CN109437752A - Photo catalytic cement based composites, preparation method and applications - Google Patents
Photo catalytic cement based composites, preparation method and applications Download PDFInfo
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- CN109437752A CN109437752A CN201811497708.7A CN201811497708A CN109437752A CN 109437752 A CN109437752 A CN 109437752A CN 201811497708 A CN201811497708 A CN 201811497708A CN 109437752 A CN109437752 A CN 109437752A
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- cement
- photochemical catalyst
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- photo catalytic
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- 239000004568 cement Substances 0.000 title claims abstract description 143
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 93
- 239000011159 matrix material Substances 0.000 claims abstract description 63
- 239000006210 lotion Substances 0.000 claims abstract description 35
- 239000011858 nanopowder Substances 0.000 claims abstract description 35
- 239000011230 binding agent Substances 0.000 claims abstract description 29
- 239000008187 granular material Substances 0.000 claims abstract description 18
- 239000011941 photocatalyst Substances 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 7
- 229930195729 fatty acid Natural products 0.000 claims abstract description 7
- 239000000194 fatty acid Substances 0.000 claims abstract description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012188 paraffin wax Substances 0.000 claims abstract description 7
- 239000005060 rubber Substances 0.000 claims abstract description 7
- 238000004528 spin coating Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000011398 Portland cement Substances 0.000 claims description 11
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 11
- 229940012189 methyl orange Drugs 0.000 claims description 11
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 claims description 10
- 239000008399 tap water Substances 0.000 claims description 9
- 235000020679 tap water Nutrition 0.000 claims description 9
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 8
- 229940043267 rhodamine b Drugs 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000011401 Portland-fly ash cement Substances 0.000 claims description 6
- 239000002957 persistent organic pollutant Substances 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 125000005313 fatty acid group Chemical group 0.000 claims description 5
- -1 poly- ethyl hydroxy siloxanes Chemical class 0.000 claims description 5
- NTWZYMJGDYYGNL-UHFFFAOYSA-N [Na].C[Si] Chemical compound [Na].C[Si] NTWZYMJGDYYGNL-UHFFFAOYSA-N 0.000 claims description 3
- VFZAYOWIXYSSBM-UHFFFAOYSA-N CC[Na].O[SiH3] Chemical compound CC[Na].O[SiH3] VFZAYOWIXYSSBM-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- 230000002335 preservative effect Effects 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000003469 silicate cement Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 5
- 150000004665 fatty acids Chemical class 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 15
- 239000000839 emulsion Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010919 dye waste Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLXGCFTYXICXJF-UHFFFAOYSA-N ethylsilicon Chemical compound CC[Si] XLXGCFTYXICXJF-UHFFFAOYSA-N 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J37/0215—Coating
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/08—Slag cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5041—Titanium oxide or titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5049—Zinc or bismuth oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5072—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with oxides or hydroxides not covered by C04B41/5025
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/65—Coating or impregnation with inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
- C04B2111/00827—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of photo catalytic cement based composites, photochemical catalyst composite granule including cement matrix and coated on the cement matrix outer surface, the photochemical catalyst composite granule includes binder and photochemical catalyst nano-powder, the mass ratio of the photochemical catalyst nano-powder and the binder is 0.01~0.1, the photochemical catalyst nano-powder is one of nano-titanium dioxide, nano zine oxide or nanometer di-iron trioxide, and the binder is one of fatty acid, organic silicon surfactant, paraffin, rubber or water-soluble resin lotion.Photo catalytic cement based composites proposed by the present invention avoid the waste of photocatalyst material while guaranteeing photocatalytic degradation effect.
Description
Technical field
The present invention relates to catalysis material technical field, in particular to a kind of photo catalytic cement based composites, preparation side
Method and its application.
Background technique
With the Fast Growth of the fast development of industrial economy, especially dyeing, results in and is promoted in foreign exchange earning,
While people's improvement of living, a large amount of organic dye waste water is also produced.In generated waste water containing can largely cause a disease,
Carcinogenic organic pollutant, thus it is extremely urgent to the processing of these organic dye waste waters.
Photocatalitic Technique of Semiconductor, by redox reaction degradable organic pollutant, is dropped using solar energy since it has
The advantages that rate is fast and mineralizing and degrading is thorough is solved, has become and solves one of environmental problem effective ways.The core of photocatalysis technology
The heart is catalysis material, and common catalysis material is usually nano-powder.Powder is since its partial size is small, large specific surface area, energy
It is enough effectively with organic dyestuff molecule contacts and to be adsorbed on dye molecule, and then effective degradating organic dye.However in order to keep away
The problems such as exempting from easy to reunite, difficult recycling caused by being used alone due to nano-powder, nano-powder is loaded to carrier by scientific research personnel
Enterprising enforcement is used.Cement-based material can make photochemical catalyst absorb sunlight to the full extent as the carrier of photochemical catalyst
Energy, and then complete Photocatalytic Degradation Process.Currently, photocatalysis nano material is loaded on cement matrix, usually there are two types of
Method: surface spraying method and internal incorporation methods.A, lotion is made in photochemical catalyst and binder by surface spraying method, is then sprayed
Coating is formed to the surface of net slurry, mortar, concrete etc., plays the effectiveness of photochemical catalyst, but the method needs to cooperate adhesive force
Stronger binder is used together；B, internal incorporation methods first by photochemical catalyst and cement powder after mixing, will after aquation
Photochemical catalyst is fixed in cement matrix, which can be fixed on intrinsic silicon for a part of photochemical catalyst, can not be played a role, be made
At waste.
Based on this, it is necessary to a kind of new photo catalytic cement based composites are developed, to guarantee in photocatalyst material
Under the premise of saving, photocatalytic degradation effect is realized to the full extent.
Summary of the invention
Photochemical catalyst and cement powder are uniformly mixed the purpose of the present invention is to solve in the prior art based on this
Afterwards, photochemical catalyst is fixed in cement matrix after aquation, a part of photochemical catalyst is fixed on intrinsic silicon, can not play work
With wasting problem.
The present invention proposes a kind of photo catalytic cement based composites, wherein including cement matrix and is coated on the water
The photochemical catalyst composite granule of mud outer surface of matrix, the photochemical catalyst composite granule include binder and photochemical catalyst nanometer
The mass ratio of powder, the photochemical catalyst nano-powder and the binder is 0.01~0.1, the photochemical catalyst nano-powder
For one of nano-titanium dioxide, nano zine oxide or nanometer di-iron trioxide, the binder is fatty acid, organosilicon table
One of face activating agent, paraffin, rubber or water-soluble resin lotion.
Photo catalytic cement based composites proposed by the present invention, including cement matrix and photochemical catalyst composite granule layer,
In the present invention, since photochemical catalyst composite granule layer to be arranged in the outer surface of cement matrix, in cement matrix not
Doped with photochemical catalyst composite granule, therefore while guaranteeing photocatalytic degradation effect, the wave of photocatalyst material is avoided
Take.
The photo catalytic cement based composites, wherein the cement matrix is portland cement, slag silicate salt water
One of mud, Portland pozzolana cement, Portland fly ash cement or composite Portland cement.
The photo catalytic cement based composites, wherein the dosage of the binder and the photochemical catalyst nano-powder
It is 1~5g/m3。
The photo catalytic cement based composites, wherein the organic silicon surfactant is methyl silicon sodium alcoholate, ethyl silicon
One of sodium alkoxide or poly- ethyl hydroxy siloxanes.
The present invention also proposes a kind of preparation method of photo catalytic cement based composites, wherein the method includes as follows
Step:
Cement matrix preparation: it after cement and tap water are stirred uniformly, are poured into mold and carry out ram-jolt, use is fresh-keeping
Film covering is demoulded afterwards for 24 hours, obtains the cement matrix after conserving in water；
The preparation of photochemical catalyst lotion: photochemical catalyst nano-powder is added in binder, carries out ultrasound point after agitated
It dissipates and obtains the photochemical catalyst lotion；
Photochemical catalyst nano-powder layer spin coating: the cement matrix is subjected to moistened surface, by the photochemical catalyst lotion
It is added dropwise on the cement matrix surface, spin coating is carried out on spin coater so that the photochemical catalyst lotion is coated uniformly on cement
Matrix surface；
Photocatalyst layer is dry: having the cement matrix of the photochemical catalyst lotion to do in an oven spin coating
It is dry, obtain the photo catalytic cement based composites.
The preparation method of photo catalytic cement based composites proposed by the present invention, is prepared separately cement matrix, then first
Photochemical catalyst lotion is prepared, by the photochemical catalyst lotion applicator being prepared in the outer surface of cement matrix, then by drying
It is dry, obtain final photochemical catalyst cement-base composite material.Due to being arranged photochemical catalyst composite granule layer in cement matrix
Outer surface, there is no doped with photochemical catalyst composite granule in cement matrix, therefore guaranteeing photocatalytic degradation effect
Meanwhile avoiding the waste of photocatalyst material.
The preparation method of the photo catalytic cement based composites, wherein in the step of prepared by the cement matrix, add
The quality of the tap water and cement that enter is 0.05~0.5 than range, and the cement of addition is portland cement, slag silicate salt water
Mud, Portland pozzolana cement Portland fly ash cement or composite Portland cement, the diameter of the mold are 10cm,
The time conserved in water is 1~28 day.
The preparation method of the photo catalytic cement based composites, wherein in the step of prepared by the photochemical catalyst lotion
In, the photochemical catalyst nano-powder is one of nano-titanium dioxide, nano zine oxide or nanometer di-iron trioxide, described
Binder is one of fatty acid, organic silicon surfactant, paraffin, rubber or water-soluble resin lotion, the binder
Dosage with the photochemical catalyst nano-powder is 1~5g/m3, carry out ultrasonic disperse ultrasonic frequency range be 60~
100Hz, the time of ultrasonic disperse are 5~15min.
The preparation method of the photo catalytic cement based composites, wherein in the photochemical catalyst nano-powder layer spin coating
The step of in, carry out spin coating when the speed of rotation be 700~1500rpm, spin-coating time be 0.5~2min.
The preparation method of the photo catalytic cement based composites, wherein in the dry step of the photocatalyst layer,
The temperature range being dried in an oven is 40 DEG C~80 DEG C, and the time being dried is 15~60min.
The present invention also proposes a kind of application of photo catalytic cement based composites, wherein applies photocatalysis as described above
Cement-base composite material carries out photocatalytic degradation to organic pollutant, and the organic pollutant is rhodamine B, methyl orange or methyl
It is blue.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Fig. 1 is the curve graph of photo catalytic cement based composites rhodamine B degradation in first embodiment of the invention；
Fig. 2 is the curve graph of photo catalytic cement based composites degradation methyl orange in second embodiment of the invention；
Fig. 3 is the curve graph of photo catalytic cement based composites degradation methyl blue in third embodiment of the invention.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing
Give preferred embodiment of the invention.But the invention can be realized in many different forms, however it is not limited to this paper institute
The embodiment of description.On the contrary, purpose of providing these embodiments is make it is more thorough and comprehensive to the disclosure.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term " and or " used herein includes one or more phases
Any and all combinations of the listed item of pass.
Currently, by internal incorporation methods first by photochemical catalyst and cement powder after mixing, by photochemical catalyst after aquation
It is fixed in cement matrix, which can be fixed on intrinsic silicon for a part of photochemical catalyst, can not play a role, cause to waste.
In order to solve this technical problem, the present invention proposes a kind of photo catalytic cement based composites, wherein the composite wood
Material includes cement matrix and the photochemical catalyst composite granule coated on cement matrix outer surface.
In this respect it is to be noted that above-mentioned photochemical catalyst composite granule includes binder and photochemical catalyst nano powder
Body.In the present invention, the mass ratio of photochemical catalyst nano-powder and binder is 0.01~0.1, and binder is received with photochemical catalyst
The dosage of rice flour body is 1~5g/m3。
In the selection of actual material, above-mentioned photochemical catalyst nano-powder is nano-titanium dioxide, nano zine oxide
Or one of nanometer di-iron trioxide.Above-mentioned binder is fatty acid, organic silicon surfactant, paraffin, rubber or water
One of soluble resin lotion.Specifically, the organic silicon surfactant can for above-mentioned organic silicon surfactant
Think one of methyl silicon sodium alcoholate, ethyl sodium silanolate or poly- ethyl hydroxy siloxanes.Above-mentioned cement matrix is silicate cement
One in mud, portland slag cement, Portland pozzolana cement, Portland fly ash cement or composite Portland cement
Kind.
Photo catalytic cement based composites proposed by the present invention, including cement matrix and photochemical catalyst composite granule layer,
In the present invention, since photochemical catalyst composite granule layer to be arranged in the outer surface of cement matrix, in cement matrix not
Doped with photochemical catalyst composite granule, therefore while guaranteeing photocatalytic degradation effect, the wave of photocatalyst material is avoided
Take.
In addition, the invention also provides a kind of preparation methods of photo catalytic cement based composites, wherein this method includes
Following steps:
(1) prepared by cement matrix: after cement and tap water are stirred uniformly, being poured into mold and carries out ram-jolt, uses
Preservative film covering is demoulded afterwards for 24 hours, obtains cement matrix after conserving in water.
In this step, the quality of the tap water and cement of addition is 0.05~0.5 than range, and the cement of addition can be
Portland cement, portland slag cement, Portland pozzolana cement Portland fly ash cement or composite Portland cement
In any one.The diameter of above-mentioned mold is 10cm, and the time conserved in water is 1~28 day.
(2) prepared by photochemical catalyst lotion: photochemical catalyst nano-powder being added in binder, carries out ultrasound after agitated
Dispersion obtains photochemical catalyst lotion.
In this step, the photochemical catalyst nano-powder of addition can be nano-titanium dioxide, nano zine oxide or nanometer
One of di-iron trioxide.Above-mentioned binder can be fatty acid, organic silicon surfactant, paraffin, rubber or water-soluble
One of property resin emulsion.
In this step, the dosage of binder and photochemical catalyst nano-powder is 1~5g/m3.Carrying out ultrasonic disperse
When, corresponding ultrasonic frequency range is 60~100Hz, and the time of ultrasonic disperse is 5~15min.
(3) photochemical catalyst nano-powder layer spin coating: cement matrix is subjected to moistened surface, photochemical catalyst emulsion droplets are added in
Cement matrix surface carries out spin coating so that photochemical catalyst lotion is coated uniformly on cement matrix surface on spin coater.
When carrying out spin coating operation, control spin coater the speed of rotation be 700~1500rpm, spin-coating time be 0.5~
2min。
(4) photocatalyst layer is dry: having the cement matrix of photochemical catalyst lotion to be dried in an oven spin coating, obtains
Photo catalytic cement based composites.
In this step, the temperature range being dried in an oven is 40 DEG C~80 DEG C, and the time being dried is 15
~60min.After the completion of to be dried, above-mentioned photo catalytic cement based composites can be obtained.
The preparation method of photo catalytic cement based composites proposed by the present invention, is prepared separately cement matrix, then first
Photochemical catalyst lotion is prepared, by the photochemical catalyst lotion applicator being prepared in the outer surface of cement matrix, then by drying
It is dry, obtain final photochemical catalyst cement-base composite material.Due to being arranged photochemical catalyst composite granule layer in cement matrix
Outer surface, there is no doped with photochemical catalyst composite granule in cement matrix, therefore guaranteeing photocatalytic degradation effect
Meanwhile avoiding the waste of photocatalyst material.
More detailed narration explanation is carried out to technical solution of the present invention with several specific embodiments below.
Embodiment one
The preparation method for the photo catalytic cement based composites that first embodiment of the invention is proposed includes the following steps:
(1) prepared by cement matrix: 100g portland cement (grade 42.5) and 25g tap water are stirred uniformly
Afterwards, it is poured into the mold that diameter is 10cm and carries out ram-jolt, winding film covering demoulds afterwards for 24 hours, conserves 1 day in water.
(2) prepared by photochemical catalyst lotion: 0.075g nano-titanium dioxide light being added into 2g fat acid binder lotion and urges
Agent nano-powder after being stirred uniformly, carries out ultrasonic disperse 15min under 60Hz frequency.
(3) photochemical catalyst nano-powder layer spin coating: the surface of cement matrix is soaked with wet cloth, by the light after dispersion
Catalyst emulsion is added drop-wise to cement matrix surface, controls spin coater with 700rpm revolving speed and carries out spin coating 1min, after removing spin coating
Cement matrix.
(4) photocatalyst layer is dry: the cement matrix after spin coating to be had to photochemical catalyst lotion carries out in 60 DEG C of baking oven
Dry 30min, finally obtains photo catalytic cement based composites.
In the present embodiment, to obtained photo catalytic cement based composites to the degradation property of rhodamine B solution into
Research is gone.Specifically, using photo catalytic cement composite degradation 50mL, concentration molten for the rhodamine B (RhB) of 10mg/L
Liquid, irradiates solution using the ultraviolet lamp of 300W at 8mm, is stirred solution with the mixing speed of 1000rpm.Wherein, light is urged
It is as shown in Figure 1 to the degradation curve of RhB solution to change cement composite material.From figure 1 it appears that when the photocatalytic degradation time reaches
When to 30min, it is substantially finished the degradation to RhB solution, has effectively eliminated pollutant.
Embodiment two
The preparation method for the photo catalytic cement based composites that second embodiment of the invention is proposed includes the following steps:
(1) prepared by cement matrix: 100g Portland pozzolana cement (grade 32.5) and 50g tap water being stirred equal
It after even, be poured into the mold that diameter is 10cm and carry out ram-jolt, winding film covering demoulds afterwards for 24 hours, conserves 7 days in water.
(2) prepared by photochemical catalyst lotion: it is nano oxidized that 0.05g being added into the poly- ethyl hydroxy silicone binder lotion of 5g
Zinc photochemical catalyst nano-powder after being stirred uniformly, carries out ultrasonic disperse 10min under 80Hz frequency.
(3) photochemical catalyst nano-powder layer spin coating: the surface of cement matrix is soaked with wet cloth, then by the light after dispersion
Catalyst emulsion is added drop-wise to cement matrix surface, controls spin coater with 1500rpm revolving speed and carries out spin coating 30s, after removing spin coating
Cement matrix.
(4) photocatalyst layer is dry: the cement matrix after spin coating to be had to photochemical catalyst lotion carries out in 80 DEG C of baking oven
Dry 15min, finally obtains photo catalytic cement based composites.
In the present embodiment, to obtained photo catalytic cement based composites to the degradation property of methyl orange (MO) solution
It is studied.Specifically, using photo catalytic cement composite degradation 50mL, concentration molten for the methyl orange (MO) of 10mg/L
Liquid irradiates solution, the speed stirring solution of 1000rpm using the ultraviolet lamp of 300W at 8mm.Wherein, photo catalytic cement is compound
Material is as shown in Figure 2 to the degradation curve of methyl orange (MO) solution.From figure 2 it can be seen that when the photocatalytic degradation time reaches
When 30min, it is substantially finished the degradation to methyl orange (MO) solution, has effectively eliminated pollutant.
Embodiment three
The preparation method for the photo catalytic cement based composites that third embodiment of the invention is proposed includes the following steps:
(1) prepared by cement matrix: 100g composite Portland cement (grade 52.5) is stirred evenly with 30g tap water
Afterwards, it is poured into the mold that diameter is 10cm and carries out ram-jolt, winding film covering demoulds afterwards for 24 hours, conserves 28 days in water.
(2) prepared by photochemical catalyst lotion: 0.1g nanometers of di-iron trioxides being added into 1g water-soluble resin emulsion binder
Photochemical catalyst nano-powder after being stirred uniformly, carries out ultrasonic disperse 5min under 100Hz frequency.
(3) photocatalyst layer spin coating: the surface of cement matrix is soaked with wet cloth, then by the photochemical catalyst cream after dispersion
Drop is added to cement matrix surface, controls spin coater with 1000rpm revolving speed and carries out spin coating 2min, the cement base after removing spin coating
Body.
(4) photocatalyst layer is dry: the cement matrix after spin coating to be had to photochemical catalyst lotion carries out in 40 DEG C of baking oven
Dry 60min, finally obtains photo catalytic cement based composites.
In the present embodiment, to obtained photo catalytic cement based composites to the degradation property of methyl blue (MB) solution
It is studied.Specifically, using photo catalytic cement composite degradation 50mL, concentration molten for the methyl blue (MB) of 10mg/L
Liquid irradiates solution, the speed stirring solution of 1000rpm using the ultraviolet lamp of 300W at 8mm.Wherein, photo catalytic cement is compound
Material is as shown in Figure 3 to the degradation curve of methyl blue (MB) solution.From figure 3, it can be seen that when the photocatalytic degradation time reaches
When 30min, it is substantially finished the degradation to methyl blue (MB) solution, has effectively eliminated pollutant.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of photo catalytic cement based composites, which is characterized in that including cement matrix and be coated on the cement matrix
The photochemical catalyst composite granule of outer surface, the photochemical catalyst composite granule include binder and photochemical catalyst nano-powder,
The mass ratio of the photochemical catalyst nano-powder and the binder is 0.01~0.1, and the photochemical catalyst nano-powder is to receive
One of rice titanium dioxide, nano zine oxide or nanometer di-iron trioxide, the binder is fatty acid, organosilyl surface is living
One of property agent, paraffin, rubber or water-soluble resin lotion.
2. photo catalytic cement based composites according to claim 1, which is characterized in that the cement matrix is silicate
One in cement, portland slag cement, Portland pozzolana cement, Portland fly ash cement or composite Portland cement
Kind.
3. photo catalytic cement based composites according to claim 2, which is characterized in that the binder is urged with the light
The dosage of agent nano-powder is 1~5g/m3。
4. photo catalytic cement based composites according to claim 2, which is characterized in that the organic silicon surfactant
For one of methyl silicon sodium alcoholate, ethyl sodium silanolate or poly- ethyl hydroxy siloxanes.
5. a kind of preparation method of photo catalytic cement based composites, which is characterized in that described method includes following steps:
Cement matrix preparation: it after cement and tap water are stirred uniformly, are poured into mold and carry out ram-jolt, covered with preservative film
Lid is demoulded afterwards for 24 hours, obtains the cement matrix after conserving in water；
The preparation of photochemical catalyst lotion: photochemical catalyst nano-powder is added in binder, is carried out ultrasonic disperse after agitated and is obtained
To the photochemical catalyst lotion；
Photochemical catalyst nano-powder layer spin coating: the cement matrix is subjected to moistened surface, the photochemical catalyst lotion is added dropwise
On the cement matrix surface, spin coating is carried out on spin coater so that the photochemical catalyst lotion is coated uniformly on cement matrix
Surface；
Photocatalyst layer is dry: having the cement matrix of the photochemical catalyst lotion to be dried in an oven spin coating, obtains
To the photo catalytic cement based composites.
6. the preparation method of photo catalytic cement based composites according to claim 5, which is characterized in that in the cement
In the step of prepared by matrix, the quality of the tap water of addition and cement is 0.05~0.5 than range, and the cement of addition is silicate
Cement, portland slag cement, Portland pozzolana cement Portland fly ash cement or composite Portland cement, the mould
The diameter of tool is 10cm, and the time conserved in water is 1~28 day.
7. the preparation method of photo catalytic cement based composites according to claim 5, which is characterized in that urged in the light
In the step of prepared by agent lotion, the photochemical catalyst nano-powder is three oxygen of nano-titanium dioxide, nano zine oxide or nanometer
Change one of two iron, the binder is fatty acid, organic silicon surfactant, paraffin, rubber or water-soluble resin lotion
One of, the dosage of the binder and the photochemical catalyst nano-powder is 1~5g/m3, carry out the super of ultrasonic disperse
Acoustic frequency range is 60~100Hz, and the time of ultrasonic disperse is 5~15min.
8. the preparation method of photo catalytic cement based composites according to claim 5, which is characterized in that urged in the light
In the step of agent nano-powder layer spin coating, carry out spin coating when the speed of rotation be 700~1500rpm, spin-coating time be 0.5~
2min。
9. the preparation method of photo catalytic cement based composites according to claim 5, which is characterized in that urged in the light
In the dry step of agent layer, the temperature range being dried in an oven is 40 DEG C~80 DEG C, and the time being dried is 15
~60min.
10. a kind of application of photo catalytic cement based composites, which is characterized in that application such as above-mentioned Claims 1-4 is any one
Photo catalytic cement based composites described in carry out photocatalytic degradation to organic pollutant, and the organic pollutant is rhodamine
B, methyl orange or methyl blue.
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