CN105498744A - Preparation method of high-activity nanometer CaCO3-TiO2 composite photocatalytic material - Google Patents
Preparation method of high-activity nanometer CaCO3-TiO2 composite photocatalytic material Download PDFInfo
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- CN105498744A CN105498744A CN201610056112.8A CN201610056112A CN105498744A CN 105498744 A CN105498744 A CN 105498744A CN 201610056112 A CN201610056112 A CN 201610056112A CN 105498744 A CN105498744 A CN 105498744A
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 230000000694 effects Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 239000011941 photocatalyst Substances 0.000 claims description 28
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 27
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 18
- 239000011575 calcium Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 12
- 239000000920 calcium hydroxide Substances 0.000 claims description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000003973 paint Substances 0.000 claims description 10
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000003916 acid precipitation Methods 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 230000002421 anti-septic effect Effects 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 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 2
- 239000000049 pigment Substances 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- 238000004448 titration Methods 0.000 claims description 2
- VAEJJMYYTOYMLE-UHFFFAOYSA-N [O].OS(O)(=O)=O Chemical compound [O].OS(O)(=O)=O VAEJJMYYTOYMLE-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 description 12
- 238000007146 photocatalysis Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- 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
-
- B01J35/39—
-
- B01J35/50—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
Abstract
The invention relates to a preparation method of a high-activity nanometer CaCO3-TiO2 composite photocatalytic material. The method is simple in process, high in operability, relatively low in cost and applicable to batch preparation and has the possibility of industrial production and wide application prospect. In addition, the preparation method has the another important advantage that the whole reaction system only adopts water as a solvent, no organic solvent such as alcohol is adopted, so that pollution to the environment is effectively reduced, and the production process safety is improved.
Description
Technical field
The invention belongs to inorganic, metal oxide preparation field, particularly high-activity nano CaCO
3-TiO
2the preparation method of composite photocatalyst material.
Background technology
Nano-TiO
2as functional inorganic material, be with a wide range of applications at numerous areas such as coating, opto-electronic conversion, catalysis, function ceramics, anti-biotic materials, its synthesis and application study are the emphasis of correlation function Material Field research always.This wherein, be a kind of emerging green technology effectively removing chemical pollutant using nano-titanium oxide as the Photocatalitic Technique of Semiconductor of photochemical catalyst, it can accelerate the degradation process of oxynitrides and sulfide.Namely the hole utilizing solid semiconductor catalysis material to produce by optical excitation, captures NO
xelectronics in system, makes it activate and be oxidized to NO
3 -stay catalyst surface, thus the NO of solidification haze
xsource.At road traffic space application photocatalytic degradation material, modification is carried out as utilized catalysis material road pavement material, or produce coating by catalysis material, what can make road paint, road equipment material possesses harmful substance in degrading tail gas, reducing tail gas to the pollution effects of air, is the effective ways of the end treatment of moving source tail gas clean-up.
Research shows, at TiO
2a small amount of metal ion is mixed in lattice, can at TiO
2surface produces defect, and what this defect became light induced electron and hole catches trap, can effectively reduce light induced electron and hole-recombination, improve photo-generated carrier efficiency.In addition, because doped metal ion can at TiO
2the doped energy-band that between valence band and conduction band, formation one is new, reduces TiO
2energy gap, and then strengthen the visible light activity of catalyst.
But conductor photocatalysis is by NO
xbe oxidized to NO
3 -reaction, through many intermediate steps, have some harmful intermediate products and generate, the NO as part is oxidized to NO
2, and be released, this is harmful to environment, can promote the formation of photochemical fog.And photocatalysis technology and adsorption technology are combined, be the primary solutions addressed this problem.High-absorption material is to NO and NO
2absorption, makes the NO generated through Photocatalytic Oxidation With Semiconductors NO
2namely also NO is oxidized to further by absorption in the moment produced
3 -, thus avoid intermediate product NO
2release.
At present, for mainly comprising the material such as active carbon, molecular sieve with the high adsorption material of nano-titanium oxide compound, but absorbent charcoal material is due to light tight, lower to the utilization rate of load catalysis material.And adopt molecular sieve as carrier, there is cost higher, back loading technique is easy to the problem of blocking pipe simultaneously.Therefore, direct doped composite metal oxide is to remove the NO of absorption
3 -ion, thus improve decomposing N O
xperformance there is important Research Significance.At present, associated materials synthetic method generally adopts respectively synthetic silica and titania meterial, then the technique of compound, and step is numerous and diverse, and there is subsequent oxidation silicon and titanium oxide cannot the problem of effective compound.Its main cause is, titanium oxide crystallization needs high temperature sintering usually, and silica generally can in liquid phase direct hydrolysis, and therefore, liquid phase is directly synthesized composite construction and had difficulties.
Summary of the invention
According to an aspect of the present invention, one object of the present invention is to provide a kind of simple and easy to control, respond well, and what be suitable for large-scale industrial production prepares high-activity nano CaCO
3-TiO
2the method of composite photocatalyst material.
In order to realize above-mentioned purpose of the present invention, high-activity nano CaCO of the present invention
3-TiO
2the preparation method of composite photocatalyst material comprises the following steps:
1) controlled hydrolysis prepares calcium hydroxide and ortho-titanic acid precipitation
By Ti-inorganic salt and calcium inorganic salts jointly soluble in water, form mixed solution, wherein the molar ratio of calcium ion and titanium ion is 0.1: 1 to 0.6: 1, and by the Ti in mixed solution
4+ion and Ca
2+total concentration of metal ions of ion is adjusted to 0.01 ~ 0.50mol/L; Joined in described mixed solution by inorganic base, the pH value making mixed solution is 5 ~ 11, obtains the co-precipitation of calcium hydroxide and ortho-titanic acid, the precipitation obtained purified process removing impurity.
2) hydrogen peroxide-ammino-complex preparation
Hydrogenperoxide steam generator dispersion steps 1 with mass percentage concentration is 10% to 60%) calcium hydroxide that obtains becomes solution state with the co-precipitation of ortho-titanic acid, wherein H
2o
2with Ca
2+ion and Ti
4+total metal ion molecule mol ratio control 1 to 25.
3) high-activity nano CaCO is prepared
3-TiO
2composite photocatalyst material
Under reaction temperature is 0 ~ 100 DEG C of stirring, to step 2) add water miscible carbonate in calcium/titanium-peroxy-complexes solution of preparing and react, wherein, the mol ratio of water soluble carbonate and calcium ion is 1: 1, heat time controls between 0.5 hour to 12 hours, after having reacted, through post-processing steps such as filtering, wash, be dry, obtain high-activity nano CaCO
3-TiO
2composite photocatalyst material.
Wherein, step 1) in titanium liquid in Ti
4+ion concentration is for being preferably 0.1 ~ 0.3mol/L, more preferably 0.2 ~ 0.3mol/L.Described inorganic base is selected from NaOH, potassium hydroxide or ammoniacal liquor.
Step 1) in described calcium inorganic salts can be selected from calcium chloride or calcium nitrate etc., be preferably calcium nitrate.
Step 1) in Ti-inorganic salt can be ilmenite, metatitanic acid compounds, titanium tetrachloride, titanium sulfate etc., be preferably titanium tetrachloride.Described purge process can by method removing impurity such as frozen recrystallizations.
Step 2) in the mass percentage concentration of hydrogenperoxide steam generator be preferably 20% to 40%, be more preferably 30%; H
2o
2with Ca
2+ion and Ti
4+total metal ion molecule mol ratio preferably control 1 to 25, be preferably 5 to 10.
Described water miscible carbonate can be sodium carbonate, potash etc., is preferably sodium carbonate.
Step 3) in described reaction temperature be preferably 10 ~ 90 DEG C, be more preferably 60 ~ 80 DEG C, the heat time is preferably between 1 hour to 8 hours, is more preferably between 3 hours to 6 hours.
Preparation method according to the present invention does not use any catalyst.
Preparation method according to the present invention does not use any organic solvent.
According to an aspect of the present invention, one object of the present invention is to provide a kind of high-activity nano CaCO
3-TiO
2composite photocatalyst material, described composite photocatalyst material is prepared by above method.
According to an aspect of the present invention, one object of the present invention is to provide a kind of coating, and described coating comprises the high-activity nano CaCO prepared according to preparation method of the present invention
3-TiO
2composite photocatalyst material, and other conventional paint ingredient, such as resin, antiseptic, levelling agent, pigment etc., as long as described conventional paint ingredient can not to described high-activity nano CaCO
3-TiO
2the catalytic performance of composite photocatalyst material causes adverse effect.Coating according to the present invention can adopt the modes such as spraying, roller coating, brushing directly to apply in addition.
Beneficial effect
The present invention is compared with the preparation method of bibliographical information, and method flow of the present invention is simple, workable, simultaneously less expensive, is applicable to batch preparation, possesses the possibility of suitability for industrialized production, be with a wide range of applications.Another considerable advantage of the present invention is that whole reaction system all only uses water as solvent in addition, and not with an organic solvent, such as alcohol etc., thus efficiently reduce the pollution to environment, improve the security of production link.
Accompanying drawing explanation
Fig. 1 is the high-activity nano CaCO prepared according to embodiment 1
3-TiO
2the SEM figure of composite photocatalyst material.
Fig. 2 is the CaCO that do not adulterate prepared according to comparative example 1
3tiO
2catalysis material SEM schemes.
Fig. 3 is the doping CaCO prepared according to embodiment 1 and comparative example 1
3do not adulterate CaCO
3the photocatalysis result of photocatalysis material of titanium dioxide.
Detailed description of the invention
After the electronics of catalysis material and hole are optically excited, hole itself has very strong electronic capability, can capture NO
xelectronics in system, makes it be oxidized by activating.Oxygen in electronics and water and air reacts and generates stronger OH and O of oxidability
2 -deng, be by NO
xfinal oxidation generates NO
3 -topmost oxidant.But oxidation NO
xthe NO generated
3 -the surface of catalyst being remained in, catalyst activity can be made when being accumulated to finite concentration low, so need clean, the regeneration of water.
The present invention mainly utilizes in catalyst and adds CaCO
3, by the NO that photocatalysis generates
3 -with CaCO
3reaction generates Ca (NO
3)
2with CO
2, prevent the reduction of catalyst photocatalytic activity and extend life-span of coating.
The CaCO of nano-scale
3belong to inorganic functional chemical filler, its advantage be evenly, exquisiteness, good in optical property, cheap, nontoxic etc., industry and the departments such as papermaking, rubber, coating, plastics, paint, ink, toothpaste, medicine can be widely used in.In addition, due to the CaCO of nano-scale
3space steric effect, can make coating suspend when density is larger, play sludge proof effect, in addition, by Nano-meter CaCO3
3add the thixotropy can improving system in water paint, the adhesive force of coating, corrosion resistance, scrub resistance, stain resistance, intensity, hardness, surface smoothness and coefficient of friction etc. are significantly improved.
Coating according to the present invention may be used for the substrate surfaces such as outdoor and indoor wall, ground, brick face and strong adhesion.Such as can by coatings according to the present invention on the surface of floor tile, for outdoor road surfacing; Or after freeway guardrail dope lacquerer sequence completes, described coating is directly coated on skin of paint, thus realizes the NO to air middle and high concentration
xdecompose.And also can directly be coated on the surface of external wall according to coating of the present invention, effectively realize pollutants in air (NO
x, SO
x, VOCs etc.) degraded and the small particles of pollution thing absorption such as PM2.5.
Following examples are only enumerate as the example of embodiment of the present invention, do not form any restriction to the present invention, it will be appreciated by those skilled in the art that the amendment in the scope not departing from essence of the present invention and design all falls into protection scope of the present invention.
Hereinafter, describe in detail with reference to the accompanying drawings preferred embodiment of the present disclosure.Before described, the term used in description and claims should be understood, and should not be construed as and be confined to general and dictionary meaning, but the principle of term suitably should be defined based on allowing the artificially best explanation of invention, make an explanation based on the meaning and concept corresponding to the technology of the present invention aspect.Therefore, at this description only preferred embodiment for the purpose of illustration, and be not mean to limit the scope of the invention, it is therefore to be understood that, can be made other equivalently to implement and amendment under without departing from the spirit and scope of the present invention.
Embodiment 1
First use 500ml deionized water dissolving 100g titanyl sulfate and 20g calcium nitrate, obtain the mixed aqueous solution of titanyl sulfate and calcium nitrate; By mass concentration be 36% ammonia water titration mixed aqueous solution be 9 be precipitated thing to PH, spend deionized water 3 times, obtain calcium hydroxide and ortho-titanic acid mixture.The calcium hydroxide obtained with the aqueous hydrogen peroxide solution dissolving 5g that 5ml mass percentage concentration is 30% and ortho-titanic acid mixture, thus obtain the aqueous solution of the titanium peroxide containing calcium hydroxide; At temperature is 100 DEG C, add 1g sodium carbonate, mechanical agitation back flow reaction 4 hours, after having reacted, product is through filtering, washing, and drying waits process to obtain high-activity nano CaCO
3-TiO
2composite photocatalyst material.
Comparative example 1
Except not adding as except calcium nitrate, the mode identical according to embodiment 1 prepares the CaCO that do not adulterate
3tiO
2catalysis material.
Fig. 1 is the high-activity nano CaCO prepared according to embodiment 1
3-TiO
2the SEM figure of composite photocatalyst material.Fig. 2 is the CaCO that do not adulterate prepared according to comparative example 1
3tiO
2catalysis material SEM schemes.As can be seen from the figure prepared according to the methods of the invention CaCO
3-TiO
2the particle of composite photocatalyst material to be diameter be several nanometer to 10 ran, and uniform particle sizes granule-morphology is even.
Embodiment 2
Except adding 5g calcium nitrate as except calcium ion source, the mode identical according to embodiment 1 prepares CaCO
3-TiO
2composite photocatalyst material.
Embodiment 3
Except adding 10g calcium nitrate as except calcium ion source, the mode identical according to embodiment 1 prepares CaCO
3-TiO
2composite photocatalyst material.
EXPERIMENTAL EXAMPLE 1:CaCO
3interpolation on the hardness of film and and the impact of adhesive force.
The preparation method of coating: respectively the coating of the composite photocatalyst material comprising embodiment 1 to 3 and comparative example 1 is evenly coated in specimen surface with plastic sheeting roll coater.
Hardness measuring method is: according to GB/T6739-86, adopts pencil hardness test to measure the hardness of film.Adopt the sharpened edge of the pencil-lead end face of a set of known hardness, draw film with film angle at 45 °, represent with the most hard pencil hardness that can not scratch film.
The method of testing of adhesive force: according to GB/T1720-89, the adhesive force of employingization circle method test paint film.
Chemical resistance method of testing: with reference to the first method in GB GB/T1763-89 " paint film chemical reagent resistance determination method ".Get film ready by metric system, by the model of 2/3 leaching people 3% salt solution, temperature is 25 DEG C ± 1 DEG C.Take out after certain hour, use water-washing desalting mark from the beginning, blot the water droplet on surface with filter paper.Observe the phenomenons such as whether paint film has bubble, peels off, rusty stain, variable color.Test data is listed in the table below in 1.
Table 1
As can be seen from the data of table 1, along with CaCO in composite photocatalyst material
3the increase of content, hardness and the adhesive force of film all increase, and are better than the CaCO that do not adulterate
3tiO
2catalysis material, this illustrates CaCO in catalysis material
3have the lifting helping catalysis material performance.
EXPERIMENTAL EXAMPLE 2:NO
xdegradation experiment
By the high-activity nano CaCO obtained
3-TiO
2composite photocatalyst material carries out NO
xdegradation experiment, described experiment is carried out as follows:
Respectively by according to embodiment 1 and prepare according to comparative example 1 be doped with CaCO
3do not adulterate CaCO
3photocatalysis material of titanium dioxide be coated on the glass plate of 10cm × 20cm, the consumption of described composite photocatalyst material is 0.5g, then with 2 μ w/cm
2white light light intensity when irradiating, flow through this glass plate with the air-flow of NO containing 1ppm, gas flow rate is 800ml/min.In addition, select the situation of not coated catalysts to test as blank, do same experiment as a comparison.Result is shown in figure 3.
As can be seen from the result of Fig. 3, when not using catalyst, the NO in gas
xsubstantially without degraded.Under white light conditions, the photocatalytic activity of single-phase photocatalysis material of titanium dioxide is lower, and it is 25% to the conversion ratio of NO, under the same conditions, and CaCO
3-TiO
2composite photocatalyst material is 74% to the conversion ratio of NO.
Claims (10)
1. a high-activity nano CaCO
3-TiO
2the preparation method of composite photocatalyst material, comprises the following steps:
1) controlled hydrolysis prepares calcium hydroxide and ortho-titanic acid precipitation
By Ti-inorganic salt and calcium inorganic salts jointly soluble in water, form mixed solution, wherein the molar ratio of calcium ion and titanium ion is 0.1: 1 to 0.6: 1, and by the Ti in mixed solution
4+ion and Ca
2+total concentration of metal ions of ion is adjusted to 0.01 ~ 0.50mol/L; Joined in described mixed solution by inorganic base, the pH value making mixed solution is 5 ~ 11, obtains the co-precipitation of calcium hydroxide and ortho-titanic acid, the precipitation obtained purified process removing impurity;
2) hydrogen peroxide-ammino-complex preparation
Hydrogenperoxide steam generator dispersion steps 1 with mass percentage concentration is 10% to 60%) calcium hydroxide that obtains becomes solution state with the co-precipitation of ortho-titanic acid, wherein H
2o
2with Ca
2+ion and Ti
4+total metal ion molecule mol ratio control 1 to 25;
3) high-activity nano CaCO is prepared
3-TiO
2composite photocatalyst material
Under reaction temperature is 0 ~ 100 DEG C of stirring, to step 2) add water miscible carbonate in calcium/titanium-peroxy-complexes solution of preparing and react, wherein, the mol ratio of water soluble carbonate and calcium ion is 1: 1, heat time controls between 0.5 hour to 12 hours, after having reacted, through post-processing steps such as filtering, wash, be dry, obtain high-activity nano CaCO
3-TiO
2composite photocatalyst material.
2. preparation method according to claim 1, is characterized in that, step 1) described in Ti4+ ion concentration in titanium liquid for being preferably 0.1 ~ 0.3mol/L, more preferably 0.2 ~ 0.3mol/L; Described inorganic base is selected from NaOH, potassium hydroxide or ammoniacal liquor.
3. preparation method according to claim 1, is characterized in that, step 1) in described calcium inorganic salts can be selected from calcium chloride or calcium nitrate etc., be preferably calcium nitrate; Described Ti-inorganic salt can be ilmenite, metatitanic acid compounds, titanium tetrachloride, titanium sulfate etc., is preferably titanium tetrachloride.Described purge process can by method removing impurity such as frozen recrystallizations.
4. preparation method according to claim 1, is characterized in that, step 2) described in the mass percentage concentration of hydrogenperoxide steam generator be preferably 20% to 40%, be more preferably 30%; H
2o
2with Ca
2+total metal ion molecule mol ratio of ion and Ti4+ preferably controls 1 to 25, is preferably 5 to 10; Described water miscible carbonate can be sodium carbonate, potash etc., is preferably sodium carbonate.
5. preparation method according to claim 1, is characterized in that, step 3) described in described reaction temperature be preferably 10 ~ 90 DEG C, be more preferably 60 ~ 80 DEG C, the heat time is preferably between 1 hour to 8 hours, is more preferably between 3 hours to 6 hours.
6. preparation method according to claim 1, is characterized in that, described preparation method does not use any catalyst, does not use any organic solvent simultaneously.
7. preparation method according to claim 1, is characterized in that, first dissolves 100 parts sulfuric acid oxygen titaniums and 20 weight portion calcium nitrate by 500 parts by weight of deionized water, obtains the mixed aqueous solution of titanyl sulfate and calcium nitrate; By mass concentration be 36% ammonia water titration mixed aqueous solution be 9 be precipitated thing to PH, spend deionized water 3 times, obtain calcium hydroxide and ortho-titanic acid mixture.Dissolve with the aqueous hydrogen peroxide solution that 5 weight portion mass percentage concentration are 30% calcium hydroxide and ortho-titanic acid mixture that 5 weight portions obtain, thus obtain the aqueous solution of the titanium peroxide containing calcium hydroxide; At temperature is 100 DEG C, add 1 parts by weight sodium carbonate, mechanical agitation back flow reaction 4 hours, after having reacted, product is through filtering, washing, and drying waits process to obtain high-activity nano CaCO
3-TiO
2composite photocatalyst material.
8. a high-activity nano CaCO
3-TiO
2composite photocatalyst material, described composite photocatalyst material is prepared by preparation method as claimed in any of claims 1 to 7.
9. a coating, described coating comprises high-activity nano CaCO according to claim 7
3-TiO
2composite photocatalyst material, and other conventional paint ingredient.
10. coating according to claim 9, is characterized in that, described conventional coating comprise be selected from resin, antiseptic, levelling agent, pigment one or more.
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| CN106582641A (en) * | 2016-12-05 | 2017-04-26 | 深圳清华大学研究院 | TiO2-based nanometer heterojunction composite photocatalytic material and preparation method thereof |
| CN108273487A (en) * | 2018-02-09 | 2018-07-13 | 纳琦环保科技有限公司 | The preparation method of titanium oxide/calcium oxide/silica composite photocatalyst material of hollow structure |
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