CN110465320A - A kind of compound photocatalytic activity coating and preparation method thereof - Google Patents
A kind of compound photocatalytic activity coating and preparation method thereof Download PDFInfo
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- CN110465320A CN110465320A CN201910799807.9A CN201910799807A CN110465320A CN 110465320 A CN110465320 A CN 110465320A CN 201910799807 A CN201910799807 A CN 201910799807A CN 110465320 A CN110465320 A CN 110465320A
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- 238000000576 coating method Methods 0.000 title claims abstract description 52
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 52
- 239000011248 coating agent Substances 0.000 title claims abstract description 50
- 150000001875 compounds Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 38
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 230000000694 effects Effects 0.000 claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 22
- 230000003287 optical effect Effects 0.000 claims abstract description 15
- 239000006210 lotion Substances 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 65
- 229910021389 graphene Inorganic materials 0.000 claims description 37
- 239000006185 dispersion Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- 229910002804 graphite Inorganic materials 0.000 claims description 19
- 239000010439 graphite Substances 0.000 claims description 19
- 239000000839 emulsion Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 230000015556 catabolic process Effects 0.000 claims description 12
- 238000006731 degradation reaction Methods 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 12
- 239000006096 absorbing agent Substances 0.000 claims description 11
- 239000003463 adsorbent Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 239000002562 thickening agent Substances 0.000 claims description 11
- 238000000643 oven drying Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 229910052613 tourmaline Inorganic materials 0.000 claims description 5
- 229940070527 tourmaline Drugs 0.000 claims description 5
- 239000011032 tourmaline Substances 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 4
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 4
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 4
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229940080314 sodium bentonite Drugs 0.000 claims description 3
- 229910000280 sodium bentonite Inorganic materials 0.000 claims description 3
- 229940117958 vinyl acetate Drugs 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- HNPDNOZNULJJDL-UHFFFAOYSA-N ethyl n-ethenylcarbamate Chemical compound CCOC(=O)NC=C HNPDNOZNULJJDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 43
- 238000007146 photocatalysis Methods 0.000 abstract description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 23
- 239000003054 catalyst Substances 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 19
- 235000010215 titanium dioxide Nutrition 0.000 description 8
- 229960005196 titanium dioxide Drugs 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 8
- 230000032683 aging Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000011481 absorbance measurement Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B01J35/61—
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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
Abstract
The present invention relates to photocatalysis coating technical fields more particularly to a kind of compound photocatalytic activity coating and preparation method thereof.Comprising the following three steps: (1) prepare composite modified TiO2Powder；(2) compound TiO is prepared2Photocatalytic activity lotion；(3) active coating is prepared.Prepared photocatalytically active coating, photocatalysis efficiency is high, optical response range is wide, efficiently solves TiO2The recycling of powder catalyst is difficult, photocatalysis efficiency is low, during light-catalyzed reaction it is easy to reunite, be also easy to produce secondary pollution problems, and photocatalytic activity coating prepared by the present invention is reusable, the usage amount for reducing catalyst, has a vast market application prospect.
Description
Technical field
The present invention relates to photocatalysis coating technical field more particularly to a kind of compound photocatalytic activity coatings
And preparation method thereof.
Background technique
Since industrial wastewater has the characteristics that complicated component, pollutant concentration are high and processing difficulty is big, so can be to ring
Serious harm is caused in border, so the harmless treatment of industrial wastewater is always the research hotspot and difficult point of environment protection field.It is conventional
Water treatment technology, such as physisorphtion, activated sludge process, biological degradation method are limited to the treatment effect of industrial wastes.Work
The processing of industry waste water focuses mostly on grinding in high-level oxidation technologies such as Ozonation, electrochemical oxidation process and photocatalytic oxidations
Study carefully.From the point of view of current present Research, TiO2Compound catalysis material is because of the strong, chemical stability with redox ability
The features such as high and low in cost, it is considered to be the most conductor photocatalysis material of the such waste liquid of processing of application potential, but its
There are still many problems to be solved and research: 1.TiO2Catalysis material is in granular form powder more, and when use easily reunites, and leads
Specific surface area is caused to reduce, photocatalytic activity reduces, and is difficult to recycle again after use；2.TiO2Although having stable photocatalysis
Performance, but the forbidden bandwidth between its valence band and conduction band is big, and corresponding light absorption threshold value is ultraviolet region, and in solar energy
It is that ultraviolet light provides only less than 5%, the efficiency of light energy utilization is low.TiO after composite modified2Catalyst and TiO2Film/coating prepares skill
Art will make TiO2Photocatalysis efficiency raising, TiO2Particle is fixed on carrier, can effectively overcome above-mentioned problem, is had good
Research and application value.
Summary of the invention
Present invention solves the technical problem that being TiO2Photocatalytic activity is low in practical applications for catalysis material, is difficult to back
Secondary use is received, secondary pollution is also easy to produce, cannot achieve large-scale application.
To solve the above problems, the present invention devises a kind of compound photocatalytic activity coating and its preparation side
Method, to TiO2Catalysis material progress is composite modified, and prepares TiO2Photocatalytically active coating can effectively improve TiO2Light
Catalytic activity and structural stability.
In order to achieve the above objectives, the following technical solution is employed: a kind of compound photocatalytic activity by the present invention
The preparation method of coating, comprising the following three steps:
(1) composite modified TiO is prepared2Powder；
(2) compound TiO is prepared2Photocatalytic activity lotion；
(3) active coating is prepared；
Wherein, step (1) be specially press volume parts, respectively weigh butyl titanate 50-70 parts, 20-50 parts of dehydrated alcohol,
0-30 parts of deionized water, mixing is made into solution A；By volume parts, graphene dispersing solution 10-30 parts, graphite oxide are weighed respectively
10-20 parts of 10-30 parts of alkene dispersion liquid, 10-30 parts of class graphite phase carbon nitride dispersion liquid, 10-30 parts of glacial acetic acid and dehydrated alcohol are gone
0-20 parts of ionized water, mixing is made into B solution；B solution is slowly added dropwise to solution A, pH value is adjusted to 1.5-2.5, mixes and stir
After mixing uniformly, it is aged 12-36h, 100 DEG C of oven dryings naturally, composite modified TiO is made in 300 DEG C of roastings2Powder.
Butyl titanate is titanium source in solution A, and dehydrated alcohol and water are solvent；
Graphene dispersing solution, graphene oxide dispersion, class graphite phase carbon nitride dispersion liquid are photocatalysis performance in B solution
Modified material, glacial acetic acid are stabilizer, and dehydrated alcohol and water are solvent.
The effect that B solution is slowly added dropwise is control reaction hydrolysis rate, inhibits precipitating to generate, forms stable sol.
It is had the following problems when titanium dioxide is as photocatalyst applications: first is that titanium dioxide is as a kind of nano material,
Easily reunite in its preparation process, the particle scale of formation is big, and reduces the specific surface area of nanoparticle, is unfavorable for the later period
Application；Second is that in the application, photocatalysis material of titanium dioxide exists mostly in the form of powder, easily cause dust degree big and former
Material bad dispersibility is easy to reunite, the problem of recycling hardly possible, causes secondary pollution to environment, is detrimental to health；Third is that titanium dioxide
Forbidden band is wider, and the recombination probability in light induced electron and hole is big, and ultraviolet light can only be absorbed and utilized, and optical response range is narrow, urges its light
Changing efficiency reduces.Therefore, titanium dioxide is modified processing and has become current research hotspot to improve its waste water treatment efficiency.This
Invention prepares composite modified TiO by addition graphene, class graphene isoreactivity substance2Photochemical catalyst makes TiO2Photocatalysis
Efficiency improves；And pass through TiO2Film/coat preparing technology is by TiO2Particle is fixed on carrier, solves powdery type titanium-dioxide photo
Catalysis material difficulty recycles, is easy to reunite, being also easy to produce secondary pollution problem.
Further, the weight ratio of the solution A and B solution is 1:1-5:1.The photocatalysis performance of material is with graphite
Alkene, class graphene isoreactivity substance additional amount increase and improve, but after additional amount reaches certain amount, photocatalysis performance will
Kept stable；Also, when graphene, class graphene isoreactivity substance additional amount are excessive, it will affect TiO2Photocatalysis
Response area, so that light-catalyzed reaction performance is influenced, so needing to control solution A and B solution within the scope of suitable weight ratio.
Further, the graphene dispersing solution, graphene oxide dispersion, graphite in class graphite phase carbon nitride dispersion liquid
Alkene, graphene oxide, class graphite phase carbon nitride mass concentration be 10-70%.Preferred mass concentration is 60%, mass concentration mistake
Low, then graphene, class graphene isoreactivity content of material are low, and photocatalysis performance improves unobvious；Mass concentration is excessively high, then active
Substance dispersion is uneven, easy to reunite, cannot uniformly be scattered in TiO2Catalysis material surface, influences modified effect.
Further, step (2) is specially and calculates by weight, the composite modified TiO that step (1) is prepared2Powder
20-50 parts, 30-70 parts of polymer emulsion, 5-10 parts of porous adsorbent, 1-5 parts of surfactant, 1-5 parts of optical absorbing agent, thickener
It 0.5-3 parts and 0.5-3 parts of other function additives, stirring at normal temperature 20-30min, is uniformly mixed, ultrasonic disperse is made compound
TiO2Photocatalytic activity lotion.Composite modified TiO2Powder is catalysis material；Polymer emulsion is TiO2The film forming matter of coating
Matter；Porous adsorbent is filler；Surfactant can reduce coating surface tension effect, play the role of evenly dispersed and defoaming；
Optical absorbing agent can enhance the photo absorption performance of coating, enhance the photocatalysis of catalysis material；Thickener can stable coatings, prevent from applying
Layer cracking；Other function auxiliary agent can enhance the resistance to UV aging of coating material, pollutant catalytic conversion efficiency, compression strength
Deng.
Further, the polymer emulsion is vinylacetate, ethylene, butadiene, acrylate, the poly- ammonia of vinyl
One of ester, polyisocyanates or more than one mixture.
Further, the porous adsorbent be one of active powdered carbon, ceramic powder, zeolite powder, glass microballoon or
More than one mixtures formed in any proportion.
Further, the surfactant is gamma-aminopropyl-triethoxy-silane (KH-550)；The optical absorbing agent is charcoal
One of black, carbon nanotube, graphite or more than one mixture.
Further, the thickener is polypropylene fibre, sodium bentonite, hydroxypropyl methyl cellulose and polyethylene
The mixture obtained after one or more kinds of combinations in any proportion of alcohol；The other function auxiliary agent be metal powder,
Tourmaline powder, nano-cerium oxide (CeO2), the mixture that is obtained after combining in any proportion of glass fibre.
Further, step (3) is specially by the compound TiO of step (2)2Photocatalytic activity Emulsion Spraying in substrate,
80 DEG C of oven drying 2h are placed in, repeat spraying several times, until coating layer thickness reaches 50-300 μm, compound titanium dioxide is made
Photocatalytically active coating.
Further, the substrate is metal, ceramics or glass.Base material component influences the adhesive force of coating, influences this hair
The service life of compound photocatalytic activity coating in bright.
A kind of compound photocatalytic activity coating prepared in aforementioned manners, in the light-catalyzed reaction of 30min
The light-catalyzed reaction degradation rate > 60,120min of the light-catalyzed reaction degradation rate > 45% of degradation rate > 24%, 60min, 90min
Light-catalyzed reaction degradation rate > 74%.
The beneficial effect is that:
(1) a kind of preparation method of active coating formed with the composite modified catalysis material of titanium dioxide is provided, at
This low, good operability, application easy to spread, can be used for industrial wastewater and organic and inorganic pollution light degradation of other waste liquids
Processing
(2) composite modified TiO2The active constituent of powder can effectively expand TiO2The optical response range of catalysis material, enhancing
TiO2Catalysis material is to ultraviolet and visible region light absorpting ability, and the efficiency of light energy utilization increases, photocatalytic activity improves.
(3) porous adsorbent and other function additives are added in compound photocatalytic activity coating, not only
Effectively extend composite modified TiO in coating2The specific surface area of powder improves photocatalysis efficiency, or obtains coating and have both anti-purple
The multi-functionals such as outer aging, antibacterial sterilization.
(4) compound photocatalytic activity coating photocatalysis efficiency is high, optical response range is wide, efficiently solves
TiO2The recycling of powder catalyst is difficult, photocatalysis efficiency is low, during light-catalyzed reaction it is easy to reunite, be also easy to produce secondary pollution etc. and ask
Topic, and it is reusable, reduce the usage amount of catalyst, has a vast market application prospect.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with implementation of the invention
Example, is clearly and completely described technical solution of the present invention.Obviously, described embodiment is that a part of the invention is real
Example is applied, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creation
Property labour under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1:
A kind of preparation method of compound photocatalytic activity coating, which comprises the following steps:
(1) composite modified TiO is prepared2Powder:
By volume parts, 60 parts of butyl titanate, 20 parts of dehydrated alcohol are weighed respectively, 20 parts of deionized water, it is molten that mixing is made into A
Liquid；
By volume parts, 20 parts of graphene dispersing solution, 20 parts of graphene oxide dispersion, the nitridation of class graphite-phase are weighed respectively
20 parts of carbon dispersion liquid, 20 parts of glacial acetic acid and 20 parts of dehydrated alcohol, mixing are made into B solution；
It is 1:1 by the weight ratio of solution A and B solution, B solution is slowly added dropwise to solution A, adjusts pH value to 2.0, mix
And after mixing evenly, for 24 hours, composite modified TiO is made in 100 DEG C of oven drying 3h, 300 DEG C of roastings for ageing naturally2Powder.
(2) compound TiO is prepared2Photocatalytic activity lotion:
It calculates by weight, by 67.5 parts of 20 parts of composite modified TiO2 powder, polymer emulsion preparing, porous absorption
5 parts of agent, 2 parts of surfactant, 3 parts of optical absorbing agent, 0.5 part of thickener and 2 parts, stirring at normal temperature 30min of other function additives, mixing
Uniformly, compound TiO is made in ultrasonic disperse 1h2Photocatalytic activity lotion.
(3) active coating is prepared:
By compound TiO2Photocatalytic activity Emulsion Spraying is placed in 80 DEG C of oven drying 2h in substrate, and repetition sprays several
It is secondary, until coating layer thickness reaches 150 μm, compound photocatalytic activity coating is made.
Wherein, the graphene dispersing solution, graphene oxide dispersion, graphene in class graphite phase carbon nitride dispersion liquid,
Graphene oxide, class graphite phase carbon nitride mass concentration be 25%.
The polymer emulsion is the mixture of vinylacetate and acrylate.
The porous adsorbent is active powdered carbon.
The surfactant is gamma-aminopropyl-triethoxy-silane (KH-550)；The optical absorbing agent is carbon black.
The thickener is the mixture of hydroxypropyl methyl cellulose and polyvinyl alcohol；The other function auxiliary agent is
Metal powder, tourmaline powder, nano-cerium oxide (CeO2), mixture of glass fibers.
Preferably, the substrate is ceramics.
Embodiment 2:
A kind of preparation method of compound photocatalytic activity coating, which comprises the following steps:
(1) composite modified TiO is prepared2Powder:
By volume parts, 60 parts of butyl titanate, 40 parts of dehydrated alcohol are weighed respectively, and mixing is made into solution A；
By volume parts, 20 parts of graphene dispersing solution, 20 parts of graphene oxide dispersion, the nitridation of class graphite-phase are weighed respectively
20 parts of carbon dispersion liquid, 20 parts of glacial acetic acid and 10 parts of dehydrated alcohol, 10 parts of deionized water, mixing is made into B solution；
It is 2:1 by the weight ratio of solution A and B solution, B solution is slowly added dropwise to solution A, adjusts pH value to 2.0, mix
And after mixing evenly, for 24 hours, composite modified TiO is made in 100 DEG C of oven drying 3h, 300 DEG C of roastings for ageing naturally2Powder.
(2) compound TiO is prepared2Photocatalytic activity lotion:
It calculates by weight, the composite modified TiO that will be prepared230 parts of powder, 60 parts of polymer emulsion, porous adsorbent
5 parts, 1 part of surfactant, 2 parts of optical absorbing agent, 0.5 part of thickener and 1.5 parts, stirring at normal temperature 30min of other function additives, mixing
Uniformly, compound TiO is made in ultrasonic disperse 1h2Photocatalytic activity lotion.
(3) active coating is prepared:
By compound TiO2Photocatalytic activity Emulsion Spraying is placed in 80 DEG C of oven drying 2h in substrate, and repetition sprays several
It is secondary, until coating layer thickness reaches 200 μm, compound photocatalytic activity coating is made.
Wherein, the graphene dispersing solution, graphene oxide dispersion, graphene in class graphite phase carbon nitride dispersion liquid,
Graphene oxide, class graphite phase carbon nitride mass concentration be 50%.
The polymer emulsion is acrylate.
The porous adsorbent is the mixture of active powdered carbon and zeolite powder.
The surfactant is gamma-aminopropyl-triethoxy-silane (KH-550)；The optical absorbing agent is carbon black.
The thickener is sodium bentonite；The other function auxiliary agent is metal powder, tourmaline powder, nano oxygen
Change cerium (CeO2), mixture of glass fibers.
The substrate is ceramics.
Embodiment 3:
A kind of preparation method of compound photocatalytic activity coating, which comprises the following steps:
(1) composite modified TiO is prepared2Powder:
By volume parts, 60 parts of butyl titanate, 40 parts of dehydrated alcohol are weighed respectively, and mixing is made into solution A；
By volume parts, 20 parts of graphene dispersing solution, 20 parts of graphene oxide dispersion, the nitridation of class graphite-phase are weighed respectively
20 parts of carbon dispersion liquid, 20 parts of glacial acetic acid and 20 parts of dehydrated alcohol, mixing are made into B solution；
It is 2.5:1 by the weight ratio of solution A and B solution, B solution is slowly added dropwise to solution A, adjusts pH value to 2.0, mix
Merge after mixing evenly, for 24 hours, composite modified TiO is made in 100 DEG C of oven drying 3h, 300 DEG C of roastings for ageing naturally2Powder.
(2) compound TiO is prepared2Photocatalytic activity lotion:
It calculates by weight, the composite modified TiO that will be prepared235 parts of powder, 55 parts of polymer emulsion, porous adsorbent
5 parts, 1 part of surfactant, 2 parts of optical absorbing agent, 0.5 part of thickener and 1.5 parts, stirring at normal temperature 20-30min of other function additives,
It is uniformly mixed, compound TiO is made in ultrasonic disperse 1h2Photocatalytic activity lotion.
(3) active coating is prepared:
By compound TiO2Photocatalytic activity Emulsion Spraying is placed in 80 DEG C of oven drying 2h in substrate, and repetition sprays several
It is secondary, until coating layer thickness reaches 250 μm, compound photocatalytic activity coating is made.
Wherein, the graphene dispersing solution, graphene oxide dispersion, graphene in class graphite phase carbon nitride dispersion liquid,
Graphene oxide, class graphite phase carbon nitride mass concentration be 60%.
The polymer emulsion is the mixture of acrylate and vinyl urethane.
The porous adsorbent is active powdered carbon.
The surfactant is gamma-aminopropyl-triethoxy-silane (KH-550)；The optical absorbing agent is graphite.
The thickener is hydroxypropyl methyl cellulose；The other function auxiliary agent be metal powder, tourmaline powder,
The mixture of nano-cerium oxide (CeO2), glass fibre.
The substrate is ceramics.
Photocatalysis effect detection method is as follows:
Use concentration for 10mgL-1Methylene blue solution as testing compound photocatalytic activity coating
Photocatalysis coating obtained by embodiment 1-3 is made the sample of 5 × 5cm specification, is respectively put by the degraded solutions of photocatalysis performance
In 100ml methylene blue solution, it is placed on shaking table to be persistently protected from light and shakes 30min, after reaching adsorption equilibrium, be placed in photochemical reaction
Photocatalytic degradation experiment is carried out in instrument, reaction 30,60 and 90min sampling finally uses spectrophotometer pair after filter separates
Degraded solutions carry out absorbance measurement, light-catalyzed reaction degradation rate are thus calculated, the results are shown in Table 1:
Table 15 × 5cm specification piece photocatalysis effect testing result
| Degradation rate (%) | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| 30min | 24.3 | 35.2 | 37.1 |
| 60min | 45.7 | 59.8 | 60.3 |
| 90min | 61.9 | 78.9 | 79.5 |
| 120min | 74.1 | 89.4 | 89.9 |
The above, only the preferred embodiment of the present invention, protection scope of the present invention are not limited merely to above-mentioned reality
Example is applied, all technical solutions belonged under the invention thinking all belong to the scope of protection of the present invention.It should be pointed out that being led for this technology
For the technical staff in domain, also it is considered as protection scope of the present invention in any improvement for not departing from the principle of the invention.
Claims (10)
1. a kind of preparation method of compound photocatalytic activity coating, it is characterised in that comprising the following three steps:
(1) composite modified TiO is prepared2Powder；
(2) compound TiO is prepared2Photocatalytic activity lotion；
(3) active coating is prepared；
Wherein, step (1) be specially press volume parts, respectively weigh butyl titanate 50-70 parts, 20-50 parts of dehydrated alcohol, go from
Sub- water 0-30 parts, mixing is made into solution A；By volume parts, graphene dispersing solution 10-30 parts, graphene oxide point are weighed respectively
10-30 parts of dispersion liquid, 10-30 parts of class graphite phase carbon nitride dispersion liquid, 10-30 parts of glacial acetic acid and 10-20 parts of dehydrated alcohol, deionization
0-20 parts of water, mixing is made into B solution；B solution is slowly added dropwise to solution A, pH value is adjusted to 1.5-2.5, is mixed and stirred for
After even, it is aged 12-36h, 100 DEG C of oven dryings naturally, composite modified TiO is made in 300 DEG C of roastings2Powder.
2. the preparation method of compound photocatalytic activity coating as described in claim 1, it is characterised in that: described
The weight ratio of solution A and B solution is 1:1-5:1.
3. the preparation method of compound photocatalytic activity coating as described in claim 1, it is characterised in that: described
Graphene dispersing solution, graphene oxide dispersion, graphene, graphene oxide, class graphite in class graphite phase carbon nitride dispersion liquid
The mass concentration of phase carbon nitride is 10-70%.
4. the preparation method of compound photocatalytic activity coating as described in claim 1, it is characterised in that: step
It (2) is specially to calculate by weight, the composite modified TiO that step (1) is prepared220-50 parts of powder, polymer emulsion 30-
70 parts, 5-10 parts of porous adsorbent, 1-5 parts of surfactant, 1-5 parts of optical absorbing agent, 0.5-3 parts of thickener and other function additives
It 0.5-3 parts, stirring at normal temperature 20-30min, is uniformly mixed, compound TiO is made in ultrasonic disperse2Photocatalytic activity lotion.
5. the preparation method of compound photocatalytic activity coating as claimed in claim 4, it is characterised in that: described
Polymer emulsion be one of vinylacetate, ethylene, butadiene, acrylate, vinyl urethane, polyisocyanates or
More than one mixture；The porous adsorbent be one of active powdered carbon, ceramic powder, zeolite powder, glass microballoon or
More than one mixtures formed in any proportion.
6. the preparation method of compound photocatalytic activity coating as claimed in claim 4, it is characterised in that: described
Surfactant is gamma-aminopropyl-triethoxy-silane；The optical absorbing agent is one of carbon black, carbon nanotube, graphite or one
Kind or more mixture.
7. the preparation method of compound photocatalytic activity coating as claimed in claim 4, it is characterised in that: described
Thickener be polypropylene fibre, sodium bentonite, hydroxypropyl methyl cellulose and polyvinyl alcohol one or more press
The mixture obtained after arbitrary proportion combination；The other function auxiliary agent be metal powder, tourmaline powder, nano-cerium oxide,
The mixture that glass fibre obtains after combining in any proportion.
8. the preparation method of compound photocatalytic activity coating as described in claim 1, it is characterised in that: step
It (3) is specially by the compound TiO of step (2)2Photocatalytic activity Emulsion Spraying is placed in 80 DEG C of oven drying 2h in substrate, weight
Several times, until coating layer thickness reaches 50-300 μm, compound photocatalytic activity coating is made in multiple spraying.
9. the preparation method of compound photocatalytic activity coating as claimed in claim 8, it is characterised in that: described
Substrate is metal, ceramics or glass.
10. a kind of compound photocatalytic activity coating prepared by the method using claim 1-9, feature exist
In: the coating light-catalyzed reaction degradation rate > 24% in 30min, the light-catalyzed reaction degradation rate > 45% of 60min,
The light-catalyzed reaction degradation rate > 74% of the light-catalyzed reaction degradation rate > 60 of 90min, 120min.
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