CN115646475B - Secondary supported photocatalytic cement-based material and preparation method thereof - Google Patents
Secondary supported photocatalytic cement-based material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 83
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 81
- 239000004568 cement Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011941 photocatalyst Substances 0.000 claims abstract description 58
- 239000011521 glass Substances 0.000 claims abstract description 51
- 239000011324 bead Substances 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000011398 Portland cement Substances 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 47
- 239000010936 titanium Substances 0.000 claims description 41
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 40
- 229910052719 titanium Inorganic materials 0.000 claims description 40
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000725 suspension Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 18
- 239000004202 carbamide Substances 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 16
- 238000004381 surface treatment Methods 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 33
- 239000004408 titanium dioxide Substances 0.000 abstract description 13
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 10
- 230000004043 responsiveness Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 description 19
- 238000002156 mixing Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [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 description 8
- 229940043267 rhodamine b Drugs 0.000 description 8
- 238000010998 test method Methods 0.000 description 8
- 239000004005 microsphere Substances 0.000 description 6
- 239000012258 stirred mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- -1 automobile exhaust Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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Abstract
The invention discloses a secondary supported photocatalytic cement-based material which comprises the following components in parts by weight: 2-10 parts of supported photocatalyst, 95-100 parts of ordinary Portland cement, and the supported photocatalyst is positioned at the top to one third of the ordinary Portland cement. The invention also discloses a preparation method of the secondary supported photocatalytic cement-based material. According to the invention, the titanium dioxide film is coated on the hollow glass beads by a sol-gel method, so that the agglomeration of titanium dioxide powder is avoided, the specific surface area of titanium dioxide is increased, and the utilization efficiency of the catalyst on light is improved; the unmodified titanium dioxide can only be subjected to photocatalysis by ultraviolet light, and the nitrogen-doped titanium dioxide is modified, so that the forbidden bandwidth of the catalyst is changed, the catalyst has visible light responsiveness, and the photocatalysis capacity under the natural light condition is improved; can effectively avoid the waste of photocatalysis components, and has simple and convenient operation.
Description
Technical Field
The invention relates to a cement-based material and a preparation method thereof, in particular to a secondary supported photocatalytic cement-based material and a preparation method thereof.
Background
With the rapid progress of urban industrialization and rapid population growth, the problem of environmental pollution is increasingly serious. At present, china is in serious atmospheric pollution. The sources of the atmospheric pollution are wide, such as industrial waste gas, automobile exhaust, powder particles generated in urban construction and the like, and the waste gas can not only harm human bodies, but also be adsorbed on the outer wall of the building, so that the wall pollution is caused, and the beautiful appearance of the building is influenced. The cleaning method of wall pollution mainly comprises the step of cleaning by workers through hanging baskets in high-altitude operation, so that the cleaning method not only consumes a great deal of labor cost and has safety problems, but also causes certain loss on the vertical surface of the outer wall when cleaning the outer wall, and causes certain influence on the appearance and durability. Therefore, analyzing the cause of the formation of the pollution of the outer wall and finding a method for solving the self-cleaning problem of the outer wall is a key for solving the pollution problem of the outer wall.
The photocatalyst is used in cement-based materials to prepare the photocatalytic self-cleaning cement-based materials, and has important practical significance for reducing urban air pollution. The method has the advantages that the photocatalyst is prepared into the coating which is coated on the surface of the cement-based material to improve the photocatalytic effect, but the method has the problems of complex process, high labor cost, easy aging and falling of the coating and the like. The existing preparation method of the photocatalysis cement-based material is to directly mix the photocatalyst into the cement-based material, but the photocatalyst is agglomerated in the cement-based material, so that the specific surface area of the photocatalyst is reduced, and the photocatalysis effect is reduced; and a large amount of photocatalysis is coated in the cement-based material, so that the photocatalysis cannot be exerted.
Disclosure of Invention
The invention aims to: in order to overcome the defects in the prior art, the invention aims to provide a secondary supported photocatalytic cement-based material with visible light responsiveness and improved photocatalytic capability under natural light conditions, and the invention also aims to provide a preparation method of the secondary supported photocatalytic cement-based material, which is capable of effectively avoiding waste of photocatalytic components and is simple and convenient to operate.
The technical scheme is as follows: the invention discloses a secondary supported photocatalytic cement-based material, which comprises the following components in parts by weight: 2-10 parts of supported photocatalyst, 95-100 parts of ordinary Portland cement, and the supported photocatalyst is positioned at the top to one third of the ordinary Portland cement.
Further, the supported photocatalyst comprises hollow glass beads and a photocatalyst, and the surface of the hollow glass beads is supported with the photocatalyst.
The preparation method of the secondary supported photocatalytic cement-based material comprises the following steps:
(a) Weighing a titanium source and absolute ethyl alcohol, dropwise adding acetylacetone, wherein the mass ratio of the titanium source to the absolute ethyl alcohol to the acetylacetone is 25:90-100:1, magnetically stirring, adding urea, slowly dropwise adding deionized water, stirring, aging, adding hollow glass microspheres subjected to surface treatment, and stirring to obtain a suspension;
(b) Filtering and drying the suspension in the step (a), calcining the powder at 450-700 ℃, grinding and sieving to obtain a supported photocatalyst;
(c) Stirring the supported photocatalyst obtained in the step (b), ordinary Portland cement and water according to the ratio of 2-10:95-100:35-50, placing the stirred mixture into a mould for vibration molding, curing the mixture under standard conditions, and removing the mould to obtain the secondary supported photocatalytic cement-based material.
Further, in the step (a), the titanium source is tetrabutyl titanate or titanium tetrachloride. The hollow glass beads are corroded by sodium hydroxide solution with the concentration of 3-5 wt%. The mass ratio of the titanium source to the hollow glass beads is 3-5:5. The aging time is 1-2 days.
Further, in the step (b), the drying temperature is 50-60 ℃, the drying time is 1-2 d, and the powder is ground and sieved to pass through a 200-mesh sieve. Heating the powder to 450-700 ℃ at 8-15 ℃/min, calcining, preserving heat for 4h, and cooling to room temperature. The calcination temperature is lower than 450 ℃, so that titanium dioxide cannot be converted from an amorphous phase to an anatase phase, and the photocatalytic activity cannot be obtained; the calcination temperature is higher than 700 ℃, so that part of glass beads are crushed and the low-density characteristic is lost.
Further, in the step (c), the standard condition is a temperature of 20.+ -. 2 ℃ and a relative humidity of 95%.
The preparation principle is as follows: because the hollow glass beads have the characteristic of low density, the photocatalytic functional material can be suspended on the upper layer of the cement-based material by utilizing vibration in the process of preparing the secondary load-type cement-based material, the utilization efficiency of the photocatalyst on sunlight is improved, and meanwhile, the available wavelength range of the catalyst on light is enlarged by nitrogen doping modification, so that the photocatalytic effect is further improved. When natural light irradiates on the surface of the secondary supported photocatalytic cement-based material polluted by organic matters, part of photon energy is absorbed by a photocatalyst and is used for catalyzing and degrading the organic pollutants.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable characteristics:
1. coating titanium dioxide film on the hollow glass beads by sol-gel method, avoiding agglomeration of titanium dioxide powder, increasing specific surface area of titanium dioxide, and improving utilization efficiency of catalyst to light;
2. The unmodified titanium dioxide can only be subjected to photocatalysis by ultraviolet light, and the nitrogen-doped titanium dioxide is modified, so that the forbidden bandwidth of the catalyst is changed, the catalyst has visible light responsiveness, and the photocatalysis capacity under the natural light condition is improved;
3. according to the invention, the photocatalytic material is mixed into the cement-based material, and the hollow glass microspheres are converged on the upper shallow layer of the cement-based material through vibration according to the low-density characteristic of the hollow glass microspheres, so that the waste of photocatalytic components can be effectively avoided, and the operation is simpler and more convenient.
Drawings
FIG. 1 is an SEM image of hollow glass microspheres of the present invention;
FIG. 2 is a schematic view of the structure of the present invention;
FIG. 3 is an SEM image of the supported photocatalyst of the present invention;
FIG. 4 is an EDS diagram of a supported photocatalyst of the present invention;
FIG. 5 is an XRD pattern of a supported photocatalyst of the present invention;
FIG. 6 is a graph showing the effect of the incorporation of different types of photocatalysts on the photocatalytic performance of a photocatalytic cement-based material in accordance with the present invention;
FIG. 7 is a graph showing the effect of different calcination temperatures on the photocatalytic performance of a secondarily-supported photocatalytic cement-based material in accordance with the present invention;
FIG. 8 is a graph showing the effect of different amounts of supported photocatalyst on the photocatalytic performance of a secondary supported photocatalytic cement-based material according to the present invention;
FIG. 9 is a degradation curve of the secondarily-supported photocatalytic cement-based material of the present invention against 0.1mL of 1wt% phenol.
Detailed Description
In the following examples, the hollow glass microspheres were about 20 to 100 μm in diameter, as shown in FIG. 1.
Example 1
The preparation method of the secondary supported photocatalytic cement-based material comprises the following steps:
a. Weighing tetrabutyl titanate as a titanium source and absolute ethyl alcohol, dropwise adding acetylacetone, wherein the mass ratio of the titanium source to the absolute ethyl alcohol to the acetylacetone is 25:100:1, placing the mixture into a magnetic stirrer for stirring, adding urea, and slowly dropwise adding deionized water, wherein the mass ratio of the titanium source to the urea to the deionized water is (25): 1:30, aging for 1d at room temperature after stirring, adding the hollow glass beads 2 subjected to surface treatment, wherein the mass ratio of the titanium source to the hollow glass beads 2 is 3:5, and stirring to obtain a suspension;
b. Preparing a sodium hydroxide solution with the mass fraction of 4wt%, and mixing the sodium hydroxide solution with the following components: hollow glass bead 2 according to 25: mixing, stirring and stirring the materials according to the mass ratio of 1, filtering, drying to obtain hollow glass beads 2 after surface treatment, filtering the suspension in the step a, drying the suspension at 50 ℃ for 2d, heating the powder to 500 ℃ at 8 ℃/min, calcining the powder, preserving heat for 4h, cooling the powder to room temperature, grinding the powder, and sieving the powder with a 200-mesh sieve to obtain the supported photocatalyst;
c. And c, stirring the supported photocatalyst obtained in the step b, ordinary Portland cement 1 and water according to a ratio of 5:100:35, putting the mixture into a mould for vibration molding, curing under standard conditions (the temperature is 20+/-2 ℃ and the relative humidity is 95%), and removing the mould to obtain the secondary supported photocatalytic cement-based material.
As shown in fig. 2, in the secondary supported photocatalytic cement-based material obtained in this example, the supported photocatalyst was present in the top to one third of the Portland cement 1. The supported photocatalyst comprises hollow glass beads 2 and a photocatalyst 3, wherein the surface of the hollow glass beads 2 is supported with the photocatalyst.
As shown in fig. 3, the surface of the hollow glass microsphere 2 can be found to be covered with a layer of titanium dioxide film by observing the microscopic morphology of the supported photocatalyst by using a field Scanning Electron Microscope (SEM).
As shown in fig. 4, the result of the surface scanning by the spectrometer shows the composition of each element on the surface of the supported photocatalyst, wherein the mass ratio of Ti element is 17.3wt% and the atomic number is 6.63%.
As shown in fig. 5, the x-ray diffractometer (XRD) results show diffraction peaks of the supported photocatalyst, which are derived from anatase, indicating that the crystalline form of titania in this example is anatase.
The prepared secondary supported photocatalytic cement-based material is polished by sand paper, rhodamine B solution is dripped, and the degradation effect of the sample on rhodamine B is tested after drying, as shown in figure 6, which is a cement-based material control group, a cement-based material (primary supported photocatalytic cement-based material) directly doped with 5% anatase type titanium dioxide and the degradation rate of the secondary supported photocatalytic cement-based material on rhodamine B. When the natural illuminance is 5-8×10 4 lux and the irradiation time is 80min, the degradation rate of rhodamine B by the supported photocatalytic cement-based material prepared in the example 1 is 50.3%, and the degradation rate of rhodamine B on the surface of the ordinary cement-based material is 17.5%. Therefore, the secondary supported photocatalytic cement-based material prepared by the invention has a better self-cleaning effect.
Example 2
The preparation method of the secondary supported photocatalytic cement-based material comprises the following steps:
a. Weighing tetrabutyl titanate as a titanium source and absolute ethyl alcohol, dropwise adding acetylacetone, wherein the mass ratio of the titanium source to the absolute ethyl alcohol to the acetylacetone is 25:100:1, placing the mixture into a magnetic stirrer for stirring, adding urea, and slowly dropwise adding deionized water, wherein the mass ratio of the titanium source to the urea to the deionized water is (25): 1:30, aging for 1d at room temperature after stirring, adding the hollow glass beads 2 subjected to surface treatment, wherein the mass ratio of the titanium source to the hollow glass beads 2 is 3:5, and stirring to obtain a suspension;
b. Preparing a sodium hydroxide solution with the mass fraction of 4wt%, and mixing the sodium hydroxide solution with the following components: hollow glass bead 2 according to 25: mixing, stirring and stirring the materials according to the mass ratio of 1, filtering, drying to obtain hollow glass beads 2 after surface treatment, filtering the suspension in the step a, drying the suspension at 50 ℃ for 2d, heating the powder to 450 ℃ at 8 ℃/min, calcining the powder, preserving heat for 4 hours, cooling the powder to room temperature, grinding the powder, and sieving the powder with a 200-mesh sieve to obtain the supported photocatalyst;
c. and c, stirring the supported photocatalyst obtained in the step b, ordinary Portland cement 1 and water according to a ratio of 5:100:35, putting the stirred mixture into a mould for vibration molding, curing under standard conditions (the temperature is 20+/-2 ℃ and the relative humidity is 95%), and removing the mould to obtain the secondary supported photocatalytic cement-based material.
The self-cleaning performance of the secondary supported photocatalytic cement-based material obtained in this example was tested by the test method of example 1, as shown in fig. 7, and the self-cleaning performance of the secondary supported photocatalytic cement-based material at different calcining temperatures was close to that of example 1 and was 45.9%. The calcination temperature is too low, so that the crystallinity of titanium dioxide in the synthesized photocatalyst 3 is poor, and the photocatalytic effect is lowered.
Example 3
The preparation method of the secondary supported photocatalytic cement-based material comprises the following steps:
a. Weighing tetrabutyl titanate as a titanium source and absolute ethyl alcohol, dropwise adding acetylacetone, wherein the mass ratio of the titanium source to the absolute ethyl alcohol to the acetylacetone is 25:100:1, placing the mixture into a magnetic stirrer for stirring, adding urea, and slowly dropwise adding deionized water, wherein the mass ratio of the titanium source to the urea to the deionized water is (25): 1:30, aging for 1d at room temperature after stirring, adding the hollow glass beads 2 subjected to surface treatment, wherein the mass ratio of the titanium source to the hollow glass beads 2 is 3:5, and stirring to obtain a suspension;
b. preparing a sodium hydroxide solution with the mass fraction of 4wt%, and mixing the sodium hydroxide solution with the following components: hollow glass bead 2 according to 25: mixing, stirring and stirring the materials according to the mass ratio of 1, filtering, drying to obtain hollow glass beads 2 after surface treatment, filtering the suspension in the step a, drying the suspension at 50 ℃ for 2d, heating the powder to 700 ℃ at 8 ℃/min, calcining the powder, preserving heat for 4h, cooling the powder to room temperature, grinding the powder, and sieving the powder with a 200-mesh sieve to obtain the supported photocatalyst;
c. and c, stirring the supported photocatalyst obtained in the step b, ordinary Portland cement 1 and water according to a ratio of 5:100:35, putting the stirred mixture into a mould for vibration molding, curing under standard conditions (the temperature is 20+/-2 ℃ and the relative humidity is 95%), and removing the mould to obtain the secondary supported photocatalytic cement-based material.
The self-cleaning performance of the secondary supported photocatalytic cement-based material obtained in this example was tested by the test method of example 1, and the result showed that the self-cleaning performance was 56.9% better than that of example 1. The calcination temperature is higher, more amorphous titanium dioxide in the synthesized catalyst is converted into an anatase crystal form, and the photocatalysis effect is improved.
Example 4
The preparation method of the secondary supported photocatalytic cement-based material comprises the following steps:
a. Weighing tetrabutyl titanate as a titanium source and absolute ethyl alcohol, dropwise adding acetylacetone, wherein the mass ratio of the titanium source to the absolute ethyl alcohol to the acetylacetone is 25:100:1, placing the mixture into a magnetic stirrer for stirring, adding urea, and slowly dropwise adding deionized water, wherein the mass ratio of the titanium source to the urea to the deionized water is (25): 1:30, aging for 1d at room temperature after stirring, adding the hollow glass beads 2 subjected to surface treatment, wherein the mass ratio of the titanium source to the hollow glass beads 2 is 3:5, and stirring to obtain a suspension;
b. preparing a sodium hydroxide solution with the mass fraction of 4wt%, and mixing the sodium hydroxide solution with the following components: hollow glass bead 2 according to 25: mixing, stirring and stirring the materials according to the mass ratio of 1, filtering, drying to obtain hollow glass beads 2 after surface treatment, filtering the suspension in the step a, drying the suspension at 50 ℃ for 2d, heating the powder to 700 ℃ at 8 ℃/min, calcining the powder, preserving heat for 4h, cooling the powder to room temperature, grinding the powder, and sieving the powder with a 200-mesh sieve to obtain the supported photocatalyst;
c. and c, stirring the supported photocatalyst obtained in the step b, ordinary Portland cement 1 and water according to a ratio of 10:100:35, putting the stirred mixture into a mould for vibration molding, curing under standard conditions (the temperature is 20+/-2 ℃ and the relative humidity is 95%), and removing the mould to obtain the secondary supported photocatalytic cement-based material.
The self-cleaning performance of the secondary supported photocatalytic cement-based material obtained in this example was tested by the test method of example 1, and fig. 8 shows that the self-cleaning performance of the secondary supported photocatalytic cement-based material with different amounts of the photocatalyst 3 is close to that of example 3 and 57.2%. Too much supported photocatalyst is doped in the cement-based material, and the excessive photocatalyst 3 is buried in the cement-based material and cannot exert the photocatalytic effect.
Example 5
The preparation method of the secondary supported photocatalytic cement-based material comprises the following steps:
a. Weighing tetrabutyl titanate as a titanium source and absolute ethyl alcohol, dropwise adding acetylacetone, wherein the mass ratio of the titanium source to the absolute ethyl alcohol to the acetylacetone is 25:100:1, placing the mixture into a magnetic stirrer for stirring, adding urea, and slowly dropwise adding deionized water, wherein the mass ratio of the titanium source to the urea to the deionized water is (25): 1:30, aging for 1d at room temperature after stirring, adding the hollow glass beads 2 subjected to surface treatment, wherein the mass ratio of the titanium source to the hollow glass beads 2 is 3:5, and stirring to obtain a suspension;
b. preparing a sodium hydroxide solution with the mass fraction of 4wt%, and mixing the sodium hydroxide solution with the following components: hollow glass bead 2 according to 25: mixing, stirring and stirring the materials according to the mass ratio of 1, filtering, drying to obtain hollow glass beads 2 after surface treatment, filtering the suspension in the step a, drying the suspension at 50 ℃ for 2d, heating the powder to 700 ℃ at 8 ℃/min, calcining the powder, preserving heat for 4h, cooling the powder to room temperature, grinding the powder, and sieving the powder with a 200-mesh sieve to obtain the supported photocatalyst;
c. And c, stirring the supported photocatalyst obtained in the step b, ordinary Portland cement 1 and water according to a ratio of 2:100:35, putting the stirred mixture into a mould for vibration molding, curing under standard conditions (the temperature is 20+/-2 ℃ and the relative humidity is 95%), and removing the mould to obtain the secondary supported photocatalytic cement-based material.
In the secondary supported photocatalytic cement-based material obtained in this example, the supported photocatalyst was present at the top to one third of the Portland cement 1. The supported photocatalyst comprises hollow glass beads 2 and a photocatalyst 3, wherein the surface of the hollow glass beads 2 is supported with the photocatalyst.
The self-cleaning performance of the secondary supported photocatalytic cement-based material of this example was tested by the test method of example 1, and the result showed that the self-cleaning performance was significantly lower than that of example 1, and was 33.5%. The amount of the supported photocatalyst is too small to completely cover the surface of the cement-based material, and the self-cleaning performance of the cement-based material is reduced.
Example 6
The preparation method of the secondary supported photocatalytic cement-based material comprises the following steps:
a. Weighing titanium tetrachloride and absolute ethyl alcohol, dropwise adding acetylacetone, wherein the mass ratio of the titanium source to the absolute ethyl alcohol to the acetylacetone is 25:90:1, placing the titanium source to the absolute ethyl alcohol to be stirred in a magnetic stirrer, adding urea, and slowly dropwise adding deionized water, wherein the mass ratio of the titanium source to the urea to the deionized water is (25): 1:30, aging for 2 days at room temperature after stirring, adding the hollow glass beads 2 subjected to surface treatment, wherein the mass ratio of a titanium source to the hollow glass beads 2 is 5:5, and stirring to obtain a suspension;
b. preparing a sodium hydroxide solution with the mass fraction of 3wt%, and mixing the sodium hydroxide solution with the following components: hollow glass bead 2 according to 25: mixing, stirring and stirring the materials according to the mass ratio of 1, filtering, drying to obtain hollow glass beads 2 after surface treatment, filtering the suspension in the step a, drying at 60 ℃ for 1d, heating the powder to 600 ℃ at 15 ℃/min, calcining, preserving heat for 4 hours, cooling to room temperature, grinding, and sieving with a 200-mesh sieve to obtain the supported photocatalyst;
c. Stirring the supported photocatalyst obtained in the step b with ordinary Portland cement 1 and water according to a ratio of 2:95:50, placing the mixture into a mould for vibration molding, curing under standard conditions (the temperature is 20+/-2 ℃ and the relative humidity is 95%), and removing the mould to obtain the secondary supported photocatalytic cement-based material.
The self-cleaning performance of the secondary supported photocatalytic cement-based material of this example was tested by the test method of example 1, and the result shows that the self-cleaning performance thereof is close to that of example 3 and is 58.3%.
Example 7
The preparation method of the secondary supported photocatalytic cement-based material comprises the following steps:
a. weighing titanium tetrachloride and absolute ethyl alcohol, dropwise adding acetylacetone, wherein the mass ratio of the titanium source to the absolute ethyl alcohol to the acetylacetone is 25:95:1, placing the titanium source to the absolute ethyl alcohol to be stirred in a magnetic stirrer, adding urea, and slowly dropwise adding deionized water, wherein the mass ratio of the titanium source to the urea to the deionized water is (25): 1:30, aging for 1.5 days at room temperature after stirring, adding the hollow glass beads 2 subjected to surface treatment, wherein the mass ratio of a titanium source to the hollow glass beads 2 is 4:5, and stirring to obtain a suspension;
b. Preparing a sodium hydroxide solution with the mass fraction of 5wt%, and mixing the sodium hydroxide solution with the following components: hollow glass bead 2 according to 25: mixing, stirring and stirring the materials according to the mass ratio of 1, filtering, drying to obtain hollow glass beads 2 after surface treatment, filtering the suspension in the step a, drying at 55 ℃ for 1.5d, heating the powder to 650 ℃ at 12 ℃/min, calcining, preserving heat for 4h, cooling to room temperature, grinding, and sieving with a 200-mesh sieve to obtain the supported photocatalyst;
c. And c, stirring the supported photocatalyst obtained in the step b, ordinary Portland cement 1 and water according to a ratio of 8:98:40, putting the stirred mixture into a mould for vibration molding, curing under standard conditions (the temperature is 20+/-2 ℃ and the relative humidity is 95%), and removing the mould to obtain the secondary supported photocatalytic cement-based material.
The self-cleaning performance of the secondary supported photocatalytic cement-based material of this example was tested by the test method of example 1, and the result showed that the degradation rate to phenol was 51.3%.
Comparative example 1
The remaining steps of this comparative example are the same as in example 3, except that: in the step (1), the titanium source is titanium tetrachloride. The degradation rate of the prepared secondary supported photocatalytic cement-based material to rhodamine B is measured to be 54.3% by adopting the test method in the embodiment 1.
From the results of the degradation rate of rhodamine B in the embodiment 3 and the comparative example 1, the titanium source is selected from tetrabutyl titanate or titanium tetrachloride, and the effect of the tetrabutyl titanate on the photocatalysis result is small, and the tetrabutyl titanate has the advantages of less toxicity, simple operation and lower cost, so that the tetrabutyl titanate is more suitable to be used as the titanium source of the invention.
Comparative example 2
The remaining steps of this comparative example are the same as in example 3, except that: in step (1), urea is not added. The degradation rate of the prepared secondary supported photocatalytic cement-based material to rhodamine B is 45.3% by adopting the test method in the example 1, and is lower than that of the example 3. The nitrogen doping modification reduces the forbidden bandwidth of the catalyst, thereby improving the utilization efficiency of the catalyst to light and enabling the secondary supported photocatalytic cement-based material to obtain more excellent photocatalytic effect.
Claims (6)
1. The preparation method of the secondary supported photocatalytic cement-based material is characterized by comprising the following steps of:
(a) Weighing a titanium source and absolute ethyl alcohol, dropwise adding acetylacetone, wherein the mass ratio of the titanium source to the absolute ethyl alcohol to the acetylacetone is 25:90-100:1, magnetically stirring, adding urea, and slowly dropwise adding deionized water, wherein the mass ratio of the titanium source to the urea to the deionized water is 25:1:30, aging after stirring, adding the hollow glass beads (2) subjected to surface treatment, and stirring to obtain a suspension;
(b) Filtering and drying the suspension in the step (a), calcining the powder at 450-700 ℃, grinding and sieving to obtain a supported photocatalyst;
(c) Placing the supported photocatalyst obtained in the step (b), ordinary Portland cement (1) and water according to a ratio of 2-10:95-100:35-50 into a mould for vibration molding, curing under standard conditions, and removing the mould to obtain a secondary supported photocatalytic cement-based material;
in the step (a), the hollow glass beads (2) are corroded by sodium hydroxide solution with the concentration of 3-5wt%;
In the step (c), the standard condition is that the temperature is 20+/-2 ℃ and the relative humidity is 95%;
The secondary supported photocatalytic cement-based material comprises the following components in parts by weight: 2-10 parts of a supported photocatalyst, 95-100 parts of ordinary Portland cement (1), wherein the supported photocatalyst is positioned at the top to one third of the ordinary Portland cement (1);
the supported photocatalyst comprises hollow glass beads (2) and a photocatalyst (3), wherein the surface of the hollow glass beads (2) is supported with the photocatalyst (3).
2. The method for preparing the secondary supported photocatalytic cement-based material according to claim 1, characterized by comprising the steps of: in the step (a), the titanium source is tetrabutyl titanate or titanium tetrachloride.
3. The method for preparing the secondary supported photocatalytic cement-based material according to claim 1, characterized by comprising the steps of: in the step (a), the mass ratio of the titanium source to the hollow glass beads (2) is 3-5:5.
4. The method for preparing the secondary supported photocatalytic cement-based material according to claim 1, characterized by comprising the steps of: in the step (a), the aging time is 1-2 days.
5. The method for preparing the secondary supported photocatalytic cement-based material according to claim 1, characterized by comprising the steps of: in the step (b), the drying temperature is 50-60 ℃, the drying time is 1-2 d, and the powder is ground and sieved to pass through a 200-mesh sieve.
6. The method for preparing the secondary supported photocatalytic cement-based material according to claim 1, characterized by comprising the steps of: in the step (b), the powder is heated to 450-700 ℃ at 8-15 ℃/min for calcination, and is cooled to room temperature after heat preservation for 4 hours.
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