CN108033719B - Efficient multipurpose photocatalytic concrete - Google Patents
Efficient multipurpose photocatalytic concrete Download PDFInfo
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- CN108033719B CN108033719B CN201711185415.0A CN201711185415A CN108033719B CN 108033719 B CN108033719 B CN 108033719B CN 201711185415 A CN201711185415 A CN 201711185415A CN 108033719 B CN108033719 B CN 108033719B
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 131
- 239000004567 concrete Substances 0.000 title claims abstract description 85
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000004568 cement Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000003980 solgel method Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011941 photocatalyst Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- 239000010457 zeolite Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 239000010451 perlite Substances 0.000 claims description 3
- 235000019362 perlite Nutrition 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 19
- 238000007146 photocatalysis Methods 0.000 abstract description 18
- 239000002245 particle Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 7
- 230000006378 damage Effects 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 16
- 239000002086 nanomaterial Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000004566 building material Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
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- 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
-
- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/04—Heat treatment
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- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1055—Coating or impregnating with inorganic materials
- C04B20/1066—Oxides, Hydroxides
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- 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
- C04B2111/00017—Aspects relating to the protection of the environment
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- 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
- C04B2111/00025—Aspects relating to the protection of the health, e.g. materials containing special additives to afford skin protection
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- 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
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Abstract
The invention discloses high-efficiency multipurpose photocatalytic concrete, which mainly comprises 5-10 wt% of photocatalytic aggregate, and the photocatalytic concrete is prepared by doping the photocatalytic aggregate in the concrete, so that the alkaline damage TiO of cement in the concrete is effectively reduced2The catalytic efficiency of the photocatalytic building cement is effectively improved, and the service life of the photocatalytic building cement is effectively prolonged. The invention adopts a sol-gel method to prepare TiO2Hydrosol, adopting a negative pressure-saturation method to dip the aggregate, and calcining to prepare photocatalytic aggregate; the preparation method of the invention avoids TiO2Agglomeration of the nanoparticles to make TiO2The particles are uniformly dispersed in the aggregate, so that the specific surface area of the photocatalysis is improved, and the photocatalysis efficiency is effectively improved; the invention prepares the photocatalytic aggregate after calcination, thereby leading TiO to be2Chemical bond bonding is generated on the surface of the aggregate, so that the bonding force is enhanced, and the durability is improved.
Description
Technical Field
The invention belongs to the technical field of photocatalytic cement-based materials, and particularly relates to efficient multipurpose photocatalytic concrete.
Background
With TiO2Typical photocatalytic materials have an excellent catalytic oxidation function, and have been widely used for environmental purification since birth. The building material represented by cement concrete has large dosage and wide application range, and is an ideal carrier of photocatalytic materials in the field of environmental purification. In recent years, photocatalytic building materials gradually play an important role in the field of environmental purification from the beginning to the end, and the preparation technology of photocatalytic building materials is continuously perfected, but the current photocatalytic building materials still have the following problems, which limit the application of the photocatalytic building materials: high alkalinity environment of cement-based material to TiO2Has a great influence on the catalytic activity of (2); secondly, the cement-based material is compact, has small specific surface area, and has no positive promotion effect on a reaction with adsorption taking a dominant effect; ③ however, directly doping nano TiO into cement2The powder loading method can lead the cement hydration product to wrap the nano particles, and the nano particles are easy to agglomerate and not easy to disperse in the water environment, so that the specific surface area of the photocatalysis effect is reduced, and the photocatalysis efficiency is reduced; fourthly, nano TiO not wrapped by cement hydration products2The binding force with the cement-based material is mainly Van der Waals force, the binding force is poor, the connection is weak, and TiO can appear after being used for many times2The peeling phenomenon reduces the durability thereof.
Disclosure of Invention
The invention aims to provide high-efficiency multipurpose photocatalytic concrete which mainly comprises 5-10 wt% of photocatalytic aggregate, wherein TiO loaded in the photocatalytic aggregate2Has better photocatalysis function; the photocatalytic concrete prepared by doping the photocatalytic aggregate in the concrete effectively reduces the alkaline damage TiO of the cement in the concrete2The catalytic efficiency of (a); the invention can effectively improve the catalysis efficiency and the service life of the photocatalytic building cement;
the invention also aims to provide a preparation method of the high-efficiency multipurpose photocatalytic concrete, and the invention adopts a sol-gel method to prepare TiO2Hydrosol, adopting a negative pressure-saturation method to dip the aggregate, and calcining to prepare photocatalytic aggregate; the preparation method is simple, and can effectively avoid TiO2Agglomeration of the nanoparticles to make TiO2The particles are uniformly dispersed in the aggregate, so that the specific surface area of the photocatalysis is improved, and the photocatalysis efficiency is effectively improved; meanwhile, the invention loads TiO on the aggregate2Then adopting a calcining method to make the TiO2Chemical bond bonding is generated on the surface of the aggregate, so that the bonding force is enhanced, and the durability is improved.
The invention is mainly realized by the following technical scheme: the efficient multipurpose photocatalytic concrete mainly comprises 5-10 wt% of photocatalytic aggregate, wherein photocatalyst TiO is loaded in the photocatalytic aggregate2. Experiments show that the photocatalytic efficiency of the concrete prepared by the invention is increased along with the increase of the photocatalytic aggregate, but when the mass fraction of the photocatalytic aggregate exceeds 10%, the photocatalytic efficiency is obviously increased, mainly because the total exposed amount of the active point sites of the catalyst is increased along with the increase of the mass of the aggregate, but the catalysts are overlapped with each other along with the further increase, and the photocatalytic rate of the concrete is not increased any more.
A preparation method of high-efficiency multipurpose photocatalytic concrete mainly comprises the following steps:
step A, preparing TiO by adopting a sol-gel method2Adding the hydrosol, mixing with the aggregate, calcining to obtain the loaded TiO2Photo catalysisA photocatalytic aggregate of a reagent;
and step B, mixing the photocatalytic aggregate prepared in the step A with cement and gravel to prepare the photocatalytic concrete.
The proportion formula of the cement, the aggregate and the sandstone in the concrete is the prior art and is not the improvement point of the invention, so the detailed description is omitted.
In order to better implement the present invention, further, the step a mainly includes the following steps:
step A1, dropwise adding n-butyl titanate into deionized water while stirring, adding a small amount of nitric acid, and stirring for 24h at 40-60 ℃ water bath temperature after dropwise adding to obtain light blue TiO2Sol;
step A2, adding aggregate to the TiO prepared in step A12Stirring for 45min in sol, ultrasonically dispersing for 1h, standing in a vacuum reaction kettle for 3-5h, and soaking the aggregate in TiO by a negative pressure-saturation method2Dissolving in sol;
and step A3, placing the aggregate obtained by the treatment in the step A2 in an oven at 100 ℃ for drying, then placing in a muffle furnace for calcining at 200-400 ℃ for 1-2h, and cooling to prepare the photocatalytic aggregate.
In order to better implement the present invention, further, in step a1, the ratio of butyl titanate: deionized water: the mass ratio of the nitric acid is 1: 8: 0.08.
in order to better implement the invention, further, the pressure of the vacuum reaction kettle in the step A2 is 0.07-0.15 MPa. The principle of the negative pressure-saturation infiltration method is that a vacuum pump is used for forming a negative pressure atmosphere of 0.07-0.15MPa to ensure that the aggregate and TiO are mixed2The sol is in a negative pressure atmosphere, TiO2The sol is pressed into the nanometer to micron pores of the aggregate under the action of negative pressure. The negative pressure-saturation infiltration method can ensure that nano-to micron-sized pores in the aggregate are fully filled with TiO2Sol impregnation, after calcination, TiO2Combined with the surface of the pores of the aggregate, such a treatment method improves the TiO content2And the loading rate of TiO is increased2The specific surface area of the photocatalyst is increasedAnd (4) chemical reaction active sites.
In order to better implement the invention, the aggregate and TiO in the step A3 are further mixed2The mass ratio of the sol is 1: 0.8 to 1.
In order to better implement the invention, further, the aggregate is any one of natural zeolite, expanded vermiculite, expanded shale, ceramsite, expanded perlite and expanded slag.
Concrete is an indispensable building material, the construction technology of concrete has been developed by air in recent years, and a batch of advanced construction technology is promoted by some advanced concrete materials and technical development. Concrete is used as a structural material and a decorative material in a novel building, research models and products combining nano photocatalyst and cement concrete are started to be carried forward, the development of the photocatalytic self-cleaning concrete has important significance for enriching the functions of the concrete, and simultaneously, the concrete is endowed with the functions of degrading pollutants in the atmosphere and microorganisms on the surface of the building, so that the concrete is one of the key technologies of the novel concrete building.
The progress of concrete building technology enables concrete as a decorative material to be widely applied to some modern buildings, and the development of self-cleaning concrete can improve the decorative effect of the concrete and endow the concrete with an environment purification function. The energy band of the semiconductor catalyst is discontinuous, a forbidden band exists between a low-energy valence band filled with electrons and an empty high-energy valence band, and the semiconductor used as the photocatalyst is mostly metal oxide and sulfide, generally has larger forbidden band width, wherein TiO is2Has the advantages of high photocatalytic activity, good stability, low cost, no harm to human body, etc. and makes TiO possess quantum size effect2The nano material has widened forbidden band, increased redox potential, increased photocatalytic reaction driving force, high specific area, high density of surface lattice defect and high surface area, and raised photocatalytic activity, so that the nano TiO material has nano TiO content2The material is the most ideal photocatalytic material for preparing photocatalytic concrete at present.
TiO2The nano material is an n-type semiconductor material and has a crystal form of 3: sharp knifeThe titanium ore type, rutile type and brookite type. Wherein the anatase form of TiO2Has the best photocatalytic activity and the forbidden band width EgThe photocatalyst is just in an ultraviolet light region with the wavelength of 3.2eV and the wavelength of λ =387nm, and the photocatalytic oxidation reaction of the photocatalyst needs an ultraviolet light source for excitation. The TiO is2The photocatalysis mechanism of the nano material is mature based on the electron-hole action principle of the semiconductor energy band theory, and the principle is the prior art, so the details are not repeated.
The photocatalytic self-cleaning concrete is prepared by introducing nano-grade TiO into concrete surface or internal aggregate by using corresponding addition technology2The concrete has photocatalytic self-cleaning performance and is a novel functional material. The invention adopts a photocatalysis carrier method to load TiO on the surface of partial aggregate in concrete2Nano material, then placing the photocatalytic aggregate on the surface of concrete block to make the coated TiO material2The nano material is partially exposed and can be used for catalyzing and degrading automobile exhaust represented by oxynitride or indoor harmful gas represented by volatile organic compounds and the like.
Butyl titanate of the invention: deionized water: nitric acid is mixed according to the mass ratio of 1: 8: 0.08 reaction to obtain TiO2Sol of TiO2The mass fraction was 2.58 wt%. The invention is realized by changing TiO2Controlling TiO in aggregate according to mass ratio of sol to aggregate2The supported amount of (2) can be obtained by experiments to obtain TiO2When the mass ratio of the sol to the aggregate is 0.8-1: 1, TiO in the aggregate2The loading rate of (2) is 85%, and the catalytic degradation effect is best.
In order to eliminate the influence of alkaline environment, the invention selects aggregate as TiO2The aggregate of the load matrix is mostly natural mineral, has stable self property, occupies most of the volume of cement concrete, and combines the cement hydration environment with TiO2Well separated. In order to enhance the adsorption performance of building materials and promote photocatalytic reaction, minerals with large specific surface area and rich pore channels are selected as aggregates, and the common aggregates comprise porous aggregates such as natural zeolite, expanded vermiculite, expanded shale, ceramsite, expanded perlite, expanded slag and the like.
Conventional twoThe titanium oxide supporting method is to directly dope TiO2Granules, or by mixing powdered TiO2Preparing suspension, soaking and spraying, and features use of nano-TiO2The particles have large specific surface, are easy to agglomerate when meeting water and are difficult to disperse. The invention adopts the tetrabutyl titanate as the titanium source to prepare the TiO by the sol-gel method2The hydrosol is prepared by performing TiO treatment on the surface of the aggregate by adopting a negative pressure-saturated infiltration method2Loading, calcining after loading, and allowing TiO to pass through2And chemical bond bonding is generated between the aggregate and the composite material, so that the bonding force is enhanced, and the durability is improved.
The invention has the beneficial effects that:
(1) the concrete mainly comprises 5-10 wt% of photocatalytic aggregate, and photocatalyst TiO is loaded in the photocatalytic aggregate2The photocatalytic efficiency of the concrete increases with the increase of photocatalytic aggregate;
(2) the invention selects the aggregate as TiO2Direct carrier of (2) cement hydration product with TiO2Separate, greatly reduce the high alkaline environment of cement to TiO2The influence of the catalytic performance of;
(3) the invention selects porous aggregate as a carrier, the aggregate has higher specific surface area and contains a large number of nano-to micron-sized pore channels which are not only TiO2Providing a loading site for TiO2Fully dispersed in nanometer to micron order, greatly increased TiO2The number of active points is large, the aggregate has super strong adsorption performance, the photocatalytic reaction can be positively promoted, and the photocatalytic performance is greatly improved;
(4) the invention adopts a sol-gel method to prepare TiO2And nanometer TiO is treated by a negative pressure-saturation infiltration method2Uniformly dispersed into the pore canal of the aggregate, thereby avoiding the nano TiO2Increase TiO content2Specific surface area of (2), increase of TiO2The number of active point positions improves the photocatalytic efficiency of the concrete;
(5) the invention adopts a calcination method to make TiO2Generates stronger chemical combination with the aggregate and effectively reducesLess TiO2The durability is improved;
(6) the preparation method is simple, low in cost and easy to realize, and has a good market application prospect.
Drawings
FIG. 1 is a schematic structural view of a concrete model with exposed aggregate;
FIG. 2 is a schematic view of the microstructure of a photocatalytic aggregate;
FIG. 3 is a graph showing the acetone degradation efficiency of photocatalytic concrete.
Detailed Description
Example 1:
the efficient multipurpose photocatalytic concrete mainly comprises 1wt% of photocatalytic aggregate, wherein photocatalyst TiO is loaded in the photocatalytic aggregate2。
The preparation method of the high-efficiency multipurpose photocatalytic concrete mainly comprises the following steps:
step A1: selecting natural zeolite with the particle size of 1-2cm, cleaning silt, drying and weighing 500g for later use; weighing 10g of butyl titanate, 80g of deionized water and 0.8g of nitric acid; adding nitric acid into deionized water completely, then adding butyl titanate dropwise at the dropping speed of 2-3 drops/second while stirring, and obtaining milky suspension after the dropwise addition; placing the milky white suspension into a water bath at 50 ℃ to be stirred and reacted for 24 hours, and finally obtaining light blue TiO2Sol;
step A2: 500g of natural zeolite was poured into TiO2Stirring the sol for 45 minutes, then dispersing the sol for 1 hour in ultrasonic, standing the sol and placing the sol in a vacuum reaction kettle, wherein the pressure of the vacuum reaction kettle is 0.07MPa, and placing the sol for 4 hours;
step A3: taking out the soaked aggregate from the vacuum reaction kettle, placing the aggregate in an oven for drying at 100 ℃, then placing the aggregate in a muffle furnace for calcining at 200 ℃ for 2 hours, and cooling to obtain the photocatalytic aggregate;
and B: and uniformly mixing the photocatalytic aggregate with cement and sandstone to prepare the concrete.
The invention adopts a method provided by a novel gas-phase photocatalysis quantitative detection device under the multi-parameter control with the patent number of CN206192955U, and tests the photodegradation rate of the acetone.
As shown in figure 1, the invention adopts a photocatalytic carrier method to load TiO on the surface of partial aggregate in concrete2The nano material, the photocatalytic aggregate is coated on the surface of the concrete block, so that the surface is coated with TiO2The nano material is partially exposed and can be used for catalyzing and degrading tail gas discharged by automobiles or harmful gases such as formaldehyde gas in buildings and the like.
As shown in FIG. 2, the TiO2Nano particles are uniformly distributed in the aggregate, and the TiO2Stacking holes are formed among the nano particles; as shown in fig. 3, acetone is gradually degraded with the increase of the catalytic time, and does not change after the catalytic degradation reaches a certain amount; the photocatalytic aggregate effectively enhances the photocatalytic efficiency of concrete.
The photocatalytic concrete prepared by doping the photocatalytic aggregate in the concrete effectively reduces the alkaline damage TiO of the cement in the concrete2The catalytic efficiency of (a); the invention can effectively improve the catalysis efficiency and the service life of the photocatalytic building cement; the invention adopts a sol-gel method to prepare TiO2Hydrosol, adopting a negative pressure-saturation method to dip the aggregate, and calcining to prepare photocatalytic aggregate; the preparation method is simple, and can effectively avoid TiO2Agglomeration of the nanoparticles to make TiO2The particles are uniformly dispersed in the aggregate, so that the specific surface area of the photocatalysis is improved, and the photocatalysis efficiency is effectively improved; meanwhile, the invention loads TiO on the aggregate2Then adopting a calcining method to make the TiO2Chemical bond bonding is generated on the surface of the aggregate, so that the bonding force is enhanced, and the durability is improved.
Example 2:
the efficient multipurpose photocatalytic concrete mainly comprises 5wt% of photocatalytic aggregate, wherein photocatalyst TiO is loaded in the photocatalytic aggregate2。
The preparation method of the high-efficiency multipurpose photocatalytic concrete mainly comprises the following steps:
step A1: selecting particle diameter of 1-2cmCleaning silt, drying and weighing 500g of the natural zeolite for later use; weighing 10g of butyl titanate, 80g of deionized water and 0.8g of nitric acid; adding nitric acid into deionized water completely, then adding butyl titanate dropwise at the dropping speed of 2-3 drops/second while stirring, and obtaining milky suspension after the dropwise addition; placing the milky white suspension into a water bath at 50 ℃ to be stirred and reacted for 24 hours, and finally obtaining light blue TiO2Sol;
step A2: 500g of natural zeolite was poured into TiO2Stirring the sol for 45 minutes, then dispersing the sol for 1 hour in ultrasonic, standing the sol and placing the sol in a vacuum reaction kettle, wherein the pressure of the vacuum reaction kettle is 0.07MPa, and placing the sol for 4 hours;
step A3: taking out the soaked aggregate from the vacuum reaction kettle, placing the aggregate in an oven for drying at 100 ℃, then placing the aggregate in a muffle furnace for calcining at 200 ℃ for 2 hours, and cooling to obtain the photocatalytic aggregate;
and B: and uniformly mixing the photocatalytic aggregate with cement and sandstone to prepare the concrete.
The invention adopts a method provided by a novel gas-phase photocatalysis quantitative detection device under the multi-parameter control with the patent number of CN206192955U, and tests the photodegradation rate of the acetone.
As shown in figure 1, the invention adopts a photocatalytic carrier method to load TiO on the surface of partial aggregate in concrete2The nano material, the photocatalytic aggregate is coated on the surface of the concrete block, so that the surface is coated with TiO2The nano material is partially exposed and can be used for catalyzing and degrading tail gas discharged by automobiles or harmful gases such as formaldehyde gas in buildings and the like.
As shown in FIG. 2, the TiO2Nano particles are uniformly distributed in the aggregate, and the TiO2Stacking holes are formed among the nano particles; as shown in fig. 3, acetone is gradually degraded with the increase of the catalytic time, and does not change after the catalytic degradation reaches a certain amount; the photocatalytic aggregate effectively enhances the photocatalytic efficiency of concrete; compared with example 1, the concrete prepared by the embodiment and containing 5wt% of photocatalytic aggregate has relatively higher acetone catalysis efficiencyBecause the surface of the aggregate is loaded with TiO2The mass of the nanoparticles increases, the catalytic efficiency of the concrete increases with TiO2The increase in nanoparticles.
The photocatalytic concrete prepared by doping the photocatalytic aggregate in the concrete effectively reduces the alkaline damage TiO of the cement in the concrete2The catalytic efficiency of (a); the invention can effectively improve the catalysis efficiency and the service life of the photocatalytic building cement; the invention adopts a sol-gel method to prepare TiO2Hydrosol, adopting a negative pressure-saturation method to dip the aggregate, and calcining to prepare photocatalytic aggregate; the preparation method is simple, and can effectively avoid TiO2Agglomeration of the nanoparticles to make TiO2The particles are uniformly dispersed in the aggregate, so that the specific surface area of the photocatalysis is improved, and the photocatalysis efficiency is effectively improved; meanwhile, the invention loads TiO on the aggregate2Then adopting a calcining method to make the TiO2Chemical bond bonding is generated on the surface of the aggregate, so that the bonding force is enhanced, and the durability is improved.
Example 3:
the efficient multipurpose photocatalytic concrete mainly comprises 10wt% of photocatalytic aggregate, wherein photocatalyst TiO is loaded in the photocatalytic aggregate2。
The preparation method of the high-efficiency multipurpose photocatalytic concrete mainly comprises the following steps:
step A1: selecting natural zeolite with the particle size of 1-2cm, cleaning silt, drying and weighing 500g for later use; weighing 10g of butyl titanate, 80g of deionized water and 0.8g of nitric acid; adding nitric acid into deionized water completely, then adding butyl titanate dropwise at the dropping speed of 2-3 drops/second while stirring, and obtaining milky suspension after the dropwise addition; placing the milky white suspension into a water bath at 50 ℃ to be stirred and reacted for 24 hours, and finally obtaining light blue TiO2Sol;
step A2: 500g of natural zeolite was poured into TiO2Stirring the sol for 45 minutes, then dispersing the sol for 1 hour in ultrasonic, standing the sol and placing the sol in a vacuum reaction kettle, wherein the pressure of the vacuum reaction kettle is 0.07MPa, and placing the sol for 4 hours;
step A3: taking out the soaked aggregate from the vacuum reaction kettle, placing the aggregate in an oven for drying at 100 ℃, then placing the aggregate in a muffle furnace for calcining at 200 ℃ for 2 hours, and cooling to obtain the photocatalytic aggregate;
and B: and uniformly mixing the photocatalytic aggregate with cement and sandstone to prepare the concrete.
The invention adopts a method provided by a novel gas-phase photocatalysis quantitative detection device under the multi-parameter control with the patent number of CN206192955U, and tests the photodegradation rate of the acetone.
As shown in figure 1, the invention adopts a photocatalytic carrier method to load TiO on the surface of partial aggregate in concrete2The nano material, the photocatalytic aggregate is coated on the surface of the concrete block, so that the surface is coated with TiO2The nano material is partially exposed and can be used for catalyzing and degrading tail gas discharged by automobiles or harmful gases such as formaldehyde gas in buildings and the like.
As shown in FIG. 2, the TiO2Nano particles are uniformly distributed in the aggregate, and the TiO2Stacking holes are formed among the nano particles; as shown in fig. 3, acetone is gradually degraded with the increase of the catalytic time, and does not change after the catalytic degradation reaches a certain amount; the photocatalytic aggregate effectively enhances the photocatalytic efficiency of concrete; compared with the concrete prepared in the example 1 and the concrete prepared in the example 2, the concrete containing 10wt% of photocatalytic aggregate has relatively higher efficiency of catalyzing acetone, and the efficiency is mainly because the surface of the aggregate is loaded with TiO2The mass of the nanoparticles increases, the catalytic efficiency of the concrete increases with TiO2Increase in nanoparticles; however, the concrete containing 10wt% photocatalytic aggregate has a reduced rate of efficiency in catalyzing acetone, mainly because of the increased efficiency with TiO in the aggregate2The increase of the nano-particles forms TiO in the aggregate2The nano particles are stacked, and the photocatalytic increase rate is effectively reduced.
The photocatalytic concrete prepared by doping the photocatalytic aggregate in the concrete effectively reduces the alkaline damage TiO of the cement in the concrete2The catalytic efficiency of (a); the invention can effectively improve the photocatalytic building cementCatalytic efficiency and service life of; the invention adopts a sol-gel method to prepare TiO2Hydrosol, adopting a negative pressure-saturation method to dip the aggregate, and calcining to prepare photocatalytic aggregate; the preparation method is simple, and can effectively avoid TiO2Agglomeration of the nanoparticles to make TiO2The particles are uniformly dispersed in the aggregate, so that the specific surface area of the photocatalysis is improved, and the photocatalysis efficiency is effectively improved; meanwhile, the invention loads TiO on the aggregate2Then adopting a calcining method to make the TiO2Chemical bond bonding is generated on the surface of the aggregate, so that the bonding force is enhanced, and the durability is improved.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (3)
1. The efficient multipurpose photocatalytic concrete is characterized by mainly comprising 10wt% of photocatalytic aggregate, wherein photocatalyst TiO is loaded in the photocatalytic aggregate2Selecting porous aggregate as a carrier; by using TiO2TiO with mass fraction of 2.58wt%2Preparing the sol and the porous aggregate according to the mass ratio of 1:1 to obtain a photocatalytic aggregate;
the preparation of the catalytic concrete mainly comprises the following steps:
step A, preparing TiO by adopting a sol-gel method2Hydrosol, then adding porous aggregate to mix, calcining and preparing to obtain the load TiO2A photocatalytic aggregate of a photocatalyst;
step B, mixing the photocatalytic aggregate prepared in the step A with cement and gravel to prepare photocatalytic concrete;
the step A mainly comprises the following steps:
step A1, dropwise adding n-butyl titanate into deionized water while stirring, adding a small amount of nitric acid, and stirring for 24h at 40-60 ℃ water bath temperature after dropwise adding to obtain light blue TiO2Sol;
step A2, adding porous aggregate to the TiO prepared in step A12Stirring for 45min in sol, ultrasonically dispersing for 1h, standing in a vacuum reaction kettle for 3-5h, and soaking porous aggregate in TiO by negative pressure-saturation method2Dissolving in sol;
step A3, placing the porous aggregate obtained by treatment in the step A2 in an oven at 100 ℃ for drying, then placing in a muffle furnace for calcining at 200-400 ℃ for 1-2h, and cooling to prepare the photocatalytic aggregate;
in the step A3, porous aggregate and TiO are added2The mass ratio of the sol is 1: 1;
butyl orthotitanate in said step a 1: deionized water: the mass ratio of the nitric acid is 1: 8: 0.08.
2. the efficient multipurpose photocatalytic concrete according to claim 1, wherein the pressure of the vacuum reaction kettle in the step A2 is 0.07-0.15 MPa.
3. The efficient multipurpose photocatalytic concrete according to claim 1 or 2, wherein the porous aggregate is any one of natural zeolite, expanded vermiculite, expanded shale, ceramsite, expanded perlite and expanded slag.
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| CN112705185A (en) * | 2020-12-29 | 2021-04-27 | 四川建筑职业技术学院 | Preparation method of quartz sand/titanium dioxide composite catalyst |
| CN112960946A (en) * | 2021-02-05 | 2021-06-15 | 广东至道先进土木工程材料技术研究有限公司 | Self-luminous efficient photocatalytic concrete and preparation method thereof |
| CN114380556B (en) * | 2022-01-26 | 2022-10-25 | 同济大学 | Concrete preparation and used aggregate treatment method considering future convenience for cyclic regeneration |
| CN114804914A (en) * | 2022-05-18 | 2022-07-29 | 广州大学 | Preparation method of efficient, green and low-cost composite photocatalyst |
| CN114907042B (en) * | 2022-05-26 | 2023-04-04 | 福建工程学院 | Photocatalytic steel slag floating concrete and preparation method thereof |
| CN115838269A (en) * | 2022-12-16 | 2023-03-24 | 东南大学 | Modified cement mortar and preparation method and application thereof |
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