CN113694949B - Hydroxylated mesoporous carbon purification material, preparation method thereof, air purification coating and backboard - Google Patents
Hydroxylated mesoporous carbon purification material, preparation method thereof, air purification coating and backboard Download PDFInfo
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- CN113694949B CN113694949B CN202110805969.6A CN202110805969A CN113694949B CN 113694949 B CN113694949 B CN 113694949B CN 202110805969 A CN202110805969 A CN 202110805969A CN 113694949 B CN113694949 B CN 113694949B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000000746 purification Methods 0.000 title claims abstract description 49
- 239000011248 coating agent Substances 0.000 title claims abstract description 33
- 238000000576 coating method Methods 0.000 title claims abstract description 33
- 238000004887 air purification Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 56
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011737 fluorine Substances 0.000 claims abstract description 41
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 41
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 29
- -1 rare earth phosphate Chemical class 0.000 claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 28
- 239000010452 phosphate Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 66
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000003973 paint Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 6
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 229910002248 LaBO3 Inorganic materials 0.000 claims description 4
- 229910002254 LaCoO3 Inorganic materials 0.000 claims description 4
- 229910002867 Sr2FeMoO6 Inorganic materials 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 9
- 231100000719 pollutant Toxicity 0.000 abstract description 9
- 239000011230 binding agent Substances 0.000 abstract description 8
- 239000011941 photocatalyst Substances 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 230000033444 hydroxylation Effects 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052909 inorganic silicate Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910017855 NH 4 F Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- USEGOPGXFRQEMV-UHFFFAOYSA-N fluoro hypofluorite titanium Chemical compound [Ti].FOF USEGOPGXFRQEMV-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 238000003905 indoor air pollution Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The application provides a hydroxylation mesoporous carbon purification material, a preparation method thereof, an air purification coating and a backboard. The method comprises the steps of carrying out nitrogen doping and fluorine doping on titanium dioxide and perovskite type composite oxide, and carrying out fluorine doping on a rare earth phosphate material to obtain a product A; carrying out hydroxylation reaction on mesoporous carbon to obtain a product B; calcining the product A and the product B under the protection of inert gas to obtain the hydroxylated mesoporous carbon purification material. The application adopts the hydroxylated mesoporous carbon as the shell of the purification factor, can be firmly combined with the binder, ensures that the photocatalyst is prevented from being directly contacted with the backboard and the binder, and can efficiently adsorb pollutants on the surface of the purification factor so as to accelerate the degradation of the pollutants. The purification factor of the application can fully utilize light energy (sunlight or artificial illumination) to realize the efficient purification of indoor air, and can degrade pollutants in the air at night without light and in dark places.
Description
Technical Field
The application belongs to the field of air purification, and particularly relates to a hydroxylation mesoporous carbon purification material, a preparation method thereof, an air purification coating and a backboard.
Background
Along with the development of the technology level, the intelligent integrated machine is widely applied to classrooms, meeting rooms and the like. The indoor space has the problems of large people flow and poor air quality. In order to solve the problem, the function of purifying air can be added on the intelligent integrated machine. The existing technology often combines a display screen and a purifying element to achieve a better air purifying effect, but has the problems of increased energy consumption, increased product weight and increased noise; there is also a method of adding a photocatalytic coating to the protective glass to achieve a purification effect, but the coating needs to be excited by an ultraviolet lamp, and the protective glass has a limited area, which limits further improvement of the purification capability. Compared with the protective glass, the area of the back plate is larger, so that the spraying of the photocatalyst on the back plate is beneficial to improving the air purifying performance of the intelligent integrated machine.
As an air purifying agent, the photocatalyst has the characteristics of high treatment speed, no secondary pollution, good treatment effect and the like, and is considered as an ideal material for treating indoor air pollution at present. TiO 2 is a widely used photocatalyst, when TiO 2 is excited, photo-generated electrons and holes can be generated, the photo-generated electrons and holes can migrate to the surface of the catalyst to react with adsorption contact O 2 or H 2 O and the like, H 2O、OH- adsorbed on the surface of hole oxidation generates hydroxyl free radicals OH which are super-strong oxidants, and organic matters can be gradually mineralized into CO 2、H2 O and inorganic salts. The holes can directly oxidize organic matters, and in the process, the TiO 2 is not lost, so that long-term air purification can be realized. The back plate is a paint-plated alloy as a basic frame of the intelligent integrated machine, and if the back plate is directly contacted with a photocatalyst, the phenomena of low bonding strength and easy yellowing and cracking of the primer exist. In addition, the back plate is positioned on the back surface, so that the contact light intensity is relatively weak, and the activity of the photocatalyst is affected.
Disclosure of Invention
In view of the shortcomings of the prior art, a first object of the present application is to provide a method for preparing a hydroxylated mesoporous carbon purification material, comprising the steps of:
nitrogen doping and fluorine doping are carried out on the titanium dioxide and the perovskite type composite oxide, and fluorine doping is carried out on the rare earth phosphate material, so that a product A is obtained;
Carrying out hydroxylation reaction on mesoporous carbon to obtain a product B;
Calcining the product A and the product B under the protection of inert gas to obtain the hydroxylated mesoporous carbon purification material.
In some embodiments of the application, the nitrogen doping is performed on the titanium dioxide and the perovskite type composite oxide before the fluorine doping is performed.
In some embodiments of the application, nitrogen doping and fluorine doping the titanium dioxide and perovskite type composite oxide and fluorine doping the rare earth phosphate material to obtain the product a includes:
Uniformly mixing the titanium dioxide and the perovskite type composite oxide, then reacting with a nitrogen source, and burning the obtained precipitate to obtain a product C;
And (3) reacting the product C, the rare earth phosphate material and a fluorine source, and calcining the obtained mixture to obtain the product A.
In some embodiments of the application, hydroxylating mesoporous carbon to produce product B comprises:
And (3) placing the mesoporous carbon into a mixed solution of hydrogen peroxide and sulfuric acid for ultrasonic treatment in a water bath, cleaning and drying to obtain the product B.
In some embodiments of the application, the nitrogen-doped nitrogen source comprises one or more of an aqueous urea solution, melamine, and dicyandiamide;
the fluorine doped fluorine source comprises ammonium fluoride;
The perovskite type composite oxide is one or more of GdFeO 3、Sr2FeMoO6、LaBO3、LaCoO3;
the rare earth phosphate material is one or more of SrCa2(PO4)2:Eu2+、Ca4La6(SiO4)(PO4)2O2、H3Sr6(PO4)5·2H2O;
The specific surface area of the mesoporous carbon is 1200m 2/g～1700m2/g, the average pore diameter is 2 mm-6 mm, and the pore volume is more than 2ml/g.
In some embodiments of the application, the mass ratio of the product A to the product B is (1-12): (2-20), the calcining temperature of the product A and the product B is 700-1100 ℃ and the calcining time is 30-80 min.
A second object of the present application is to provide a hydroxylated mesoporous carbon purification material comprising hydroxylated mesoporous carbon as a shell and a purification factor encapsulated within the hydroxylated mesoporous carbon;
The purification factors comprise nitrogen and fluorine doped TiO 2, nitrogen and fluorine doped perovskite type composite oxide and fluorinated rare earth phosphate material.
The third object of the application is to provide an air purification coating, which comprises the hydroxylated mesoporous carbon purification material.
In some embodiments of the present application, the above-described air cleaning coating further comprises a dispersant, a surfactant, 3- (methacryloyloxy) propyl trimethoxysilane, and a solvent;
Wherein the solvent is one or more of acrylic emulsion, isopropanol and ethanol;
the mass ratio of the hydroxylated mesoporous carbon purifying material to the dispersing agent to the surfactant to the 3- (methacryloyloxy) propyl trimethoxy silane to the solvent is (30-50)/(2-8)/(1-5)/(1-10)/(40-80).
A fourth object of the present application is to provide a back sheet comprising a lacquer alloy and coated with the above air cleaning paint;
Wherein the surface layer of the paint-plated alloy is an organic coating, and the organic coating contains one or more groups of hydroxyl, carboxyl and double bonds.
The preparation method disclosed by the application is simple in process, easy to control, good in repeatability, environment-friendly and easy for industrial production.
The application adopts the hydroxylated mesoporous carbon as the shell of the purification factor, the shell structure can be firmly combined with the binder, the photocatalyst can be prevented from being directly contacted with the backboard and the binder, and the hydroxylated mesoporous carbon can efficiently adsorb pollutants on the surface of the purification factor, so that the degradation of the pollutants is accelerated. The nitrogen and fluorine doped titanium dioxide and the perovskite type composite oxide are used as main components in the purification factors, so that the purification factors can fully utilize light energy (sunlight or artificial illumination) to realize efficient purification of indoor air. The fluorine element is introduced into the rare earth phosphate light storage material, so that the light released by the rare earth phosphate light storage material in a dark environment is more sufficient, and the coating can be ensured to degrade pollutants in the air at dark night and in dark places.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
Fig. 1 is a schematic process flow diagram of a preparation process of a hydroxylated mesoporous carbon purification material according to an embodiment of the present application.
Detailed Description
The following detailed description of specific embodiments of the invention is provided in connection with the accompanying drawings and examples in order to provide a better understanding of the aspects of the invention and advantages thereof. However, the following description of specific embodiments and examples is for illustrative purposes only and is not intended to be limiting of the invention.
It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention.
Fig. 1 shows a preparation method of a hydroxylated mesoporous carbon purification material according to an embodiment of the present application. As shown in fig. 1, the method comprises the steps of:
S1: and (3) carrying out nitrogen doping and fluorine doping on the titanium dioxide and the perovskite type composite oxide, and carrying out fluorine doping on the rare earth phosphate material to obtain a product A.
Optionally, the titanium dioxide and the perovskite type composite oxide are doped with nitrogen and then doped with fluorine.
This step may include:
Preparing titanium dioxide;
uniformly mixing titanium dioxide and the perovskite type composite oxide, then reacting with a nitrogen source, and burning the obtained precipitate to obtain a product C;
and (3) reacting the product C and the rare earth phosphate material with a fluorine source, and calcining the obtained mixture to obtain a product A.
Optionally, the nitrogen-doped nitrogen source comprises one or more of an aqueous urea solution, melamine, and dicyandiamide.
Optionally, the fluorine doped fluorine source comprises ammonium fluoride.
Specifically, this step may be:
Dispersing titanium sulfate in an aqueous solution of n-propanol, then adding a perovskite type composite oxide, uniformly dispersing, then adding an aqueous solution of urea, and burning the obtained precipitate to obtain a product C;
And (3) reacting the product C, the rare earth phosphate material and ammonium fluoride in a nitric acid aqueous solution, and calcining the obtained mixture to obtain a product A.
Firstly preparing titanium dioxide, then mixing the titanium dioxide with the perovskite type composite oxide, then carrying out nitrogen doping, and then carrying out fluorine doping together with a rare earth phosphate material.
Of course, the present application may not include the step of forming titanium dioxide, and the nitrogen doping may be performed directly after mixing the titanium dioxide and the perovskite type composite oxide.
Alternatively, the titanium sulfate in the above step may be replaced with titanium tetrachloride, tetrabutyl titanate, titanium isopropoxide, titanium sulfate, titanyl sulfate, titanium difluorooxide, titanium flakes, or the like.
Optionally, the perovskite-type composite oxide used is one or more of GdFeO 3、Sr2FeMoO6、LaBO3、LaCoO3.
Optionally, the volume solubility of the n-propanol aqueous solution is 50-80%, namely, the volume ratio of n-propanol to water is (2-4) (1-2) when the water is prepared. Optionally, the aqueous urea solution is used at a mass concentration of 25% to 35%. The volume concentration (expressed in% v/v in the lower part) as referred to in the present application means the volume percentage concentration, and the mass concentration (expressed in% wt in the lower part) means the mass percentage concentration.
Optionally, in the step S1, the mass ratio of the titanium sulfate to the perovskite type composite oxide is (3-10): (5-20), the volume ratio of the n-propanol aqueous solution to the urea aqueous solution is (3-6): (2-10), and the dosage ratio of the titanium sulfate to the n-propanol aqueous solution is (3-10): (150-300) g/mL.
Optionally, the temperature for firing the precipitate is 300-500 ℃ and the time is 3-10 h.
Optionally, the volume concentration of the nitric acid aqueous solution is 5% -15%.
Optionally, the mass ratio of the product C to the ammonium fluoride to the rare earth phosphate material is (10-50), the mass ratio of the product C to the ammonium fluoride to the rare earth phosphate material is (2-10), the mass ratio of the product C to the nitric acid aqueous solution is (5-50), and the dosage ratio of the product C to the nitric acid aqueous solution is (1-5), the mass ratio of the product C to the rare earth phosphate material is (50-150) g/mL.
Optionally, after uniformly dispersing the product C, ammonium fluoride and rare earth phosphate material in the nitric acid aqueous solution, reacting for 5-15 h.
Optionally, the resulting mixture is calcined at a temperature of 300 to 500 ℃ for a time of 3 to 10 hours. Preferably, the temperature is raised to 300-500 ℃ by adopting a gradual temperature raising mode, and calcination is carried out for 3-10 hours.
Optionally, the rare earth phosphate material is one or more of SrCa2(PO4)2:Eu2+、Ca4La6(SiO4)(PO4)2O2、H3Sr6(PO4)5·2H2O.
S2: and (3) carrying out hydroxylation reaction on the mesoporous carbon to obtain a product B.
Specifically, the present step may be:
And (3) placing the mesoporous carbon into a mixed solution of hydrogen peroxide and sulfuric acid for ultrasonic treatment in a water bath, cleaning and drying to obtain a product B.
It should be noted that other reagents may be used in the present application to carry out hydroxylation reaction on mesoporous carbon.
Alternatively, the specific surface area of the mesoporous carbon used is 1200m 2/g～1700m2/g, the average pore diameter is 2 mm-6 mm, and the pore volume is >2ml/g.
Optionally, the mass concentration of the hydrogen peroxide is about 30%, the mass concentration of the sulfuric acid is about 98%, and the mass ratio of the hydrogen peroxide to the sulfuric acid is 1:10-10:1.
Optionally, the time of the ultrasound is 30 min-90 min. After the ultrasonic treatment is completed, water bath treatment is carried out, and optionally, the temperature of the water bath treatment is 50-80 ℃ and the time is 20-50 min.
Optionally, water and absolute ethyl alcohol are adopted to clean the treated mesoporous carbon. Preferably, the washing is performed with water and then with absolute ethanol.
S3: calcining the product A and the product B under the protection of inert gas to obtain the hydroxylated mesoporous carbon purification material.
Optionally, the mass ratio of the product A to the product B is (1-12) (2-20), the calcining temperature of the product A and the product B is 700-1100 ℃ and the calcining time is 30-80 min.
And step S3, coating the product A by the product B, so that the nitrogen and fluorine doped TiO 2, the nitrogen and fluorine doped perovskite type composite oxide and the rare earth fluoride phosphate material are coated by the hydroxylated mesoporous carbon.
The preparation method disclosed by the application is simple in process, easy to control, good in repeatability, environment-friendly and easy for industrial production.
The application further provides a hydroxylated mesoporous carbon purification material, which comprises hydroxylated mesoporous carbon serving as a shell and a purification factor wrapped in the hydroxylated mesoporous carbon, wherein the purification factor comprises nitrogen and fluorine doped TiO 2, nitrogen and fluorine doped perovskite type composite oxide and a rare earth fluoride phosphate material.
Optionally, the hydroxylated mesoporous carbon is prepared by hydroxylation reaction of mesoporous carbon with the specific surface area of 1200-1700 m 2/g, the average pore diameter of 2-6 mm and the pore volume of more than 2 ml/g.
Optionally, the nitrogen and fluorine doped perovskite type composite oxide is prepared by doping one or more perovskite type composite oxides in GdFeO 3、Sr2FeMoO6、LaBO3、LaCoO3 with nitrogen and fluorine.
Optionally, the rare earth phosphate material is prepared from one or more rare earth phosphate materials of SrCa2(PO4)2:Eu2+、Ca4La6(SiO4)(PO4)2O2、H3Sr6(PO4)5·2H2O by fluorine doping.
The application adopts the hydroxylated mesoporous carbon as the shell of the purification factor, the shell structure can be firmly combined with the binder, the photocatalyst can be prevented from being directly contacted with the backboard and the binder, and the hydroxylated mesoporous carbon can efficiently adsorb pollutants on the surface of the purification factor, so that the degradation of the pollutants is accelerated. The nitrogen and fluorine doped titanium dioxide and the perovskite type composite oxide are used as main components in the purification factors, so that the purification factors can fully utilize light energy (sunlight or artificial illumination) to realize efficient purification of indoor air. The fluorine element is introduced into the rare earth phosphate light storage material, so that the light released by the rare earth phosphate light storage material in a dark environment is more sufficient, and the coating can be ensured to degrade pollutants in the air at dark night and in dark places.
The application also provides an air purification coating, which comprises the hydroxylated mesoporous carbon purification material.
Optionally, the air cleaning coating further comprises a dispersant, a surfactant, 3- (methacryloyloxy) propyl trimethoxysilane, and a solvent.
Optionally, the solvent used is one or more of acrylic emulsion, isopropanol, ethanol.
The application adopts 3- (methacryloyloxy) propyl trimethoxy silane as the binder to connect the backboard, and the binder has rich double bonds and methoxy groups, and can form stable covalent bonds with the organic coating and the hydroxylated mesoporous carbon of the backboard respectively, so that the coating and the backboard are firmly combined.
The application also provides a backboard which comprises the paint-plated alloy and is coated with the air purification paint. The coating layer formed after the air-purifying paint is coated on the back plate is located at the outermost layer (i.e., in contact with air).
Wherein, the surface layer of the paint-plated alloy is an organic coating, and the organic coating contains one or more groups of hydroxyl, carboxyl and double bonds.
The backsheet of the present application is organically bonded to 3- (methacryloyloxy) propyl trimethoxysilane through these groups in the organic coating.
Alternatively, the paint-coated alloy is a machined alloy, preferably an alloy with rust inhibitive paint deposited on the surface, which may be 0.5mm to 1.5mm thick.
Optionally, the organic coating thickness in the lacquer alloy is 3 μm to 20 μm.
Alternatively, the thickness of the air cleaning paint coated on the back plate is 10 μm to 50 μm.
Optionally, the purification paint is fixed on the surface of the backboard by adopting modes of coating, spraying, dip coating and the like, and is dried at 60-150 ℃ to obtain the composite material.
The invention will now be described with reference to specific examples. The values of the process conditions taken in the examples described below are exemplary and can be obtained in the ranges indicated in the foregoing, and for process parameters not specifically identified, reference may be made to conventional techniques. The detection methods used in the examples below are all conventional in the industry. Reagents and apparatus used in the technical scheme provided by the invention are available from conventional channels or markets unless otherwise specified.
Example 1
The method for preparing the backboard specifically comprises the following steps:
S01: 5.0g of Ti (SO 4)2 was dispersed in a mixture of 150ml of n-propanol and 80ml of water, and 10g of GdFeO 3 was added thereto, and after uniform dispersion, 250ml of 30wt% urea aqueous solution was added thereto, and the obtained precipitate was burned at 300℃for 5 hours to obtain a product C.
S02: 0.5g of NH 4 F, 2.0g of product C and 3.0g of Ca 4La6(SiO4)(PO4)2O2 were dispersed in 100ml of a 5% (v/v) aqueous nitric acid solution and reacted for 10 hours, and the resultant mixture was calcined by gradually heating to 400℃for 5 hours to obtain product A.
S03: 3.0g of mesoporous carbon (specific surface area 1500m 2/g, average pore size 4mm, pore volume 3 ml/g) was placed at a ratio of 7:3 (98.3 wt%) in a mixed H 2O2(30wt％)：H2SO4 (98.3 wt%) solution, carrying out water bath treatment at 60 ℃ for 30min after ultrasonic treatment for 60min, washing with water, washing with absolute ethyl alcohol, and drying for standby to obtain a product B.
S04: 2.0g of the product A and 5.0g of the product B are calcined for 30min at 900 ℃ under the protection of N 2, so as to obtain the hydroxylation mesoporous carbon purification material.
S05: uniformly mixing 40wt% of hydroxylated mesoporous carbon purification material, 5.0wt% of sodium polyacrylate, 2.0wt% of organopolysiloxane defoamer, 5.0wt% of 3- (methacryloyloxy) propyl trimethoxy silane and 48wt% of acrylic emulsion, coating the mixture on the surface of a backboard, and drying the mixture at 80 ℃ to obtain the backboard with the air purification coating;
Wherein the surface layer of the backboard is an organic coating containing carboxyl.
Example 2
The method for preparing the backboard specifically comprises the following steps:
S01: 5.0g of Ti (SO 4)2 was dispersed in a mixture of 150ml of n-propanol and 80ml of water, 10g of LaBO 3 was added thereto, 250ml of 30wt% aqueous urea solution was added thereto after the dispersion was uniform, and the obtained precipitate was burned at 300℃for 5 hours to obtain a product C.
The rest of the procedure is the same as in example 1.
Example 3
The method for preparing the backboard specifically comprises the following steps:
S01: as in example 1.
S02: 0.5g of NH 4 F, 2.0g of product C and 3.0g of g H 3Sr6(PO4)5·2H2 O were dispersed in 100ml of 5% (v/v) nitric acid aqueous solution and reacted for 10 hours, and the resultant mixture was calcined by gradually heating to 400℃for 5 hours to obtain product A.
The rest of the procedure is the same as in example 1.
Comparative example 1
S01: 5.0g of Ti (SO 4)2) was dispersed in a mixture of 150ml of n-propanol and 80ml of water, and after uniform dispersion, 250ml of 30% (v/v) aqueous urea solution was added, and the obtained precipitate was burned at 300℃for 5 hours to obtain product C.
The rest of the procedure is the same as in example 1.
Comparative example 2
S01: as in example 1.
S02: dispersing 0.5g of NH 4 F and 2.0g of product C in 100ml of 5% (v/v) nitric acid aqueous solution, reacting for 10 hours, and calcining the obtained mixture by gradually heating to 400 ℃ for 5 hours to obtain a product A;
the rest of the procedure is the same as in example 1.
Comparative example 3
In comparative example 3, the preparation method omits step S03 in example 1, and directly uses mesoporous carbon as a product B to carry out S04, and the rest steps and formulation proportion are the same as example 1.
Effect detection
(1) Air purifying effect
The air purification effect of the product was examined by referring to the method in QB/T2761-2006 with untreated glass as a control group and glass prepared in different examples as an experimental group and formaldehyde as a contaminant, and the results are shown in Table 1.
(2) Adhesion properties
The evaluation was performed according to the cross-cut test standard in GB/T13448-2006 and the results are shown in Table 1.
TABLE 1
The purification factor of the hydroxylated mesoporous carbon purification material prepared in comparative example 1 contains no nitrogen and fluorine doped perovskite type composite oxide, the purification factor of the hydroxylated mesoporous carbon purification material prepared in comparative example 2 contains no rare earth fluoride phosphate material, and the mesoporous carbon of the hydroxylated mesoporous carbon purification material prepared in comparative example 3 is not hydroxylated.
As can be seen from Table 1, the hydroxylated mesoporous carbon purification material of the present application has excellent air purification effect and excellent adhesion to the back plate.
The air cleaning effect of the back sheets produced in comparative examples 1 to 3 was significantly lowered compared to examples 1 to 3. Furthermore, as is clear from the results of comparative example 3, the mesoporous carbon as the shell was not hydroxylated, and its adhesion ability was greatly reduced.
It is apparent that the above examples are only illustrative of the present invention and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (9)
1. An air purification paint is characterized by comprising a hydroxylated mesoporous carbon purification material, a dispersing agent, a surfactant, 3- (methacryloyloxy) propyl trimethoxysilane and a solvent;
Wherein the hydroxylated mesoporous carbon purification material comprises hydroxylated mesoporous carbon serving as a shell and purification factors wrapped in the hydroxylated mesoporous carbon; the purification factors comprise titanium dioxide doped with nitrogen and fluorine, a perovskite type composite oxide doped with nitrogen and fluorine and a rare earth phosphate material doped with fluorine;
The perovskite type composite oxide is one or more of GdFeO 3、Sr2FeMoO6、LaBO3、LaCoO3;
The rare earth phosphate material is SrCa 2(PO4)2:Eu2+ and/or H 3Sr6(PO4)5·2H2 O.
2. The air purification coating of claim 1, wherein the method of preparing the hydroxylated mesoporous carbon purification material comprises the steps of:
nitrogen doping and fluorine doping are carried out on the titanium dioxide and the perovskite type composite oxide, and fluorine doping is carried out on the rare earth phosphate material, so that a product A is obtained;
Carrying out hydroxylation reaction on mesoporous carbon to obtain a product B;
Calcining the product A and the product B under the protection of inert gas to obtain the hydroxylated mesoporous carbon purification material.
3. The air cleaning paint according to claim 2, wherein the titanium oxide and the perovskite type composite oxide are doped with nitrogen before being doped with fluorine.
4. The air purification coating of claim 2, wherein nitrogen doping and fluorine doping the titanium dioxide and perovskite type composite oxide and fluorine doping the rare earth phosphate material to obtain the product a comprises:
dispersing titanium sulfate or titanium tetrachloride in an aqueous solution of n-propanol, adding the perovskite type composite oxide, uniformly dispersing, adding an aqueous solution of urea, and burning the obtained precipitate to obtain a product C;
And (3) reacting the product C and the rare earth phosphate material with a fluorine source, and calcining the obtained mixture to obtain the product A.
5. The air purification coating of claim 2, wherein the hydroxylation reaction of mesoporous carbon to produce product B comprises:
And (3) placing the mesoporous carbon into a mixed solution of hydrogen peroxide and sulfuric acid, performing ultrasonic treatment in a water bath, cleaning and drying to obtain the product B.
6. The air purification coating of claim 4, wherein the fluorine source comprises ammonium fluoride;
The specific surface area of the mesoporous carbon is 1200m 2/g~1700m2/g, the average pore diameter is 2 mm-6 mm, and the pore volume is more than 2mL/g.
7. The air purification coating according to claim 2, wherein the mass ratio of the product A to the product B is (1-12): (2-20), the calcination temperature of the product A and the product B is 700 ℃ -1100 ℃ and the calcination time is 30-80 min.
8. The air purification coating of claim 1, wherein the solvent is one or more of an acrylic emulsion, isopropyl alcohol, and ethanol;
The mass ratio of the hydroxylated mesoporous carbon purifying material, the dispersing agent, the surfactant and the 3- (methacryloyloxy) propyl trimethoxy silane to the solvent is (30-50)/(2-8)/(1-5)/(1-10)/(40-80).
9. A back sheet having an air-purifying paint, characterized by comprising a paint-plated alloy whose surface is coated with the air-purifying paint according to any one of claims 1 to 8,
Wherein the surface layer of the paint-plated alloy is an organic coating, and the organic coating contains one or more groups of hydroxyl, carboxyl and double bonds.
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