CN104789067A - Carbon quantum dot visible light photocatalyst coating and preparation method thereof - Google Patents
Carbon quantum dot visible light photocatalyst coating and preparation method thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 238000000576 coating method Methods 0.000 title claims abstract description 69
- 239000011248 coating agent Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011941 photocatalyst Substances 0.000 title abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
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- 230000001699 photocatalysis Effects 0.000 claims description 54
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- 239000006185 dispersion Substances 0.000 claims description 29
- 239000013530 defoamer Substances 0.000 claims description 20
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Abstract
The invention discloses a carbon quantum dot visible light photocatalyst coating and a preparation method thereof. The coating comprises the following raw materials in parts by weight: 1-100 parts of carbon quantum dot aqueous solution, 5-50 parts of polymer emulsion, 0-50 parts of titanium dioxide, 2-20 parts of auxiliary agent and 10-50 parts of deionized water. The invention also discloses a preparation method of the coating. The carbon quantum dot photocatalyst coating prepared by the invention can efficiently absorb and utilize visible light (400-800 nm) in sunlight; under the irradiation of visible light, singlet oxygen can be efficiently generated, harmful gas in the environment can be removed in all directions (the removal rate is more than 90 percent) and harmful microorganisms can be killed efficiently (the bacteriostasis rate is more than 95 percent); the photocatalyst coating overcomes the defect that nano particles are easy to agglomerate, improves the storage stability, has good film forming property, is washable and can be used for a long time.
Description
Technical field
The present invention relates to photo-catalytic coating technical field.More specifically, a kind of carbon quantum dot visible ray photo-catalytic coating and preparation method thereof is related to.
Background technology
Research shows, the many building and ornament materials meeting slow releasing such as small molecules such as aldehydes, phenols objectionable impurities, causes serious harm to HUMAN HEALTH.In addition, along with increasingly sharpening of human industryization and urbanization, a large amount of sulfurous gas that seted off by industry, vehicle exhaust etc. gives off, carbon monoxide, the atmospheric pollution that the obnoxious flavour of lower valency nitride causes are day by day serious.In addition, microbial contamination be cause various poisoning, infect, one of the inducement of anaphylactic disease and communicable disease.Therefore research and develop that a class is comprehensive, surrounding purifying material is very urgent fast and efficiently.
In recent years, a large amount of novel environment-friendly type coating such as photo-catalytic coating etc. constantly occurs.But these photo-catalytic coatings photocatalyst used is mostly the mixture of some nano level metal oxides such as titanium dioxide or titanium dioxide and zinc oxide, it coats substrate surface, under the irradiation of light, there is transition of electron, valence-band electrons is excited to conduction band and produces hole in valence band, make the oxygen in air and water molecule activation, produce the active oxygen radical with high reaction activity, obnoxious flavour in these active oxygen radical decomposable asymmetric choice net air and kill harmful microorganism, play the object of environment purification.But these nano-metal-oxide photocatalysts can only absorb the UV-light (being less than 388 nanometers) in sunlight or fluorescent lamp, the visible ray (400 ~ 800 nanometer) in sunlight effectively can not be absorbed.Therefore, in order to sunlight can be made full use of, actively find focus and difficult point that preparation photoresponse wide ranges and the high photocatalyst of quantum yield can become photocatalyst research field.
Applicant has invented a kind of carbon quantum dot of Heteroatom doping recently, the absorption spectrum of this carbon quantum dot is between 300 ~ 850 nanometers, under simulated solar irradiation (400 ~ 800 nanometer) irradiates, its absorb energy by energy trasfer to the oxygen of surrounding, efficient generation singlet oxygen, singlet oxygen quantum yield in water is greater than 1.3, is the pioneering (granted patent number: 201210277190.2 in the world; NatureCommunications, 2014,5,4596).201310053616.0) and kill harmful microorganism (granted patent number: 201310053636.8) this carbon quantum dot not only has water-soluble preferably, and the obnoxious flavour in air of can effectively degrading (granted patent number:.But the simple carbon quantum dot that uses does photocatalyst, there is nano particle and easily reunite, spray and uneven, directly affect the deficiencies such as photocatalyst performance.
Therefore, in order to overcome the deficiencies in the prior art, the present invention proposes a kind of carbon quantum dot visible ray photo-catalytic coating and preparation method thereof, prepares visible ray photo-catalytic coating by adding the carbon quantum dot aqueous solution in polymer emulsion.
Summary of the invention
One object of the present invention is to provide a kind of carbon quantum dot visible ray photo-catalytic coating.
Another object of the present invention is the preparation method providing a kind of carbon quantum dot visible ray photo-catalytic coating, is specially a kind of method of adding the carbon quantum dot aqueous solution and preparing visible ray photo-catalytic coating in polymer emulsion.
For reaching above-mentioned first object, the present invention adopts following technical proposals:
A kind of carbon quantum dot visible ray photo-catalytic coating, comprises the raw material of following parts by weight:
Preferably, a kind of carbon quantum dot visible ray photo-catalytic coating, comprises the raw material of following parts by weight:
Preferably, described carbon quantum dot contains one or more in O, N, S, Se, P and As atom.
Preferably, the absorption spectrum wavelength of described carbon quantum dot is 300 ~ 850nm.
Preferably, the innovation and creation that the preferred the applicant of described carbon quantum dot is early stage, authorize.The absorption spectrum of this carbon quantum dot is between 300 ~ 850 nanometers, under simulated solar irradiation (400 ~ 800 nanometer) irradiates, its absorb energy by energy trasfer to the oxygen of surrounding, efficient generation singlet oxygen, singlet oxygen quantum yield in water is greater than 1.3, is the pioneering (number of patent application: 201210277190.2 in the world; Nature Communications, 2014,5,4596).201310053616.0) and kill harmful microorganism (number of patent application: 201310053636.8) this carbon quantum dot not only has water-soluble preferably, and the obnoxious flavour in air of can effectively degrading (number of patent application:.
But, use described carbon quantum dot to do photocatalyst if simple, there is nano particle and easily reunite, spray and uneven, directly affect the deficiencies such as photocatalyst performance.Adopt technical scheme of the present invention, carbon quantum dot is added in polymer emulsion, and by rational formulation optimization, the advantage of carbon quantum dot is combined with the Dominant Facies of polymer emulsion, overcome nano particle easily to reunite, spray uneven shortcoming, carbon quantum dot photocatalyst can be scattered in polymer emulsion uniformly, stability in storage is high, photocatalysis performance is high, can obnoxious flavour (clearance rate more than 90%) in comprehensive removing environment and efficiently kill harmful microorganism (bacteriostasis rate more than 95%).And obtained photo-catalytic coating film-forming properties, weathering resistance and washing fastness are good, can purify air fast, lastingly, in all directions, effectively suppress harmful microorganism, can be widely used in the outside surface of the objects such as building, the vehicles, bin.
Preferably, the mass percent in the described carbon quantum dot aqueous solution shared by carbon quantum dot is 0.5%.
Preferably, described polymer emulsion is polyacrylate emulsion, organosilicon crylic acid latex, benzene emulsion or pure-acrylic emulsion.
Preferably, described auxiliary agent is selected from one or more in dispersion agent, defoamer, mould inhibitor, coupling agent, film coalescence aid and wetting agent.
For reaching above-mentioned second object, the present invention adopts following technical proposals:
A preparation method for carbon quantum dot visible ray photo-catalytic coating as above, comprises the following steps:
The auxiliary agent of 5% of the deionized water of all wts number and all wts number is joined in whipping appts, then adds the titanium dioxide of all wts number, stir, through skin grinder by titanium dioxide slurry abrasive;
Then add the polymer emulsion of all wts number and the auxiliary agent of residuals weight number, finally add the carbon quantum dot aqueous solution of all wts number, fully disperse, filter, namely obtain carbon quantum dot visible ray photo-catalytic coating.
Preferably, the time of stirring is 0.5-2 hour; More preferably, the time of stirring is 1.5 hours.
Preferably, the fineness of the titanium dioxide slurries after skin grinder grinding is 60-120 order.
Beneficial effect of the present invention is as follows:
1) the carbon quantum dot photo-catalytic coating prepared of the present invention efficient absorption can utilize visible ray (400 ~ 800nm) in sunlight.
2) the carbon quantum dot photo-catalytic coating prepared of the present invention under visible light illumination, efficiently can produce singlet oxygen, can obnoxious flavour (clearance rate more than 90%) in comprehensive removing environment and efficiently kill harmful microorganism (bacteriostasis rate more than 95%).
3) the carbon quantum dot photo-catalytic coating that prepared by the present invention overcomes the weakness that nano particle is easily reunited.Stability in storage is improved, and photo-catalytic coating good film-forming property, washability, can use for a long time.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is the sterilization effect figure of a kind of carbon quantum dot visible ray photo-catalytic coating of the embodiment of the present invention 2.
Embodiment
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiments and drawings, the present invention is described further.Parts similar in accompanying drawing represent with identical Reference numeral.It will be appreciated by those skilled in the art that specifically described content is illustrative and nonrestrictive, should not limit the scope of the invention with this below.
Embodiment 1
A kind of carbon quantum dot visible ray photo-catalytic coating, comprises the raw material of following parts by weight: the aqueous solution 100g (mass percent in the carbon quantum dot aqueous solution shared by carbon quantum dot is 0.5%) of the carbon quantum dot containing heteroatoms O doping, benzene emulsion 30g, titanium dioxide 5g, dispersion agent 3g, membrane-forming agent 1g, defoamer 0.5g, wetting agent 0.8g, deionized water 30g.The preparation method of this coating is as follows:
The various auxiliary agents such as precise deionized water and dispersion agent, defoamer, wetting agent, membrane-forming agent, the auxiliary agent of the deionized water of all wts and 5% of all wts is joined in whipping appts, add the titanium dioxide of all wts number again, stir 0.5 hour, through skin grinder, titanium dioxide slurries are milled to fineness and reach 60-12 order, then the benzene emulsion of all wts is added, add remaining auxiliary agent again, finally add the carbon quantum dot aqueous solution of all wts, abundant dispersion, filter, obtain carbon quantum dot visible ray photo-catalytic coating.
Embodiment 2
A kind of carbon quantum dot visible ray photo-catalytic coating, comprises the raw material of following parts by weight: the aqueous solution 80g (mass percent in the carbon quantum dot aqueous solution shared by carbon quantum dot is 0.1%) of the carbon quantum dot containing heteroatoms Se doping, polyacrylate emulsion 40g, titanium dioxide 2g, dispersion agent 2g, membrane-forming agent 0.5g, defoamer 0.3g, wetting agent 1g, deionized water 50g.The preparation method of this coating is as follows:
The various auxiliary agents such as precise deionized water and dispersion agent, defoamer, wetting agent, membrane-forming agent, the auxiliary agent of the deionized water of all wts and 5% of all wts is joined in whipping appts, add the titanium dioxide of all wts number again, stir 1 hour, through skin grinder, titanium dioxide slurries are milled to fineness and reach 100 orders, then the polyacrylate emulsion of all wts is added, add remaining auxiliary agent again, finally add the carbon quantum dot aqueous solution of all wts, abundant dispersion, filter, obtain carbon quantum dot visible ray photo-catalytic coating.
Fig. 1 is the sterilization effect figure of a kind of carbon quantum dot visible ray photo-catalytic coating of the present embodiment.
Table 1 is the effect data of a kind of carbon quantum dot visible ray photo-catalytic coating removal indoor harmful gas of the present embodiment.
Table 1 carbon quantum dot visible ray photo-catalytic coating removes the effect data of indoor harmful gas
The detection method that above test item all specifies by " Indoor Air Quality standards " (GB/T18883-2002) is carried out, detected result shows: the carbon quantum dot photo-catalytic coating that the present embodiment obtains effectively can suppress harmful microorganism, and the surviving rate of illumination bacterium after 12 hours is less than 5%; Purifying formaldehyde efficiency is high simultaneously, and the formaldehyde total removal rate after 24 hours reaches 92.2%.
Embodiment 3
A kind of carbon quantum dot visible ray photo-catalytic coating, comprises the raw material of following parts by weight: the aqueous solution 50g (mass percent in the carbon quantum dot aqueous solution shared by carbon quantum dot is 0.2%) of the carbon quantum dot containing heteroatoms P doping, organosilicon crylic acid latex 50g, titanium dioxide 50g, dispersion agent 5g, membrane-forming agent 5g, defoamer 1g, wetting agent 2g, mould inhibitor 1g, deionized water 40g.The preparation method of this coating is as follows:
Precise deionized water and dispersion agent, defoamer, wetting agent, membrane-forming agent, the various auxiliary agent such as mould inhibitor, the auxiliary agent of the deionized water of all wts and 5% of all wts is joined in whipping appts, add the titanium dioxide of all wts number again, stir 0.8 hour, through skin grinder, titanium dioxide slurries are milled to fineness and reach 100 orders, then the benzene emulsion of all wts is added, add remaining auxiliary agent again, finally add the carbon quantum dot aqueous solution of all wts, abundant dispersion, filter, obtain carbon quantum dot visible ray photo-catalytic coating, it removes obnoxious flavour in environment and to kill harmful microbe effect similar to embodiment 2.
Embodiment 4
A kind of carbon quantum dot visible ray photo-catalytic coating, comprises the raw material of following parts by weight: the aqueous solution 5g (mass percent in the carbon quantum dot aqueous solution shared by carbon quantum dot is 0.3%) of the carbon quantum dot containing heteroatoms S and Se doping, pure-acrylic emulsion 5g, dispersion agent 0.2g, membrane-forming agent 0.2g, defoamer 0.2g, wetting agent 0.2g, mould inhibitor 0.2g, deionized water 10g.The preparation method of this coating is as follows:
The various auxiliary agents such as precise deionized water and dispersion agent, defoamer, wetting agent, membrane-forming agent, mould inhibitor, the auxiliary agent of the deionized water of all wts and 5% of all wts is joined in whipping appts, stir 0.7 hour, then the benzene emulsion of all wts is added, add remaining auxiliary agent again, finally add the carbon quantum dot aqueous solution of all wts, abundant dispersion, filter, obtain carbon quantum dot visible ray photo-catalytic coating, it removes obnoxious flavour in environment and to kill harmful microbe effect similar to embodiment 2.
Embodiment 5
A kind of carbon quantum dot visible ray photo-catalytic coating, comprises the raw material of following parts by weight: the aqueous solution 20g (mass percent in the carbon quantum dot aqueous solution shared by carbon quantum dot is 0.5%) of the carbon quantum dot containing heteroatoms O and P doping, benzene emulsion 100g, dispersion agent 15g, membrane-forming agent 10g, defoamer 5g, wetting agent 10g, deionized water 200g.The preparation method of this coating is as follows:
Precise deionized water and dispersion agent, defoamer, wetting agent, the various auxiliary agent such as membrane-forming agent, the auxiliary agent of the deionized water of all wts and 5% of all wts is joined in whipping appts, add the titanium dioxide of all wts number again, stir 0.5 hour, through skin grinder, titanium dioxide slurries are milled to fineness and reach 60-12 order, then the benzene emulsion of all wts is added, add remaining auxiliary agent again, finally add the carbon quantum dot aqueous solution of all wts, abundant dispersion, filter, obtain carbon quantum dot visible ray photo-catalytic coating, it removes obnoxious flavour in environment and to kill harmful microbe effect similar to embodiment 2.
Embodiment 6
A kind of carbon quantum dot visible ray photo-catalytic coating, comprises the raw material of following parts by weight: the aqueous solution 100g (mass percent in the carbon quantum dot aqueous solution shared by carbon quantum dot is 3%) of the carbon quantum dot containing heteroatoms N doping, benzene emulsion 50g, titanium dioxide 50g, dispersion agent 5g, membrane-forming agent 5g, defoamer 5g, wetting agent 5g, deionized water 50g.The preparation method of this coating is as follows:
Precise deionized water and dispersion agent, defoamer, wetting agent, the various auxiliary agent such as membrane-forming agent, the auxiliary agent of the deionized water of all wts and 5% of all wts is joined in whipping appts, add the titanium dioxide of all wts number again, stir 2 hours, through skin grinder, titanium dioxide slurries are milled to fineness and reach 60-12 order, then the benzene emulsion of all wts is added, add remaining auxiliary agent again, finally add the carbon quantum dot aqueous solution of all wts, abundant dispersion, filter, obtain carbon quantum dot visible ray photo-catalytic coating, it removes obnoxious flavour in environment and to kill harmful microbe effect similar to embodiment 2.
Embodiment 7
A kind of carbon quantum dot visible ray photo-catalytic coating, comprises the raw material of following parts by weight: the aqueous solution 60g (mass percent in the carbon quantum dot aqueous solution shared by carbon quantum dot is 2%) of the carbon quantum dot containing heteroatoms As doping, organosilicon crylic acid latex 40g, titanium dioxide 30g, dispersion agent 8g, membrane-forming agent 6g, defoamer 3g, wetting agent 3g, deionized water 50g.The preparation method of this coating is as follows:
Precise deionized water and dispersion agent, defoamer, wetting agent, the various auxiliary agent such as membrane-forming agent, the auxiliary agent of the deionized water of all wts and 5% of all wts is joined in whipping appts, add the titanium dioxide of all wts number again, stir 2 hours, through skin grinder, titanium dioxide slurries are milled to fineness and reach 60-12 order, then the benzene emulsion of all wts is added, add remaining auxiliary agent again, finally add the carbon quantum dot aqueous solution of all wts, abundant dispersion, filter, obtain carbon quantum dot visible ray photo-catalytic coating, it removes obnoxious flavour in environment and to kill harmful microbe effect similar to embodiment 2.
Embodiment 8
A kind of carbon quantum dot visible ray photo-catalytic coating, comprises the raw material of following parts by weight: the aqueous solution 30g (mass percent in the carbon quantum dot aqueous solution shared by carbon quantum dot is 0.5%) of the carbon quantum dot containing heteroatoms N and As doping, polyacrylate emulsion 150g, dispersion agent 20g, membrane-forming agent 20g, defoamer 10g, wetting agent 10g, deionized water 600g.The preparation method of this coating is as follows:
Precise deionized water and dispersion agent, defoamer, wetting agent, the various auxiliary agent such as membrane-forming agent, the auxiliary agent of the deionized water of all wts and 5% of all wts is joined in whipping appts, add the titanium dioxide of all wts number again, stir 2 hours, through skin grinder, titanium dioxide slurries are milled to fineness and reach 60-12 order, then the benzene emulsion of all wts is added, add remaining auxiliary agent again, finally add the carbon quantum dot aqueous solution of all wts, abundant dispersion, filter, obtain carbon quantum dot visible ray photo-catalytic coating, it removes obnoxious flavour in environment and to kill harmful microbe effect similar to embodiment 2.
Embodiment 9
A kind of carbon quantum dot visible ray photo-catalytic coating, comprises the raw material of following parts by weight: the aqueous solution 50g (mass percent in the carbon quantum dot aqueous solution shared by carbon quantum dot is 0.5%) of the carbon quantum dot containing heteroatoms Se doping, polyacrylate emulsion 35g, titanium dioxide 2g, dispersion agent 2g, membrane-forming agent 0.5g, defoamer 0.3g, wetting agent 1g, deionized water 45g.The preparation method of this coating is as follows:
Precise deionized water and dispersion agent, defoamer, wetting agent, the various auxiliary agent such as membrane-forming agent, the auxiliary agent of the deionized water of all wts and 5% of all wts is joined in whipping appts, add the titanium dioxide of all wts number again, stir 1 hour, through skin grinder, titanium dioxide slurries are milled to fineness and reach 100 orders, then the polyacrylate emulsion of all wts is added, add remaining auxiliary agent again, finally add the carbon quantum dot aqueous solution of all wts, abundant dispersion, filter, obtain carbon quantum dot visible ray photo-catalytic coating, it removes obnoxious flavour in environment and to kill harmful microbe effect similar to embodiment 2.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (10)
1. a carbon quantum dot visible ray photo-catalytic coating, is characterized in that, comprises the raw material of following parts by weight:
2. a kind of carbon quantum dot visible ray photo-catalytic coating according to claim 1, is characterized in that, comprise the raw material of following parts by weight:
3. a kind of carbon quantum dot visible ray photo-catalytic coating according to claim 1, is characterized in that: described carbon quantum dot contains one or more in O, N, S, Se, P and As atom.
4. a kind of carbon quantum dot visible ray photo-catalytic coating according to claim 1, is characterized in that: the absorption spectrum wavelength of described carbon quantum dot is 300 ~ 850nm.
5. a kind of carbon quantum dot visible ray photo-catalytic coating according to claim 1, is characterized in that: in the described carbon quantum dot aqueous solution, the mass percent of carbon quantum dot is 0.5-3%.
6. a kind of carbon quantum dot visible ray photo-catalytic coating according to claim 1, is characterized in that: described polymer emulsion is polyacrylate emulsion, organosilicon crylic acid latex, benzene emulsion or pure-acrylic emulsion.
7. a kind of carbon quantum dot visible ray photo-catalytic coating according to claim 1, is characterized in that: described auxiliary agent be selected from dispersion agent, defoamer, mould inhibitor, coupling agent, film coalescence aid and wetting agent one or more.
8. the preparation method of the carbon quantum dot visible ray photo-catalytic coating as described in as arbitrary in claim 1-7, is characterized in that, comprise the following steps:
The auxiliary agent of 5% of the deionized water of all wts number and all wts number is joined in whipping appts, adds the titanium dioxide of all wts number, stir, through skin grinder by titanium dioxide slurry abrasive;
Then add the polymer emulsion of all wts number and the auxiliary agent of residuals weight number, finally add the carbon quantum dot aqueous solution of all wts number, fully disperse, filter, namely obtain carbon quantum dot visible ray photo-catalytic coating.
9. the preparation method of carbon quantum dot visible ray photo-catalytic coating according to claim 8, is characterized in that: the time of stirring is 0.5-2 hour.
10. the preparation method of carbon quantum dot visible ray photo-catalytic coating according to claim 8, is characterized in that: the fineness of the titanium dioxide slurries after skin grinder grinding is 60-120 order.
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