lamp.
The organic pollutant be one of dyestuff, antibiotic, pesticide or and it is several, the concentration of degradation product is 1~
200mg/L。
The present invention cellulose based fabric surface modified in carboxylated using ion layer assembly BiOBr nanometer sheet, it is ultraviolet
Photo-reduction is adsorbed on the silver ion on BiOBr micron chip surface, constructs and is knitted by the BiOBr nanometer sheet of silver particles modification in cellulose base
Object surface has been obviously improved the ability of Ag/BiOBr nanometer sheet cellulosic fabric Visible Light Induced Photocatalytic organic pollutant.In xenon lamp
Under irradiation, > 99% can be reached to rhodamine B degradation rate (20mg/l) at 90 minutes, 180 minutes to herbicide isoproturon (20mg/
L) degradation rate reaches > 95%, meanwhile, it is convenient which recycles, and catalytic stability is good, recycles by 5 times
Afterwards, can still degrade in 180 minutes > 90% rhodamine B.
It is simple in the preparation method of cellulose based fabric that the present invention loads BiOBr nanometer sheet, and realizes silver particles and BiOBr
Nanometer sheet it is effective compound, be obviously improved the catalytic degradation efficiency of photochemical catalyst.
Detailed description of the invention
The XRD spectra that Fig. 1 is Ag/BiOBr-CMF in CMF and BiOBr-CMF and embodiment 3 in embodiment 1；Wherein illustration
For Ag/BiOBr-CMF (S2) partial enlarged view；
(a) and (e) are respectively the number of Ag/BiOBr-CMF (S2) in BiOBr-CMF and embodiment 3 in embodiment 1 in Fig. 2
Code picture, (b-d) and (f-h) are respectively that the field of Ag/BiOBr-CMF (S2) in BiOBr-CMF and embodiment 3 in embodiment 1 is sent out
Penetrate electron microscope；
It is the ultraviolet unrestrained anti-of Ag/BiOBr-CMF (S2) F in CMF, BiOBr-CMF and embodiment 3 in embodiment 1 in Fig. 3
Penetrate absorption spectrum (a) and fluorescence spectra (b)；
Fig. 4 is the test result of the circulation rhodamine B degradation of Ag/BiOBr-CMF (S2) under radiation of visible light
Fig. 5 is under radiation of visible light, and Ag/BiOBr-CMF (S2) is used as photochemical catalyst, the efficient liquid of isoproturon degradation raffinate
Phase chromatography.
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) sodium hydroxide 2g is weighed, is dissolved in 100g ethanol water (mass fraction 85%), cotton fabric 2g is added, is turned
Move to conical flask and shake 30min, 0.45g monoxone is added, is warming up to 70 DEG C, keep the temperature 3h, be cooled to 40 DEG C hereinafter, neutralize,
Washing, drying, obtain carboxymethyl modified cotton fabric (CMF), carboxyl-content 1.35mmol/g.
(2) carboxymethylated cotton fabric is soaked in 30s in the aqueous bismuth nitrate solution that concentration is 4mmol/L, pulls out and is used in combination
Ultrapure water cleaning, then being immersed in concentration is 30s in 4mmol/L potassium bromide solution, finally, being cleaned again with ultrapure water, by upper
State 15 numbers of step cycle, washing, ethyl alcohol wash, 80 DEG C of drying, obtains BiOBr-CMF.
(3) photocatalytic activity characterizes: taking the BiOBr-CMF (8cm × 8cm) prepared in step (2), being laid in diameter is
In the square polyethylene box of 9cm, then it is separately added into equipped with the rhodamine B and isoproturon solution that 50ml concentration is 20mg/L
In, it is placed in II type photochemical reactor of BL-GHX-, under the irradiation of 300W xenon lamp, takes a certain amount of reaction solution at regular intervals,
Using the concentration of visible spectrophotometer analysis rhodamine B degradation solution, using liquid-phase chromatographic analysis isoproturon degradation solution concentration,
The result shows that: the degradation rate of rhodamine B is 77.5% (radiation of visible light 90min), the 70.5% (visible light of degradation rate of isoproturon
Irradiate 180min).
Embodiment 2
(1) BiOBr-CMF prepared by embodiment 1 is immersed in the silver nitrate solution that 200mL concentration is 0.5g/L, concussion 1
It takes out, is placed in the surface plate for filling ultrapure water, fabric uses emission wavelength for the purple of 235nm apart from liquid level~1cm after hour
Outer light irradiation 1min is to get Ag/BiOBr-CMF (S1).
(2) photocatalytic activity characterizes: taking the Ag/BiOBr-CMF prepared in step (1), is separately added into equipped with 50ml concentration
To be placed in II type photochemical reactor of BL-GHX- in the rhodamine B of 20mg/L and isoproturon solution, irradiated in 300W xenon lamp
Under, a certain amount of reaction solution is taken at regular intervals, using the concentration of visible spectrophotometer analysis rhodamine B degradation solution, is adopted
With liquid-phase chromatographic analysis isoproturon degradation solution concentration, the results showed that the degradation rate of rhodamine B is 85.3% (radiation of visible light
90min), the degradation rate 86.7% (radiation of visible light 180min) of isoproturon.
Embodiment 3
(1) BiOBr-CMF prepared by embodiment 1 is immersed in the silver nitrate solution that 200ml concentration is 1g/L, concussion 1 is small
When after take out, be placed in the surface plate for filling ultrapure water, fabric uses emission wavelength for the ultraviolet of 235nm apart from liquid level~1cm
Light irradiation 10min is to get Ag/BiOBr-CMF (S2).
(2) photocatalytic activity characterizes: taking the Ag/BiOBr-CMF prepared in step (1), is separately added into equipped with 50ml concentration
To be placed in II type photochemical reactor of BL-GHX- in the rhodamine B of 20mg/L and isoproturon solution, irradiated in 300W xenon lamp
Under, a certain amount of reaction solution is taken at regular intervals, using the concentration of visible spectrophotometer analysis rhodamine B degradation solution, is adopted
With liquid-phase chromatographic analysis isoproturon degradation solution concentration, the results showed that the degradation rate of rhodamine B is > 99% (radiation of visible light
90min), degradation rate > 95% (radiation of visible light 180min) of isoproturon.
In embodiment 1 in CMF and BiOBr-CMF and embodiment 3 XRD spectra of Ag/BiOBr-CMF as shown in Figure 1, spectrogram
Display: complete using the diffraction maximum and BiOBr and Ag standard diffraction peak of catalyst prepared by LBL self-assembly method and photoreduction met hod
It is complete consistent.
In embodiment 1 in BiOBr-CMF and embodiment 3 Ag/BiOBr-CMF Flied emission electron microscope, as shown in Fig. 2, from
It can be seen that BiOBr is the nanometer sheet of thickness 40nm or so, from Fig. 2 (h) it can be seen that BiOBr nanometer sheet surface cloth in Fig. 2 (d)
Nanometer little particle is expired.
In embodiment 1 the uv drs absorption spectrum of CMF, BiOBr-CMF and the Ag/BiOBr-CMF in embodiment 3 and
For fluorescence spectra as shown in figure 3, for opposite BiOBr-CMF, Ag/BiOBr-CMF (S2) has stronger suction in visible light region
It receives, and photoluminescence intensity is significantly reduced.
Under 1 radiation of visible light of table, the degradation rate of rhodamine B was compared in 90 minutes
| Catalyst | Effective mass | Degradation rate (rhodamine B) |
| TiO2 | 25mg | 5% |
| BiOBr | 25mg | 60.5% |
| BiOBr-CMF | 25mg | 77.5% |
| Ag/BiOBr-CMF (photo-reduction 1min) | 25mg | 85.3% |
| Ag/BiOBr-CMF (photo-reduction 5min) | 25mg | 93.4% |
| Ag/BiOBr-CMF (photo-reduction 10min) | 25mg | > 99% |
| Ag/BiOBr-CMF (photo-reduction 20min) | 25mg | 97.2% |
Note: BiOBr-CMF in table 1 is immersed in 1g/L silver nitrate solution referring to embodiment 1 by the BiOBr-CMF in table 1
In, and shake 1 hour, then, be placed in the surface plate for filling ultrapure water, fabric apart from liquid level~1cm, use emission wavelength for
The ultraviolet light irradiation of 235nm, irradiation time are respectively 1min, 5min, 10min and 20min, prepare different photo-reduction Ag/
BiOBr-CMF sample.
Claims (10)
1. a kind of loaded Ag/BiOBr nanometer sheet cellulose based fabric preparation method, comprising:
(1) cellulosic fabric surface is carried out carboxylated to be modified, obtains carboxymethyl-modification cellulosic fabric CMF；
(2) under room temperature, CMF is soaked in 10~120s in aqueous bismuth nitrate solution, pulls out and cleaned, then be immersed in bromine
10~120s in solion, then clean, aforesaid operations are recycled, washing, drying obtain BiOBr-CMF；
(3) by above-mentioned BiOBr-CMF impregnate silver nitrate solution, then carry out photo-reduction, wash, drying to get loaded Ag/
BiOBr nanometer sheet cellulose based fabric.
2. preparation method according to claim 1, which is characterized in that cellulosic fabric is cotton fabric in the step (1), is glued
Glue fabric, one of linen.
3. preparation method according to claim 1, which is characterized in that cellulosic fabric surface carries out carboxylic in the step (1)
Baseization is modified specifically: cellulosic fabric is added in sodium hydroxide solution, quaternization is carried out, chlorine is added after alkalization
Acetic acid is warming up to etherification temperature and is reacted, and cools to room temperature after reaction, and reaction is adjusted between pH=7~8, pulls out
Fabric is simultaneously washed, drying；Wherein the mass ratio of monoxone and cellulose based fabric is 0.1~1:1.
4. preparation method according to claim 3, which is characterized in that the mass fraction of the sodium hydroxide solution be 1~
10%；The solvent of sodium hydroxide solution is the ethanol water that mass fraction is 70%~90%.
5. preparation method according to claim 3, which is characterized in that the quaternization are as follows: quaternization at 10~30 DEG C
10~60min；Etherification temperature is reacted: etherification temperature is 50~70 DEG C, reaction time 60-300min.
6. preparation method according to claim 1, which is characterized in that the concentration of aqueous bismuth nitrate solution is in the step (2)
0.5~10mmol/L；The concentration of bromide ion solution is 0.5~10mmol/L.
7. preparation method according to claim 1, which is characterized in that the concentration of silver nitrate solution is in the step (3)
0.2-3g/L。
8. preparation method according to claim 1, which is characterized in that photo-reduction in the step (3) are as follows: the ultraviolet light of use
Wavelength is 235nm, and the photo-reduction time is 1~60min.
9. a kind of loaded Ag/BiOBr nanometer sheet cellulose based fabric of claim 1 the method preparation.
10. a kind of loaded Ag described in claim 9/BiOBr nanometer sheet cellulose based fabric organic contamination in light degradation sewage
Application in object.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112206792A (en) * | 2020-10-22 | 2021-01-12 | 广州绿然环保新材料科技有限公司 | Catalyst for heavy metal sewage treatment and preparation method thereof |
| CN114160173A (en) * | 2021-12-24 | 2022-03-11 | 盐城工学院 | Application of bismuth oxyiodide photocatalytic material based on insoluble metal salt in fabric finishing |
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| CN101850263A (en) * | 2010-06-17 | 2010-10-06 | 江西理工大学 | Ag doped BiOBr catalytic material and preparation method and application thereof |
| CN106978715A (en) * | 2017-04-20 | 2017-07-25 | 武汉工程大学 | A kind of weaving cloth composite with photocatalysis and anti-microbial property and preparation method thereof |
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| CN101850263A (en) * | 2010-06-17 | 2010-10-06 | 江西理工大学 | Ag doped BiOBr catalytic material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112206792A (en) * | 2020-10-22 | 2021-01-12 | 广州绿然环保新材料科技有限公司 | Catalyst for heavy metal sewage treatment and preparation method thereof |
| CN114160173A (en) * | 2021-12-24 | 2022-03-11 | 盐城工学院 | Application of bismuth oxyiodide photocatalytic material based on insoluble metal salt in fabric finishing |
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