CN112960946A - Self-luminous efficient photocatalytic concrete and preparation method thereof - Google Patents
Self-luminous efficient photocatalytic concrete and preparation method thereof Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 76
- 239000004567 concrete Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 239000004568 cement Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- 239000004575 stone Substances 0.000 claims description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 14
- 239000011651 chromium Substances 0.000 claims description 14
- 229910001650 dmitryivanovite Inorganic materials 0.000 claims description 14
- 229910001707 krotite Inorganic materials 0.000 claims description 14
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 12
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000004576 sand Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000011398 Portland cement Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 21
- 239000011941 photocatalyst Substances 0.000 abstract description 20
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 30
- 238000012360 testing method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000005084 Strontium aluminate Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
- 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
-
- 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
- C04B2111/00008—Obtaining or using nanotechnology related 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
- C04B2111/80—Optical properties, e.g. transparency or reflexibility
- C04B2111/807—Luminescent or fluorescent materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses self-luminous high-efficiency photocatalytic concrete and a preparation method thereof, wherein the self-luminous high-efficiency photocatalytic concrete comprises the following raw materials in parts by weight: 19-21 parts of cement, 25-28 parts of water, 190-200 parts of coarse aggregate, 2-3 parts of water reducing agent, 2-3 parts of chromium-doped nano titanium dioxide, and CaAl2O 4: 4-5 parts of Eu2+ and Nd3+ photoinduced self-luminous material. According to the technical scheme, the photo-induced self-luminous material and the photocatalyst are jointly used, so that the photocatalytic concrete can play a catalytic degradation role under the dark condition at night. Further provides a preparation method of the self-luminous high-efficiency photocatalytic concrete, which has simple steps and strong operability and overcomes the defects in the prior art.
Description
Technical Field
The invention relates to the technical field of photocatalytic concrete, in particular to self-luminous efficient photocatalytic concrete and a preparation method thereof.
Background
In recent years, urban air pollution in China is serious, but the treatment difficulty is high due to the fact that harmful gas emission sources are numerous, constituent components of the emitted gas are complex, and gas emission amount is large. Although concrete materials have been used for hundreds of years in construction, with the development of society, the traditional concrete has been increasingly difficult to meet the requirements of people on resources, environment, construction and performance. The concrete made of the novel material is developed rapidly due to a large amount of experiments and researches, wherein the photocatalytic concrete has the characteristics of energy conservation and environmental protection, also has the function of degrading pollutants, is an important research direction in the field of environmental protection, and has wide prospects in the aspects of treating atmospheric pollutants and indoor formaldehyde.
At present, the photocatalytic concrete in the prior art can exert the photocatalytic effect only under the light condition, the photocatalytic reaction can not be carried out under the dark condition at night, and the concentration of nitrogen oxides in the atmosphere is increased at night due to the passing of a large number of heavy vehicles, which is the time period most needing the catalyst to exert the efficacy.
Disclosure of Invention
The invention aims to provide self-luminous efficient photocatalytic concrete, and the self-luminous material and a photocatalyst are jointly used, so that the photocatalytic concrete can play a role in catalytic degradation under the dark condition at night, and the defects of the prior art are overcome.
The invention also aims to provide a preparation method of the self-luminous high-efficiency photocatalytic concrete, which has simple steps and strong operability and overcomes the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
self-luminous efficient photocatalytic concrete, which comprises the following components in parts by massThe preparation method comprises the following steps: 19-21 parts of cement, 25-28 parts of water, 190-200 parts of coarse aggregate, 2-3 parts of water reducing agent, 2-3 parts of chromium-doped nano titanium dioxide and CaAl2O4：Eu2 +，Nd3+4-5 parts of a light-induced self-luminous material.
Preferably, the chromium doping amount of the chromium-doped nano titanium dioxide is 1-2% by mass.
Preferably, the fineness of the chromium-doped nano titanium dioxide is 5-10 nm.
Preferably, the CaAl2O4：Eu2+，Nd3+The mesh number of the light-induced self-luminous material is 200-300 meshes.
Preferably, the cement is 42.5-grade portland cement, and the water reducing agent is a polycarboxylic acid water reducing agent.
Preferably, the feed comprises the following raw materials in parts by weight: 19-21 parts of cement, 25-28 parts of water, 95-100 parts of sand, 95-100 parts of stone, 2-3 parts of water reducing agent, 2-3 parts of chromium-doped nano titanium dioxide and CaAl2O4：Eu2+，Nd3+4-5 parts of a light-induced self-luminous material.
Preferably, the fineness of the stone is 5-25 mm, and the crushing value of the stone is less than 15.
A preparation method of self-luminous high-efficiency photocatalytic concrete is used for preparing the self-luminous high-efficiency photocatalytic concrete and comprises the following steps:
A. preparing chromium-doped nano titanium dioxide;
B. mixing chromium with nano titanium dioxide, cement and CaAl according to a certain proportion2O4：Eu2+，Nd3+Adding the photoinduced self-luminous material into a stirrer for primary stirring;
C. uniformly mixing water and a water reducing agent according to a ratio, and adding the mixture into a stirrer for secondary stirring;
D. and adding the coarse aggregate into a stirrer according to the proportion, and stirring for three times to obtain the self-luminous efficient photocatalytic concrete.
Preferably, step a specifically comprises the following steps:
a1, weighing 1-2 parts of analytically pure chromium chloride, putting the analytically pure chromium chloride into a three-neck flask filled with 98-102 parts of analytically pure absolute ethanol solution, slowly adding 105-110 parts of titanium tetrachloride solution into the three-neck flask to obtain a mixture, and keeping magnetic stirring in the whole process;
a2, placing the mixture into a high-pressure hydrothermal reaction kettle;
and A3, centrifuging, washing and drying the reacted mixture, and grinding to obtain the chromium-doped nano titanium dioxide.
Preferably, in the step A2, the reaction temperature of the high-pressure hydrothermal reaction kettle is 500-550 ℃, and the reaction time is 2-24 hours.
The invention has the beneficial effects that:
1. according to the technical scheme, the photo-induced self-luminous material and the photocatalyst chromium-doped nano titanium dioxide are jointly used, the photo-induced self-luminous material absorbs light energy under the condition of sunshine in the daytime and emits light at night to release the light energy, so that the photo-catalytic concrete can catalyze nitrogen oxides in the atmosphere under the condition of no light at night, and the photo-catalytic concrete can better exert the photo-catalytic effect.
2. The technical scheme modifies the nano titanium dioxide into chromium-doped nano titanium dioxide. According to the technical scheme, the chromium-doped nano titanium dioxide is used as the photocatalyst, so that the absorption spectrum of the photocatalyst can be enlarged to 600nm, the photocatalyst has very high photocatalytic efficiency under the illumination of 400-500 nm, and the catalytic efficiency of the photocatalyst under visible light is improved.
Detailed Description
At present, the photocatalytic concrete in the prior art can exert the photocatalytic effect only under the light condition, the photocatalytic reaction can not be carried out under the dark condition at night, and the concentration of nitrogen oxides in the atmosphere is increased at night due to the passing of a large number of heavy vehicles, which is the time period most needing the catalyst to exert the efficacy.
In order to enable the photocatalytic concrete to play a role in catalytic degradation at night, the technical scheme provides the self-luminous efficient photocatalytic concrete which comprises the following raw materials in parts by weight: 19-21 parts of cement, 25-28 parts of water, 190-200 parts of coarse aggregate, 2-3 parts of water reducing agent, 2-3 parts of chromium-doped nano titanium dioxide, and CaAl2O 4: 4-5 parts of Eu2+ and Nd3+ photoinduced self-luminous material. According to the technical scheme, the photo-induced self-luminous material and the photocatalyst chromium-doped nano titanium dioxide are jointly used, the photo-induced self-luminous material absorbs light energy under the condition of sunshine in the daytime and emits light at night to release the light energy, so that the photo-catalytic concrete can catalyze nitrogen oxides in the atmosphere under the condition of no light at night, and the photo-catalytic concrete can better exert the photo-catalytic effect.
In particular, there are many types of photo-luminescent materials, such as CaAl2O4：Eu2+，Nd3+、Sr4Al14O25：Eu2+，Dy3+And SrAl2O4：Eu2+，Dy3+Etc. in the technical scheme, CaAl is selected2O4：Eu2+，Nd3+As a light-induced self-luminescent material, this is due to CaAl2O4：Eu2+，Nd3+The light-induced self-luminous material has a light-emitting spectrum of 400-500 nm and a peak value of 440nm, and is the long-afterglow self-luminous material closest to ultraviolet light. If Sr is selected4Al14O25：Eu2+Or Dy3+And SrAl2O4：Eu2+，Dy3+As a luminescent material, NO is greatly reduced2 ofRemoval rate, and selecting Sr4Al14O25：Eu2+Or Dy3+And SrAl2O4：Eu2+，Dy3+As a luminescent material, the light-emitting material mainly emits visible light and rarely emits ultraviolet light, and because the absorption spectrum of the nano titanium dioxide used as a photocatalyst is less than 387nm, if Sr is selected4Al14O25：Eu2+Or Dy3+And SrAl2O4：Eu2+，Dy3+As a luminescent material, the absorption rate of nano titanium dioxide is easily reduced, and the catalytic efficiency is easily reduced.
In the prior art, nano titanium dioxide is generally used as a photocatalyst, and the titanium dioxide has the advantages of high catalytic activity, high chemical inertness, no toxicity, low price and the like, and has a very good application prospect. However, the forbidden band width of the nano titanium dioxide is relatively large, and the nano titanium dioxide can only be activated by ultraviolet rays with the wavelength of 387nm or less, so that the catalytic efficiency under visible light is low. Because ultraviolet light only accounts for 5% of the solar spectrum, the energy utilization rate is low, and photoproduction electrons and holes are easy to recombine, so that the catalytic efficiency of light is reduced.
In order to improve the photocatalytic efficiency of the photocatalyst, the technical scheme modifies the nano titanium dioxide into chromium-doped nano titanium dioxide. According to the technical scheme, the chromium-doped nano titanium dioxide is used as the photocatalyst, so that the absorption spectrum of the photocatalyst can be enlarged to 600nm, the photocatalyst has very high photocatalytic efficiency under the illumination of 400-500 nm, and the catalytic efficiency of the photocatalyst under visible light is improved. Further, in order to improve the photocatalytic efficiency of the photocatalyst, in the prior art, nitrogen-doped nano titanium dioxide is used as the photocatalyst, but under the irradiation of ultraviolet light (λ <380nm), chromium-doped nano titanium dioxide shows the same photocatalytic activity as pure nano titanium dioxide, but the photocatalytic efficiency of nitrogen-doped nano titanium dioxide is greatly reduced. The chromium-doped nano titanium dioxide has high catalytic efficiency under visible light and ultraviolet light, and although the nitrogen-doped nano titanium dioxide improves the catalytic efficiency under the visible light, the catalytic efficiency under the ultraviolet light is low. In the daytime, a large amount of ultraviolet rays exist in sunlight, and nitrogen-doped nano titanium dioxide cannot play a good role in photocatalysis, so that the technical scheme uses the chromium-doped nano titanium dioxide, so that the photocatalyst has higher photocatalysis efficiency.
More specifically, the technical scheme also limits the proportion of the high-efficiency photocatalytic concrete. The cement, the water and the water reducing agent are matched with each other, so that the workability and the workability of the concrete can be optimal. If the addition amount of cement, water or a water reducing agent is too small, poor workability of concrete is easily caused, cavities are easily formed due to uneven vibration in construction, the durability is poor, and the catalytic effect is not durable; if the amount of cement, water or water reducing agent added is too large, the wrapping property of the concrete is poor, the aggregate and the slurry are likely to be separated, the durability is poor, and the catalytic effect is not durable.
Chromium-doped nano titanium dioxide and CaAl2O4：Eu2+，Nd3+The light-induced self-luminous materials are matched with each other, so that the catalysis efficiency of the concrete can reach the highest. If the amount of chromium-doped nano titanium dioxide is reduced, the photocatalytic efficiency is reduced due to the reduction of photocatalytic media; if the amount of the chromium-doped nano titanium dioxide is increased, the chromium-doped nano titanium dioxide covers the surface of the concrete, so that the chromium-doped nano titanium dioxide covering the inside of the concrete cannot play a role easily. If the luminescent material is reduced, the luminescent effect is poor at night, and the catalytic efficiency is also reduced; if the luminescent materials are increased, the luminescent intensity at night exceeds the brightness required by exciting the chromium-doped nano titanium dioxide, and the waste of the luminescent materials is caused.
Further, according to the mass percentage, the chromium doping amount of the chromium-doped nano titanium dioxide is 1-2%.
In one embodiment of the technical scheme, the chromium doping amount of the chromium-doped nano titanium dioxide is 1-2% by mass, because the chromium doping amount has an influence on the catalytic efficiency, within a range of 1-2%, the higher the doping amount is, the higher the catalytic efficiency is, but when the chromium doping amount exceeds 2%, the catalytic efficiency of the photocatalyst is not improved by increasing the content of chromium, and the raw material waste is caused.
Furthermore, the fineness of the chromium-doped nano titanium dioxide is 5-10 nm.
In one embodiment of the technical scheme, the fineness of the chromium-doped nano titanium dioxide is limited to 5-10 nm. The reason is that the nano titanium dioxide with small particle size has obvious quantum size effect and high catalytic efficiency. If the size of the nano titanium dioxide is increased, the catalytic efficiency is reduced, and the nano titanium dioxide with the size of more than 100nm basically has no catalytic effect.
In further detail, the CaAl2O4：Eu2+，Nd3+Of photo-luminescent materialsThe mesh number is 200-300 meshes.
In one embodiment of the present disclosure, CaAl is used2O4：Eu2+，Nd3+The mesh number of the light-induced self-luminous material is limited to 200-300 meshes. If the particle size of the luminescent material is smaller than 200 meshes, the luminescent material which cannot be irradiated by sunlight exists in the solid interior of the luminescent material, and the luminescent material cannot be excited to emit light, so that the luminous efficiency is low; if the particle size of the luminescent material is larger than 300 meshes, the luminescent material has too fine particle size, is easy to agglomerate and is not easy to separate, and luminescent materials which cannot be irradiated by sunlight also exist in the agglomeration, so that the luminescent efficiency is low.
Further, the cement is 42.5-grade portland cement, and the water reducing agent is a polycarboxylic acid water reducing agent.
Further, the feed comprises the following raw materials in parts by weight: 19-21 parts of cement, 25-28 parts of water, 95-100 parts of sand, 95-100 parts of stone, 2-3 parts of water reducing agent, 2-3 parts of chromium-doped nano titanium dioxide and CaAl2O4：Eu2+，Nd3+4-5 parts of a light-induced self-luminous material.
According to the technical scheme, sand and stone are selected as coarse aggregates in the photocatalytic concrete, and the proportion of the sand and the stone is further limited.
Further, the fineness of the stone is 5-25 mm, and the crushing value of the stone is less than 15.
The technical scheme provides a preparation method of self-luminous efficient photocatalytic concrete, which is used for preparing the self-luminous efficient photocatalytic concrete and comprises the following steps:
A. preparing chromium-doped nano titanium dioxide;
B. mixing chromium with nano titanium dioxide, cement and CaAl according to a certain proportion2O4：Eu2+，Nd3+Photoinduced selfAdding the luminescent material into a stirrer for primary stirring;
C. uniformly mixing water and a water reducing agent according to a ratio, and adding the mixture into a stirrer for secondary stirring;
D. and adding the coarse aggregate into a stirrer according to the proportion, and stirring for three times to obtain the self-luminous efficient photocatalytic concrete.
The technical scheme also provides a preparation method of the self-luminous efficient photocatalytic concrete, the chromium-doped nano titanium dioxide is prepared, the photocatalytic concrete raw materials are stirred to prepare the self-luminous efficient photocatalytic concrete, and the steps are simple and the operability is high.
Further, step a specifically includes the following steps:
a1, weighing 1-2 parts of analytically pure chromium chloride, putting the analytically pure chromium chloride into a three-neck flask filled with 98-102 parts of analytically pure absolute ethanol solution, slowly adding 105-110 parts of titanium tetrachloride solution into the three-neck flask to obtain a mixture, and keeping magnetic stirring in the whole process;
a2, placing the mixture into a high-pressure hydrothermal reaction kettle;
and A3, centrifuging, washing and drying the reacted mixture, and grinding to obtain the chromium-doped nano titanium dioxide.
The existing modified nano titanium dioxide is nitrogen-doped nano titanium dioxide, but the visible light photocatalytic efficiency of the catalyst obtained by some doping processes in the prior art is not ideal, and some doping processes can deteriorate certain performances of the catalyst to a certain extent, for example, the subsequent heat treatment of titanium dioxide in ammonia gas inevitably causes the growth of crystal grains and the improvement of specific surface area, and simultaneously, the production cost is also improved. In order to ensure that the photocatalytic efficiency of the modified nano titanium dioxide is improved, the technical scheme also discloses a preparation process of the chromium-doped nano titanium dioxide, which is beneficial to effectively improving the photocatalytic efficiency of the modified nano titanium dioxide and reducing the production cost.
In step A2, the reaction temperature of the high-pressure hydrothermal reaction kettle is 500-550 ℃ and the reaction time is 2-24 hours.
The technical solution of the present invention is further explained by the following embodiments.
Example 1-preparation of self-luminous high-efficiency photocatalytic concrete
A1, weighing 1 part of analytically pure chromium chloride, putting the analytically pure chromium chloride into a three-neck flask filled with 100 parts of analytically pure absolute ethanol solution, slowly adding 105 parts of titanium tetrachloride solution into the three-neck flask to obtain a mixture, and keeping magnetic stirring in the whole process;
a2, stirring at room temperature for 10min, putting the mixture into a high-pressure hydrothermal reaction kettle, and reacting at 500-550 ℃ for 24 h;
a3, centrifuging, washing and drying the reacted mixture, and then grinding to obtain chromium-doped nano titanium dioxide with the fineness of 10nm and the chromium doping amount of 2%;
B. 2 parts of chromium-doped nano titanium dioxide, 20 parts of 42.5-grade portland cement and 4 parts of CaAl2O4：Eu2+，Nd3+Adding the photoinduced self-luminous material into a stirrer for primary stirring;
C. uniformly mixing 25 parts of water and 3 parts of polycarboxylic acid water reducing agent, and adding the mixture into a stirrer for secondary stirring;
D. and adding 95 parts of sand and 100 parts of stone with the fineness of 25mm and the crushing value of 12 into a stirrer for stirring for three times to obtain the self-luminous efficient photocatalytic concrete.
Example 2-preparation of self-luminous high-efficiency photocatalytic concrete
A1, weighing 2 parts of analytically pure chromium chloride, putting the analytically pure chromium chloride into a three-neck flask filled with 100 parts of analytically pure absolute ethanol solution, slowly adding 105 parts of titanium tetrachloride solution into the three-neck flask to obtain a mixture, and keeping magnetic stirring in the whole process;
a2, stirring at room temperature for 10min, putting the mixture into a high-pressure hydrothermal reaction kettle, and reacting at 500-550 ℃ for 24 h;
a3, centrifuging, washing and drying the reacted mixture, and then grinding to obtain chromium-doped nano titanium dioxide with the fineness of 10nm and the chromium doping amount of 2%;
B. 2 parts of chromium is doped with sodiumRice titanium dioxide, 20 parts of 42.5-grade portland cement and 4 parts of CaAl2O4：Eu2+，Nd3+Adding the photoinduced self-luminous material into a stirrer for primary stirring;
C. uniformly mixing 25 parts of water and 3 parts of polycarboxylic acid water reducing agent, and adding the mixture into a stirrer for secondary stirring;
D. and adding 95 parts of sand and 100 parts of stone with the fineness of 25mm and the crushing value of 12 into a stirrer for stirring for three times to obtain the self-luminous efficient photocatalytic concrete.
Example 3-preparation of self-luminous high-efficiency photocatalytic concrete
A1, weighing 2 parts of analytically pure chromium chloride, putting the analytically pure chromium chloride into a three-neck flask filled with 100 parts of analytically pure absolute ethanol solution, slowly adding 105 parts of titanium tetrachloride solution into the three-neck flask to obtain a mixture, and keeping magnetic stirring in the whole process;
a2, stirring at room temperature for 10min, putting the mixture into a high-pressure hydrothermal reaction kettle, and reacting at 500-550 ℃ for 24 h;
a3, centrifuging, washing and drying the reacted mixture, and then grinding to obtain chromium-doped nano titanium dioxide with the fineness of 10nm and the chromium doping amount of 2%;
B. 3 parts of chromium-doped nano titanium dioxide, 21 parts of 42.5-grade portland cement and 5 parts of CaAl2O4：Eu2+，Nd3+Adding the photoinduced self-luminous material into a stirrer for primary stirring;
C. uniformly mixing 28 parts of water and 2 parts of polycarboxylic acid water reducing agent, and adding the mixture into a stirrer for secondary stirring;
D. and adding 100 parts of sand and 95 parts of stone with the fineness of 20mm and the crushing value of 10 into a stirrer for stirring for three times to obtain the self-luminous efficient photocatalytic concrete.
Comparative example 1 preparation of photocatalytic concrete
1. Adding 2 parts of pure nano titanium dioxide and 20 parts of 42.5-grade portland cement into a stirrer for primary stirring;
2. uniformly mixing 25 parts of water and 3 parts of polycarboxylic acid water reducing agent, and adding the mixture into a stirrer for secondary stirring;
3. and adding 95 parts of sand and 100 parts of stone with the fineness of 25mm and the crushing value of 12 into a stirrer for stirring for three times to obtain the photocatalytic concrete.
Experimental NO2Concentration reduction test
1. Pouring the photocatalytic concrete obtained in the examples 1-3 and the comparative example 1 into a plastic steel mould with the thickness of 100mm x 100mm, inserting and tamping for 25 hours, demoulding after 18 hours, and putting the photocatalytic concrete into a standard curing room for curing for 7 days to obtain a photocatalytic concrete test block;
2. placing a test block into a nitrogen oxide reactor, wherein the reactor is a sealed transparent box, the size of the reactor is 700mm long, 400mm wide and 130mm high, an opening of the transparent box is sealed by organic glass cement, and the test block is placed on a fixer in the center of the reactor;
3. zero-order air and standard nitrogen dioxide gas are mixed to form NO with the concentration of 3000ppb2The test gas flow is introduced into the nitrogen oxide reactor at a speed of 3L/min, the relative humidity in the reactor is controlled within the range of 45-55%, and the test gas is introduced into the reactor for 30min to ensure that NO is generated2The gas concentration reaches an equilibrium state;
4. the whole test instrument is moved out of the laboratory and placed in the open air, the test is started at 8 am, and the NO in the reactor is measured by a chemiluminescence analyzer (provided by Saimer fly instruments, USA) after 24h2The results are shown in Table 1 below.
TABLE 1 Nitrogen oxide in-reactor NO2Concentration of
As can be seen from the comparative results of the performance tests in Table 1, NO in the nitrogen oxide reactor is generated within 24 hours after the photocatalytic concrete prepared in examples 1-3 of the present embodiment is used2The concentration can be reduced to below 30ppbNO in nitrogen oxide reactor within 24h after using photocatalytic concrete in prior art2The concentration can only be reduced to 350 ppb. Therefore, the self-luminous efficient photocatalytic concrete in the technical scheme has the advantages that the photoinduced self-luminous material and the photocatalyst are combined for use, the photoinduced self-luminous material absorbs light energy under the condition of sunshine in the daytime and emits light at night to release the light energy, so that the photocatalytic concrete can catalyze nitrogen oxides in the atmosphere under the condition of NO light at night, and NO in the environment can be effectively reduced2And (4) concentration.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (10)
1. The self-luminous efficient photocatalytic concrete is characterized by comprising the following raw materials in parts by weight: 19-21 parts of cement, 25-28 parts of water, 190-200 parts of coarse aggregate, 2-3 parts of water reducing agent, 2-3 parts of chromium-doped nano titanium dioxide and CaAl2O4：Eu2+，Nd3+4-5 parts of a light-induced self-luminous material.
2. The self-luminous high-efficiency photocatalytic concrete according to claim 1, characterized in that: according to the mass percentage, the chromium doping amount of the chromium-doped nano titanium dioxide is 1-2%.
3. The self-luminous high-efficiency photocatalytic concrete according to claim 2, characterized in that: the fineness of the chromium-doped nano titanium dioxide is 5-10 nm.
4. The self-luminous high-efficiency photocatalytic concrete according to claim 1, characterized in that: the CaAl2O4：Eu2+，Nd3+The mesh number of the light-induced self-luminous material is 200-300 meshes.
5. The self-luminous high-efficiency photocatalytic concrete according to claim 1, characterized in that: the cement is 42.5-grade portland cement, and the water reducing agent is a polycarboxylic acid water reducing agent.
6. The self-luminous high-efficiency photocatalytic concrete according to claim 1, characterized in that: the composite material comprises the following raw materials in parts by weight: 19-21 parts of cement, 25-28 parts of water, 95-100 parts of sand, 95-100 parts of stone, 2-3 parts of water reducing agent, 2-3 parts of chromium-doped nano titanium dioxide and CaAl2O4：Eu2+，Nd3+4-5 parts of a light-induced self-luminous material.
7. The self-luminous high-efficiency photocatalytic concrete according to claim 6, characterized in that: the fineness of the stone is 5-25 mm, and the crushing value of the stone is less than 15.
8. A preparation method of self-luminous high-efficiency photocatalytic concrete is characterized by being used for preparing the self-luminous high-efficiency photocatalytic concrete according to any one of claims 1 to 7, and comprising the following steps of:
A. preparing chromium-doped nano titanium dioxide;
B. mixing chromium with nano titanium dioxide, cement and CaAl according to a certain proportion2O4：Eu2+，Nd3+Adding the photoinduced self-luminous material into a stirrer for primary stirring;
C. uniformly mixing water and a water reducing agent according to a ratio, and adding the mixture into a stirrer for secondary stirring;
D. and adding the coarse aggregate into a stirrer according to the proportion, and stirring for three times to obtain the self-luminous efficient photocatalytic concrete.
9. The preparation method of the self-luminous high-efficiency photocatalytic concrete according to claim 8, wherein the step A specifically comprises the following steps:
a1, weighing 1-2 parts of analytically pure chromium chloride, putting the analytically pure chromium chloride into a three-neck flask filled with 98-102 parts of analytically pure absolute ethanol solution, slowly adding 105-110 parts of titanium tetrachloride solution into the three-neck flask to obtain a mixture, and keeping magnetic stirring in the whole process;
a2, placing the mixture into a high-pressure hydrothermal reaction kettle;
and A3, centrifuging, washing and drying the reacted mixture, and grinding to obtain the chromium-doped nano titanium dioxide.
10. The preparation method of the self-luminous high-efficiency photocatalytic concrete according to claim 9, characterized in that: in the step A2, the reaction temperature of the high-pressure hydrothermal reaction kettle is 500-550 ℃, and the reaction time is 2-24 hours.
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