CN109550524A - A kind of textile fabric/BiVO4The preparation method of/CoO composite photocatalyst material - Google Patents
A kind of textile fabric/BiVO4The preparation method of/CoO composite photocatalyst material Download PDFInfo
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- CN109550524A CN109550524A CN201811503363.1A CN201811503363A CN109550524A CN 109550524 A CN109550524 A CN 109550524A CN 201811503363 A CN201811503363 A CN 201811503363A CN 109550524 A CN109550524 A CN 109550524A
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- bivo
- coo
- textile fabric
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- coo composite
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- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000004744 fabric Substances 0.000 title claims abstract description 29
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000004753 textile Substances 0.000 title claims abstract description 22
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000008187 granular material Substances 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- XPCTZQVDEJYUGT-UHFFFAOYSA-N 3-hydroxy-2-methyl-4-pyrone Chemical compound CC=1OC=CC(=O)C=1O XPCTZQVDEJYUGT-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- HYMLWHLQFGRFIY-UHFFFAOYSA-N Maltol Natural products CC1OC=CC(=O)C1=O HYMLWHLQFGRFIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229940043353 maltol Drugs 0.000 claims description 6
- 229920000128 polypyrrole Polymers 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229920003043 Cellulose fiber Polymers 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012209 synthetic fiber Substances 0.000 claims description 2
- 229920002994 synthetic fiber Polymers 0.000 claims description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims 2
- 230000008929 regeneration Effects 0.000 claims 1
- 238000011069 regeneration method Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910002445 Co(NO3)3·6H2O Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000004098 Tetracycline Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229960002180 tetracycline Drugs 0.000 description 2
- 229930101283 tetracycline Natural products 0.000 description 2
- 235000019364 tetracycline Nutrition 0.000 description 2
- 150000003522 tetracyclines Chemical class 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229920004934 Dacron® Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- -1 mercapto propyl Chemical group 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 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
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 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 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite 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
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
-
- B01J35/39—
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of textile fabric/BiVO4The preparation method of/CoO composite photocatalyst material.This method comprises: BiVO4The preparation of/CoO composite granule, BiVO4The preparation of/CoO composite catalyst, textile fabric/BiVO4The preparation of/CoO composite photocatalyst material.This method is simple, at low cost, easy to industrialized production；The composite catalyzing material catalytic performance of preparation is good, and can be recycled.
Description
Technical field
The invention belongs to the preparation method field of environmental catalysis material, in particular to a kind of textile fabric/BiVO4/ CoO is multiple
The preparation method of light combination catalysis material.
Background technique
As size of population growth and industrialization development, water pollution problems have become one of environmental problem of most serious,
Different degrees of threat is caused to human health and social development, problem of environmental pollution receives more and more attention.Industry
Dyeing waste water amount is big, contained pollutant kind is more, difficult to degrade, becomes the important factor in order of pollution, and people have studied many kinds
Method solves problem of environmental pollution, especially organic pollutant pollution problem, however traditional processing method is such as: physical absorption
Method, electrolysis method, microorganism treatment, biochemical degradation method etc.；Wherein physical treatment method is simple adsorption treatment, and
Unresolved substantive issue；Though and some chemical oxidation techniques can degradation of organic substances but time-consuming, effort and at high cost, or even can produce
Raw secondary pollution, cannot be used in large scale investment water.Therefore a kind of energy conservation and environmental protection, without secondary pollution, efficient green is designed
Color catalyst has a very important significance.
Pucherite (BiVO4) due to its low band gaps, good dispersion, nontoxicity, corrosion resistance and visible light catalytic drop
The excellent performance of solution organic pollutant etc. and the extensive concern for causing people.The forbidden bandwidth of pucherite is 2.3~2.4eV,
Belong to the range of low-gap semiconductor, and its oxidizing potential is located near 2.4eV, possesses very strong organic pollutant degradation energy
Power, compared to traditional catalysis material (TiO2, ZnO etc.), development prospect is more wide.Pucherite semiconductor conduction band current potential is
0V causes its photo-catalysis capability limited with the low defect of light absorpting ability difference and photo-generated carrier separation rate.The addition of CoO
The absorption intensity to visible light is enhanced, the hetero-junctions having widened the response range to visible light, and having been formed therebetween has
The compound of inhibition, obstruction light induced electron and hole is imitated, the catalytic performance of catalyst is further improved.
There are two major classes in powder photocatalyst: first is that easy cluster when using in use；Second is that difficult after use
Recycling, this substantially reduces process of manufacture efficiency.But nowadays it is not still about the research of catalyst loading problem
It is very deep, it needs us to continue research and pays close attention to and improved.Researchers are in textile fabric surface construction high-specific surface area
Micro nano structure, and overcoming adhesive, various slurries is the starting point to the adverse effect of catalysis fibre performance, attempts to use
Sol-gel dressed method prepares photo-catalysis function fiber, the results showed that the catalysis fibre of this method preparation has certain catalysis
Performance, but there is following problems: hot setting arranges process and textile fabric mechanical performance is severely impacted, molten
Glue-gel process manufacturing cycle is longer, inefficiency etc..For synthesis, the application of this method is extremely restricted.Therefore,
Under cryogenic, realize that nano-photocatalyst is converted into current research hotspot to setting from amorphous.The problem
Solution is to seek a kind of side of low temperature preparation high efficiency photocatalyst that can bypass high temperature crystal growth and phase transformation link
Then method again processes textile fabric.
Chinese invention patent application number (CN201810123820.8) discloses a kind of pucherite photocatalytic functional fabric
Preparation method: first by zeolites imidazole skeleton material (ZIF#8) processing to fabric, in situ synthesis is then used, by vanadic acid
Bismuth (BiVO4) load on the fabric handled with ZIF#8, the photocatalytic functional fabric of the method preparation under visible light illumination can
Efficient catalytic degradable organic pollutant can be used for treatment of dyeing wastewater and air cleaning.But degradation results show: to work
Property black KN#B photocatalytic activity up to 85% or more, active black KN#B photocatalytic activity is protected after reusing 3 times
It holds 65% or more, 87% or more is reached to the Degradation Formaldehyde rate in air.
Chinese invention patent application number (201710383499.2) discloses a kind of compound pucherite of monoclinic form tungsten oxide
Catalysis material and its preparation method and application, using sol-gal process, configuration joined appropriate C6H807The Bi of (citric acid)
(NO)3.5H2O nitric acid solution；With joined appropriate C6H807The NH of (citric acid)4VO3Aqueous solution is equal using magnetic agitation mixing
It is even, appropriate (NH is added4)6H2W12O40The forerunner's reaction source of (metatungstic acid ammonia) as tungsten oxide, is placed on 80-100 DEG C of water-bath
Under the conditions of react 4 hours, through Muffle furnace take off fire after drying grinding；By optimization reaction process in pH value, reaction temperature and
The amount of substance and fiery parameter is taken off, the compound pucherite material of monoclinic form tungsten oxide with good photocatalysis performance can be prepared.
Reach 97% or more in degradation rate of the 120min to rhodamine B.
Chinese invention patent application number (201710148502.2) discloses a kind of Z-type catalysis material pucherite-silver-bromine
Change the preparation method of silver, pucherite-silver-silver bromide preparation method is the following steps are included: firstly, by bismuth vanadate microcrystalline point
It is scattered in aqueous solution, certain silver nitrate is added and is irradiated 3 hours with 300W xenon lamp after stirring to silver nitrate dissolution, makes silver ion
On pucherite surface by in-situ reducing at Nano silver grain (suspension becomes celadon from faint yellow)；Then, heavy by what is obtained
Starch centrifuge washing 3 times, foreign ion is removed, drying obtains pucherite-silver；Finally, dispersing aqueous solution for pucherite-silver
In, ferric nitrate and potassium bromide solution is added, reacts 1 hour, centrifuge washing obtains AgBr-Ag-BiV04 catalysis material.The party
Method has the advantages that easy to operate, reaction condition is mild, short preparation period.Prepared Z-type catalysis material can be used for degrading
The environmental contaminants such as tetracycline, 80min can reach 95% or more to the degradation rate of tetracycline, but the presence of Ag makes catalyst
Performance is unstable, has photoetch.
According to examples detailed above, although the effect of the photocatalytic degradation of each method plays sewage treatment also than more significant
Certain effect, but degradation takes a long time, and it is not good enough that performance is recycled.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of textile fabric/BiVO4/ CoO composite photocatalyst material
Preparation method, to overcome, the catalytic performance of composite catalyst in the prior art is poor, recycling performance is bad and composite catalyzing
The defects of agent preparation needs high temperature.
The present invention is prepared for a kind of composite photocatalyst material, while improving photocatalytic degradation efficiency, is recycled
Performance is also ensured.
A kind of textile fabric/BiVO of the invention4The preparation method of/CoO composite photocatalyst material, comprising:
(1) by Bi (NO3)3·5H2O is added to NH4VO3In aqueous solution, certain proportion Co (NO is added in stirring3)3·6H2O,
Hydro-thermal reaction, cooling, filtering and washing, drying obtain BiVO4/ CoO composite granule is calcined, cooling, obtains BiVO4/ CoO is compound
Catalyst, wherein Bi (NO3)3·5H2O、NH4VO3With Co (NO3)3·6H2The molar ratio of O are as follows: 25:25:2~5:5:2；
(2) textile fabric is impregnated in BiVO in step (1)4In the aqueous dispersion of/CoO composite catalyst, it is added and uses
Measure the PEG of 0.1g/L~0.3g/L, the maltol of dosage 0.5g/L-1.5g/L, the polypyrrole of dosage 0.2g/L-0.6g/L, use
Measure the hexadecyltrimethylammonium chloride of 0.03g/L-0.07g/L and the mercapto propyl-triethoxysilicane of dosage 0.1g/L-0.3g/L
Alkane stirs, and washs, and drying bakes, obtains textile fabric/BiVO4/ CoO composite photocatalyst material, wherein the bath raio impregnated is
100:1~200:1.
Hydrothermal temperature is 140 DEG C~180 DEG C in the step (1), and the hydro-thermal reaction time is 4h~8h.
Calcination temperature is 300 DEG C~500 DEG C in the step (1), and calcination time is 2~4h.
BiVO in the step (1)4BiVO in/CoO composite catalyst4Mass ratio with CoO is 10:1~50:1.
Washing includes: to be washed with deionized 3 times in the step (1), (2)；Drying temperature is 60 DEG C.
Textile fabric is ultrasonically treated 30min using preceding putting it into 100mL acetone in the step (2), then vacuum
It is dry.
In the step (2) textile fabric be cellulose fibre, it is protein fibre, regenerated fiber, a kind of in synthetic fibers
Or it is several.
BiVO in the step (2)4The concentration of the aqueous dispersion of/CoO composite catalyst is 0.5~1.5mg/mL.
Whipping temp is 55 DEG C~85 DEG C in the step (2), and mixing time is 0.5h~1.5h.
Baking temperature is 160~180 DEG C in the step (2), and baking the time is 3~7min.
PEG, the maltol, polypyrrole, hexadecyltrimethylammonium chloride, three second of mercapto propyl being added in the step (2)
The auxiliary agents such as oxysilane be in order to improve the fastness that powder catalyst adheres in fabric surface, with increase textile fabric/
BiVO4The recycling performance of/CoO composite photocatalyst material.
The present invention utilizes n-type semiconductor BiVO4BiVO is prepared with p-type semiconductor CoO4/ CoO composite highly effective catalyst, herein
On the basis of further construct the nano semiconductor material with controllable appearance, composition, size and porous structure, to be formed novel
Textile fabric/BiVO4/ CoO catalysis material makes fiber can using the good physical and chemical performance of flexible fibrous material
Pollutant is adsorbed to a certain degree, and can provide the reaction bad border of high concentration by absorption pollutant for nano-photocatalyst material, it is bright
It is aobvious to improve photocatalytic degradation reaction rate.In addition, the suction-operated of fiber is also possible to make in photocatalytic degradation reaction generation
Between by-product be adsorbed and be further oxided and be degraded to simple inorganic matter when generating, such as carbon dioxide and water.Therefore,
Composite photocatalyst material can not only assemble pollutant, accelerate photocatalytic degradation reaction, can also reduce intermediate by-products to ring
The secondary pollution in border；BiVO4Hetero-junctions between/CoO ensures to realize the directional transmissions of light induced electron, effectively improves electron hole
Separative efficiency；The addition of textile fabric simultaneously increases the contact area of catalyst and pollutant, provides more for light-catalyzed reaction
Reactive site, improve its photocatalytic activity, be conducive to recycling.
Beneficial effect
(1) present invention is simple, at low cost, easy to industrialized production；
(2) composite catalyzing material catalytic performance prepared by the present invention is good, degradation rate 100% or so, and can recycle and make
With.
Detailed description of the invention
Fig. 1 is fiber (a) and fiber/BiVO in embodiment 14/ CoO composite photocatalyst material (b) sample drawing.
Fig. 2 is that dye liquor sample (a) and composite photocatalyst material use when composite photocatalyst material is not added in embodiment 1
Once (b) and 10 (c) dye liquor samples of use.
Fig. 3 is fiber (a) and fiber/BiVO in embodiment 24/ CoO composite photocatalyst material (b) sample drawing.
Fig. 4 is that dye liquor sample (a) and composite photocatalyst material use when composite photocatalyst material is not added in embodiment 2
Once (b) and 10 (c) dye liquor samples of use.
Fig. 5 is fiber (a) and fiber/BiVO in embodiment 34/ CoO composite photocatalyst material (b) sample drawing.
Fig. 6 is that dye liquor sample (a) and composite photocatalyst material use when composite photocatalyst material is not added in embodiment 3
Once (b) and 10 (c) dye liquor samples of use.
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.
The preparation method of dye liquor used in main agents and test material source (being shown in Table 1) and degradation process is as follows:
Table 1
The preparation method of the reactive blue RB-19 dye liquor of used 50mg/L: the reactive blue RB-19 for weighing 50mg is added
In the deionized water of 500mL, ultrasonic 1h is poured into the volumetric flask of 1L and is settled to graduation mark, and it is spare to continue ultrasound 1h.
Embodiment 1
(1) by the Bi (NO of 5mmoL3)3·5H2O is added to the NH of the 0.25moL/L of 20mL4VO3In aqueous solution, stirring,
Add 0.126g Co (NO3)3·6H2O, 140 DEG C of hydro-thermal reaction 4h, cooling, suction filtration, are distinguished with dehydrated alcohol and deionized water
Washing 3 times, 60 DEG C of drying, obtains BiVO4The composite granule of/CoO；Gained powder is put into 300 DEG C of calcining 2h of Muffle furnace, it is cooling
Obtain BiVO4/ CoO composite catalyst.
(2) cotton fabric is impregnated in 0.5mg/mL BiVO4/ CoO composite catalyst aqueous dispersion (bath raio 100:
1) it in, is added PEG (dosage 0.1g/L), maltol (dosage 0.5g/L), polypyrrole (dosage 0.2g/L), cetyl trimethyl
Ammonium chloride (dosage 0.04g/L) and mercaptopropyltriethoxysilane (dosage 0.1g/L), in 55 DEG C of heating stirring 0.5h, go from
Sub- water washing, 60 DEG C drying, 160 DEG C bake 3min and obtain cotton fiber/BiVO4/ CoO composite photocatalyst material.
Embodiment 2
(1) by the Bi (NO of 5mmoL3)3·5H2O is added to the NH of the 0.25moL/L of 20mL4VO3In aqueous solution, stirring,
Add 0.315g Co (NO3)3·6H2O, 160 DEG C of hydro-thermal reaction 6h, cooling, suction filtration, are distinguished with dehydrated alcohol and deionized water
Washing 3 times, 60 DEG C of drying, obtains BiVO4The composite granule of/CoO；Gained powder is put into 400 DEG C of calcining 3h of Muffle furnace, it is cooling
Obtain BiVO4/ CoO composite catalyst.
(2) wool fabric is impregnated in 1.0mg/mL BiVO4(bath raio is the aqueous dispersion of/CoO composite catalyst
In 150:1), it is added PEG (dosage 0.2g/L), maltol (dosage 1.0g/L), polypyrrole (dosage 0.4g/L), cetyl three
Ammonio methacrylate (dosage 0.05g/L) and mercaptopropyltriethoxysilane (dosage 0.2g/L) are gone in 70 DEG C of heating stirring 1h
Ion water washing, 60 DEG C drying, 170 DEG C bake 5min and obtain wool fiber/BiVO4/ CoO composite photocatalyst material.
Embodiment 3
(1) by the Bi (NO of 5mmoL3)3·5H2O is added to the NH of the 0.25moL/L of 20mL4VO3In aqueous solution, stirring,
Add 0.63g Co (NO3)3·6H2O, 180 DEG C of hydro-thermal reaction 8h, cooling, suction filtration, are distinguished with dehydrated alcohol and deionized water
Washing 3 times, 60 DEG C of drying, obtains BiVO4The composite granule of/CoO；Gained powder is put into 500 DEG C of calcining 4h of Muffle furnace, it is cooling
Obtain BiVO4/ CoO composite catalyst.
(2) dacron is impregnated in 1.5mg/mL BiVO4(bath raio is the aqueous dispersion of/CoO composite catalyst
In 200:1), it is added PEG (dosage 0.3g/L), maltol (dosage 1.5g/L), polypyrrole (dosage 0.6g/L), cetyl three
Ammonio methacrylate (dosage 0.06g/L) and mercaptopropyltriethoxysilane (dosage 0.3g/L), in 85 DEG C of heating stirring 1.5h,
Deionized water washing, 60 DEG C drying, 180 DEG C bake 7min and obtain polyester fiber/BiVO4/ CoO composite photocatalyst material.
Using the reactive blue RB-19 of 50mg/L made from the above-mentioned same time as process object, in 50mL dye liquor respectively
The resulting water treatment agent of Examples 1 to 3 is added, after 2 hours xenon lamps irradiate, degradation rate such as table 2 of the water treatment agent to dye liquor
It is shown.
Table 2
| Water treatment agent | Degradation rate (%) | Dye liquor degradation rate (%) after reusing 10 times |
| Embodiment 1 | 99.6 | 91.2 |
| Embodiment 2 | 98.5 | 90.5 |
| Embodiment 3 | 99.8 | 91.8 |
Claims (9)
1. a kind of textile fabric/BiVO4The preparation method of/CoO composite photocatalyst material, comprising:
(1) by Bi (NO3)3·5H2O is added to NH4VO3In aqueous solution, Co (NO is added in stirring3)3·6H2O, hydro-thermal reaction are cold
But, filtering and washing, drying, obtain BiVO4/ CoO composite granule is calcined, cooling, obtains BiVO4/ CoO composite catalyst, wherein
Bi(NO3)3·5H2O、NH4VO3With Co (NO3)3·6H2The molar ratio of O is 25:25:2~5:5:2；
(2) textile fabric is impregnated in BiVO in step (1)4In the aqueous dispersion of/CoO composite catalyst, dosage is added
The PEG of 0.1g/L~0.3g/L, the maltol of dosage 0.5g/L-1.5g/L, the polypyrrole of dosage 0.2g/L-0.6g/L, dosage
The hexadecyltrimethylammonium chloride of 0.03g/L-0.07g/L and the mercaptopropyltriethoxysilane of dosage 0.1g/L-0.3g/L,
Stirring is washed, and drying bakes, obtains textile fabric/BiVO4/ CoO composite photocatalyst material, wherein the bath raio impregnated is 100:
1~200:1.
2. the method according to claim 1, wherein in the step (1) hydrothermal temperature be 140 DEG C~
180 DEG C, the hydro-thermal reaction time is 4h~8h.
3. the method according to claim 1, wherein in the step (1) calcination temperature be 300 DEG C~500 DEG C,
Calcination time is 2~4h.
4. the method according to claim 1, wherein BiVO in the step (1)4In/CoO composite catalyst
BiVO4Mass ratio with CoO is 10:1~50:1.
5. the method according to claim 1, wherein washing includes: to use deionized water in the step (1), (2)
Washing 3 times；Drying temperature is 60 DEG C.
6. the method according to claim 1, wherein textile fabric is using preceding putting it into the step (2)
It is ultrasonically treated 30min in 100mL acetone, is then dried in vacuo；Textile fabric is cellulose fibre, protein fibre, regeneration fibre
One of dimension, synthetic fibers are several.
7. the method according to claim 1, wherein BiVO in the step (2)4Point of/CoO composite catalyst
The concentration of aproll solution is 0.5~1.5mg/mL.
8. being stirred the method according to claim 1, wherein whipping temp is 55 DEG C~85 DEG C in the step (2)
Mixing the time is 0.5h~1.5h.
9. being roasted the method according to claim 1, wherein baking temperature is 160~180 DEG C in the step (2)
The baking time is 3~7min.
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| JP2006256901A (en) * | 2005-03-17 | 2006-09-28 | Nissan Motor Co Ltd | Hydrogen production apparatus, hydrogen production method and hydrogen production system |
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