CN112573882B - A kind of photocatalytic cement mortar containing boron, carbon and nitrogen and preparation method thereof - Google Patents
A kind of photocatalytic cement mortar containing boron, carbon and nitrogen and preparation method thereof Download PDFInfo
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- CN112573882B CN112573882B CN202110055931.1A CN202110055931A CN112573882B CN 112573882 B CN112573882 B CN 112573882B CN 202110055931 A CN202110055931 A CN 202110055931A CN 112573882 B CN112573882 B CN 112573882B
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000011083 cement mortar Substances 0.000 title claims abstract description 71
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 44
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006902 nitrogenation reaction Methods 0.000 title description 2
- 239000004576 sand Substances 0.000 claims abstract description 96
- DZVPMKQTULWACF-UHFFFAOYSA-N [B].[C].[N] Chemical compound [B].[C].[N] DZVPMKQTULWACF-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 40
- 239000004568 cement Substances 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- 239000008247 solid mixture Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims description 61
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000012528 membrane Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000008399 tap water Substances 0.000 claims description 12
- 235000020679 tap water Nutrition 0.000 claims description 12
- PPWPWBNSKBDSPK-UHFFFAOYSA-N [B].[C] Chemical compound [B].[C] PPWPWBNSKBDSPK-UHFFFAOYSA-N 0.000 claims description 11
- 239000011398 Portland cement Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical group O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 3
- 239000011941 photocatalyst Substances 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 230000001737 promoting effect Effects 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 13
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 12
- 239000004408 titanium dioxide Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000009825 accumulation Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/32—Carbides; Nitrides; Borides ; Silicides
- C04B14/325—Nitrides
- C04B14/327—Boron nitride
-
- 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
- C04B28/021—Ash cements, e.g. fly ash cements ; Cements based on incineration residues, e.g. alkali-activated slags from waste incineration ; Kiln dust 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/08—Slag cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
- C04B2111/00827—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Civil Engineering (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种含硼碳氮的光催化水泥砂浆及其制备方法，光催化水泥砂浆按重量份的原料配比包括：水泥4~10份、机制砂10~35份、硼碳氮0.004~0.02份、纳米蒙脱土0.005~0.014份、去离子水2~6份；制备方法按如下步骤进行：步骤一：制备附膜液；步骤二：机制砂表面附膜；步骤三：制备固体拌合物；步骤四：制备硼碳氮分散液；步骤五：制备光催化水泥砂浆；本发明采用三维层状多孔硼碳氮作为水泥砂浆的纳米光催化材料，在可见光照射下可显著提高降解污染物的效率；通过将硼碳氮分别加入水泥和水中，提高硼碳氮在水泥砂浆中的分散性，保证光催化降解污染物的效果，为推动光催化水泥砂浆的应用起到积极的促进作用。The invention relates to a photocatalytic cement mortar containing boron, carbon and nitrogen and a preparation method thereof. The raw material ratio of the photocatalytic cement mortar by weight includes: 4-10 parts of cement, 10-35 parts of machine-made sand, and 0.004-35 parts of boron, carbon and nitrogen. 0.02 part, 0.005-0.014 part of nano-montmorillonite, and 2-6 parts of deionized water; the preparation method is as follows: step 1: prepare film-attached liquid; step 2: attach film on the surface of machine-made sand; step 3: prepare solid mixture step 4: preparing boron carbon nitrogen dispersion; step 5: preparing photocatalytic cement mortar; the present invention adopts three-dimensional layered porous boron carbon nitrogen as the nano photocatalytic material of cement mortar, which can significantly improve degradation pollution under visible light irradiation By adding boron, carbon and nitrogen to cement and water respectively, the dispersibility of boron, carbon and nitrogen in cement mortar is improved, and the effect of photocatalytic degradation of pollutants is ensured, which plays a positive role in promoting the application of photocatalytic cement mortar. .
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a boron-carbon-nitrogen-containing photocatalytic cement mortar and a preparation method thereof.
Background
The cement mortar is an engineering material which is prepared by mixing cement, fine aggregate and water as main raw materials and has strength after hardening, and is mainly used for masonry, plastering, decoration engineering and the like. The photocatalytic cement mortar is a composite material which is doped with a nano photocatalytic material in the process of preparing the cement mortar and realizes the degradation of pollutants under the action of sunlight. The photocatalytic cement mortar is mainly applied to the surface of building engineering or pavement materials and plays a role in purifying air. The application effect of the photocatalytic cement mortar is directly influenced by the properties of the nano photocatalytic material, the contact area with a light source and the composite effect of the nano photocatalytic material and materials such as cement. At present, common nano photocatalytic materials applied to cement-based materials are titanium dioxide, graphite-phase carbon nitride and the like, but the titanium dioxide and the graphite-phase carbon nitride have a plurality of problems in practical application, and the problems are summarized as follows:
(1) because of the limitation of the forbidden band width of the material, the photocatalysis of the titanium dioxide mainly depends on ultraviolet rays, and the ultraviolet rays account for about 4.5 percent of sunlight; graphite-phase carbon nitride has no photocatalytic performance or mainly depends on blue-violet light in a solar spectrum for photocatalytic reaction, and the utilization rate of sunlight by the two materials is low, so that the popularization and application of photocatalytic cement mortar are hindered to a certain extent.
(2) The common structural forms of titanium dioxide and graphite phase carbon nitride are mainly one-dimensional structures and two-dimensional structures, the structural forms determine that the specific surface areas of the titanium dioxide and the graphite phase carbon nitride are small, photo-generated electrons and holes are easy to combine, and the photocatalysis effect is poor.
(3) At present, most of nano photocatalytic materials are directly mixed in cement, and because the nano materials are easy to agglomerate and are difficult to be uniformly mixed with the cement and sand, the strength of cement mortar is influenced, and the contact area of the nano photocatalytic materials and a light source is reduced, so that the photocatalytic effect in the use process is influenced.
Boron carbon nitride is a non-metallic inorganic semiconductor material emerging in recent years, and has been gradually applied to lithium ion batteries, gas adsorption, supercapacitors and the like, but no relevant documents for preparing photocatalytic cement mortar and a preparation method thereof are found. Therefore, in order to improve the photocatalytic effect, the design of a novel photocatalytic cement mortar and a manufacturing method thereof have important significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the photocatalytic cement mortar containing boron, carbon and nitrogen and the preparation method thereof, which obviously improve the efficiency of degrading pollutants and play a positive promoting role in promoting the large-scale application of the photocatalytic cement mortar.
In order to achieve the purpose, the invention adopts the following technical scheme:
the photocatalytic cement mortar containing boron, carbon and nitrogen comprises the following raw materials in parts by weight: 4-10 parts of cement, 10-35 parts of machine-made sand, 0.004-0.02 part of boron-carbon-nitrogen, 0.005-0.014 part of nano montmorillonite and 2-6 parts of deionized water.
Further, the photocatalytic cement mortar comprises the following raw materials in parts by weight: 4.5-8 parts of cement, 13-25 parts of machine-made sand, 0.004-0.015 part of boron-carbon-nitrogen, 0.0053-0.011 part of nano montmorillonite and 2.2-4.8 parts of deionized water.
Preferably, the photocatalytic cement mortar comprises the following raw materials in parts by weight: 5 parts of cement, 15 parts of machine-made sand, 0.005 part of boron carbon nitrogen, 0.006 part of nano montmorillonite and 2.5 parts of deionized water.
Further, the grain size of the machine-made sand is 0.25-4.75 mm, and the grain size of the nano montmorillonite is 20-65 nm.
Further, the cement is any one of ordinary portland cement, slag portland cement and fly ash portland cement.
Further, the boron carbon nitride is nano boron carbon nitride with a three-dimensional layered porous structure.
The boron-nitrogen-carbon photocatalyst is obtained by carbon doping of h-BN, and the specific method is that 2 parts by weight of boron source, 2-7 parts by weight of carbon source and 2-4 parts by weight of urea are adopted and prepared under the condition of 1250 ℃ in ammonia atmosphere; the boron source is boron oxide or boric acid; the carbon source is glucose or sucrose or fructose.
The preparation method of the boron-carbon nitrogen-containing photocatalytic cement mortar comprises the following steps:
the method comprises the following steps: preparing membrane attaching liquid; adding nano montmorillonite with volume of V1Stirring the raw materials in the tap water for 25-50 minutes by a dispersion instrument at a rotating speed of 5500-9000 r/min to obtain a membrane-attaching solution; the V is1=（0.45~0.9）V2In which V is2The stacking volume of the machine-made sand;
step two: coating a film on the surface of the machine-made sand; stirring and washing the machine-made sand for 5-8 minutes by using a stirring and washing barrel, then airing the machine-made sand on a mesh screen for 25-40 minutes, and then placing the machine-made sand in an oven for heating and drying; adding the dried machine-made sand into membrane attaching liquid, stirring for 5-8 minutes, pouring into a tray, placing in an oven, heating and drying to attach the nano montmorillonite to the surface of the machine-made sand, and obtaining the machine-made sand by a film attaching machine;
step three: preparing a solid mixture; equally dividing boron, carbon and nitrogen into two parts according to weight, adding one part of boron, carbon and nitrogen and cement into a stirrer, mixing and stirring for 2-3.5 minutes, adding film-coated machine-made sand, and continuously stirring for 1-2 minutes to obtain a solid mixture;
step four: preparing boron carbon nitrogen dispersion liquid; adding another part of boron-carbon-nitrogen into deionized water for ultrasonic dispersion for 10-30 minutes to obtain a boron-carbon-nitrogen dispersion liquid;
step five: preparing photocatalytic cement mortar; and adding the boron-carbon-nitrogen dispersion liquid into the solid mixture, and stirring for 2-3.5 minutes to prepare the photocatalytic cement mortar.
Further, the temperature of the oven in the second step is 65-110 ℃, and the time for heating and drying each time is 180-360 minutes.
Further, the frequency of ultrasonic dispersion in the fourth step is 18-26 kHz.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, boron carbon nitride is used as a nano photocatalytic material of cement mortar, and as the nano photocatalytic material has three-dimensional layered porous structure and large specific surface area, more reactive active sites can be effectively exposed, and the efficiency of degrading pollutants can be obviously improved; in addition, the boron carbon nitrogen can be excited by purple light, blue light, green light or red light in a spectrum to carry out photocatalytic reaction, and the photocatalytic efficiency is higher.
2. The nano montmorillonite is adsorbed on the surface of the machine-made sand, and can fill the pores in the interface area of the machine-made sand and the cement paste, so that the composite strength of the aggregate and the cement paste is enhanced; in addition, the nano montmorillonite is attached to the surface of the machine-made sand, so that the lubrication degree of the surface of the machine-made sand can be improved, and the mixing uniformity of materials in a solid mixture is improved, thereby ensuring the exposure quantity and the light receiving area of boron carbon nitrogen in the photocatalytic cement mortar.
3. According to the invention, the boron, carbon and nitrogen are respectively added into cement mortar and water to be doped into the cement mortar, so that the dispersibility of the boron, carbon and nitrogen in the cement mortar is improved, the exposure quantity of reactive active sites is ensured, and the purpose of efficiently degrading pollutants is achieved.
4. The three-dimensional layered porous boron carbon nitride adopted by the invention has good adsorption performance and can enhance the integrity of cement mortar; in addition, the three-dimensional layered porous boron carbon nitride material has the advantages of green and safe property, simple preparation and the like, and plays a positive promoting role in promoting the large-scale application of the photocatalytic cement mortar.
Detailed Description
The invention provides a boron-carbon nitrogen containing photocatalytic cement mortar and a preparation method thereof. In order to further explain the technical means and effects of the present invention, the following detailed description of the present invention is provided in conjunction with the embodiments.
In the embodiment, the photocatalytic cement mortar containing boron, carbon and nitrogen comprises the following raw materials in parts by weight: 4-10 parts of cement, 10-35 parts of machine-made sand, 0.004-0.02 part of boron-carbon-nitrogen, 0.005-0.014 part of nano montmorillonite and 2-6 parts of deionized water.
The cement mortar comprises the following raw materials in parts by weight: 4.5-8 parts of cement, 13-25 parts of machine-made sand, 0.004-0.015 part of boron-carbon-nitrogen, 0.0053-0.011 part of nano montmorillonite and 2.2-4.8 parts of deionized water.
The cement mortar comprises the following raw materials in parts by weight: 5 parts of cement, 15 parts of machine-made sand, 0.005 part of boron carbon nitrogen, 0.006 part of nano montmorillonite and 2.5 parts of deionized water.
The boron-nitrogen-carbon photocatalyst is obtained by carbon doping of h-BN, and the specific method is that 2 parts of boron source, 4.5 parts of carbon source and 3.5 parts of urea are adopted and prepared under the condition of 1250 ℃ in the atmosphere of ammonia gas; the boron source is boron oxide; the carbon source is glucose.
The preparation method of the boron-carbon nitrogen-containing photocatalytic cement mortar comprises the following steps:
the method comprises the following steps: preparing membrane attaching liquid; adding nano montmorillonite with volume of V1In the running water, miningStirring the mixture for 25 to 50 minutes by using a dispersion instrument at the rotating speed of 5500 to 9000r/min to obtain a membrane attaching solution; the V is1=（0.45~0.9）V2In which V is2The stacking volume of the machine-made sand;
step two: coating a film on the surface of the machine-made sand; stirring and washing the machine-made sand for 5-8 minutes by using a stirring and washing barrel, then airing the machine-made sand on a mesh screen for 25-40 minutes, and then placing the machine-made sand in an oven for heating and drying; adding the dried machine-made sand into membrane attaching liquid, stirring for 5-8 minutes, pouring into a tray, placing in an oven, heating and drying to attach the nano montmorillonite to the surface of the machine-made sand, and obtaining the machine-made sand by a film attaching machine;
step three: preparing a solid mixture; equally dividing boron, carbon and nitrogen into two parts according to weight, adding one part of boron, carbon and nitrogen and cement into a stirrer, mixing and stirring for 2-3.5 minutes, adding film-coated machine-made sand, and continuously stirring for 1-2 minutes to obtain a solid mixture;
step four: preparing boron carbon nitrogen dispersion liquid; adding another part of boron-carbon-nitrogen into deionized water for ultrasonic dispersion for 10-30 minutes to obtain a boron-carbon-nitrogen dispersion liquid;
step five: preparing photocatalytic cement mortar; and adding the boron-carbon-nitrogen dispersion liquid into the solid mixture, and stirring for 2-3.5 minutes to prepare the photocatalytic cement mortar.
The boron carbon nitride is nano boron carbon nitride with a three-dimensional layered porous structure.
And in the second step, the temperature of the oven is 80 ℃, and the time for heating and drying each time is 240 minutes.
The grain size of the machine-made sand is 0.25-4.75 mm; the particle size of the nano montmorillonite is 20-65 nm; the cement is ordinary portland cement; the temperature of the deionized water is 25 ℃; the frequency adopted by the ultrasonic dispersion is 20 kHz.
Example 1
In the embodiment, the cement mortar comprises the following raw materials in parts by weight: 4 parts of cement, 10 parts of machine-made sand, 0.004 part of boron-carbon-nitrogen, 0.005 part of nano montmorillonite and 2 parts of deionized water.
In the embodiment, the preparation method of the photocatalytic cement mortar comprises the following steps:
the method comprises the following steps: adding nano montmorillonite into tap water, and stirring for 30 minutes by adopting a dispersion instrument at the rotating speed of 6000r/min to obtain a membrane-attaching solution; the volume of the tap water is 0.5 times of the accumulation volume of the machine-made sand;
step two: stirring and washing the machine-made sand for 5 minutes by using a stirring and washing barrel, then placing the machine-made sand on a mesh screen for airing for 25 minutes, and then placing the machine-made sand in an oven for heating and drying; adding the dried machine-made sand into membrane attaching liquid, stirring for 5 minutes, pouring into a tray, placing in an oven, heating and drying to attach the nano montmorillonite to the surface of the machine-made sand, and obtaining the machine-made sand attached with a membrane;
step three: dividing boron, carbon and nitrogen into two parts according to the weight, adding one part of boron, carbon and nitrogen and cement into a stirrer, mixing and stirring for 2 minutes, adding film-coated machine-made sand, and continuously stirring for 1 minute to obtain a solid mixture;
step four: adding another part of boron, carbon and nitrogen into deionized water for ultrasonic dispersion for 12 minutes to obtain boron, carbon and nitrogen dispersion liquid;
step five: and adding the boron-carbon-nitrogen dispersion liquid into the solid mixture, and stirring for 2 minutes to prepare the photocatalytic cement mortar.
Example 2
In the embodiment, the cement mortar comprises the following raw materials in parts by weight: 5 parts of cement, 15 parts of machine-made sand, 0.005 part of boron carbon nitrogen, 0.006 part of nano montmorillonite and 2.5 parts of deionized water.
In the embodiment, the preparation method of the photocatalytic cement mortar comprises the following steps:
the method comprises the following steps: adding nano montmorillonite into tap water, and stirring for 40 minutes at a rotating speed of 5500r/min by using a dispersion instrument to obtain a membrane-attaching solution; the volume of the tap water is 0.52 times of the accumulation volume of the machine-made sand;
step two: stirring and washing the machine-made sand for 5.5 minutes by using a stirring and washing barrel, then placing the machine-made sand on a mesh screen for airing for 30 minutes, and then placing the machine-made sand in an oven for heating and drying; adding the dried machine-made sand into membrane attaching liquid, stirring for 6 minutes, pouring into a tray, placing in an oven, heating and drying to attach the nano montmorillonite to the surface of the machine-made sand, and obtaining the machine-made sand attached with a membrane;
step three: dividing boron, carbon and nitrogen into two parts according to the weight, adding one part of boron, carbon and nitrogen and cement into a stirrer, mixing and stirring for 2 minutes, adding film-coated machine-made sand, and continuously stirring for 1.5 minutes to obtain a solid mixture;
step four: adding another part of boron, carbon and nitrogen into deionized water for ultrasonic dispersion for 15 minutes to obtain boron, carbon and nitrogen dispersion liquid;
step five: and adding the boron-carbon-nitrogen dispersion liquid into the solid mixture, and stirring for 2.5 minutes to prepare the photocatalytic cement mortar.
Example 3
In the embodiment, the cement mortar comprises the following raw materials in parts by weight: 8 parts of cement, 25 parts of machine-made sand, 0.015 part of boron carbon nitrogen, 0.011 part of nano montmorillonite and 4.5 parts of deionized water.
In the embodiment, the preparation method of the photocatalytic cement mortar comprises the following steps:
the method comprises the following steps: adding nano montmorillonite into tap water, and stirring for 30 minutes at 7000r/min by using a dispersion instrument to obtain a membrane-attaching solution; the volume of the tap water is 0.6 times of the accumulation volume of the machine-made sand;
step two: stirring and washing machine-made sand for 6 minutes by using a stirring and washing barrel, then placing the machine-made sand on a mesh screen for airing for 35 minutes, and then placing the machine-made sand in an oven for heating and drying; adding the dried machine-made sand into membrane attaching liquid, stirring for 6.5 minutes, pouring into a tray, placing in an oven, heating and drying to attach the nano montmorillonite to the surface of the machine-made sand, and obtaining the machine-made sand by a film attaching machine;
step three: dividing boron, carbon and nitrogen into two parts according to the weight, adding one part of boron, carbon and nitrogen and cement into a stirrer, mixing and stirring for 2.5 minutes, adding film-coated machine-made sand, and continuously stirring for 1.5 minutes to obtain a solid mixture;
step four: adding another part of boron, carbon and nitrogen into deionized water for ultrasonic dispersion for 20 minutes to obtain boron, carbon and nitrogen dispersion liquid;
step five: and adding the boron-carbon-nitrogen dispersion liquid into the solid mixture, and stirring for 2.5 minutes to prepare the photocatalytic cement mortar.
Comparative example 1: without adding nano montmorillonite
In the comparative example, the cement mortar comprises the following raw materials in parts by weight: 5 parts of cement, 15 parts of machine-made sand, 0.005 part of boron, carbon and nitrogen and 2.5 parts of deionized water.
In the comparative example, the preparation method of the photocatalytic cement mortar is carried out according to the following steps:
the method comprises the following steps: dividing boron, carbon and nitrogen into two parts according to the weight, adding one part of boron, carbon and nitrogen and cement into a stirrer, mixing and stirring for 2 minutes, adding machine-made sand, and continuously stirring for 1 minute to obtain a solid mixture;
step two: adding another part of boron, carbon and nitrogen into deionized water for ultrasonic dispersion for 15 minutes to obtain boron, carbon and nitrogen dispersion liquid;
step three: and adding the boron-carbon-nitrogen dispersion liquid into the solid mixture, and stirring for 2.5 minutes to prepare the photocatalytic cement mortar.
Comparative example 2: the nano-montmorillonite is not attached to the surface of the machine-made sand
In the comparative example, the cement mortar comprises the following raw materials in parts by weight: 5 parts of cement, 15 parts of machine-made sand, 0.005 part of boron-carbon-nitrogen, 0.006 part of nano montmorillonite and 2.5 parts of deionized water.
In the comparative example, the preparation method of the photocatalytic cement mortar is carried out according to the following steps:
the method comprises the following steps: dividing boron, carbon and nitrogen into two parts according to the weight, adding one part of boron, carbon and nitrogen, cement and nano montmorillonite into a stirrer, mixing and stirring for 3 minutes, adding machine-made sand, and continuously stirring for 1 minute to obtain a solid mixture;
step two: adding another part of boron, carbon and nitrogen into deionized water for ultrasonic dispersion for 15 minutes to obtain boron, carbon and nitrogen dispersion liquid;
step three: and adding the boron-carbon-nitrogen dispersion liquid into the solid mixture, and stirring for 2.5 minutes to prepare the photocatalytic cement mortar.
Comparative example 3: the photocatalytic material is titanium dioxide
In the comparative example, the cement mortar comprises the following raw materials in parts by weight: 5 parts of cement, 15 parts of machine-made sand, 0.005 part of titanium dioxide, 0.006 part of nano montmorillonite and 2.5 parts of deionized water.
In the comparative example, the preparation method of the photocatalytic cement mortar is carried out according to the following steps:
the method comprises the following steps: adding nano montmorillonite into tap water, and stirring for 40 minutes at a rotating speed of 5500r/min by using a dispersion instrument to obtain a membrane-attaching solution; the volume of the tap water is 0.52 times of the accumulation volume of the machine-made sand;
step two: stirring and washing the machine-made sand for 5.5 minutes by using a stirring and washing barrel, then placing the machine-made sand on a mesh screen for airing for 30 minutes, and then placing the machine-made sand in an oven for heating and drying; adding the dried machine-made sand into membrane attaching liquid, stirring for 6 minutes, pouring into a tray, placing in an oven, heating and drying to attach the nano montmorillonite to the surface of the machine-made sand, and obtaining the machine-made sand attached with a membrane;
step three: dividing titanium dioxide into two parts according to weight, adding one part of titanium dioxide and cement into a stirrer, mixing and stirring for 2 minutes, adding film-coated machine-made sand, and continuously stirring for 1.5 minutes to obtain a solid mixture;
step four: adding the other part of titanium dioxide into deionized water for ultrasonic dispersion for 15 minutes to obtain a titanium dioxide dispersion liquid;
step five: and adding the titanium dioxide dispersion liquid into the solid mixture, and stirring for 2.5 minutes to prepare the photocatalytic cement mortar.
Comparative example 4: the photocatalytic material is graphite phase carbon nitride
In the comparative example, the cement mortar comprises the following raw materials in parts by weight: 5 parts of cement, 15 parts of machine-made sand, 0.005 part of graphite-phase carbon nitride, 0.006 part of nano montmorillonite and 2.5 parts of deionized water.
In the comparative example, the preparation method of the photocatalytic cement mortar is carried out according to the following steps:
the method comprises the following steps: adding nano montmorillonite into tap water, and stirring for 40 minutes at a rotating speed of 5500r/min by using a dispersion instrument to obtain a membrane-attaching solution; the volume of the tap water is 0.52 times of the accumulation volume of the machine-made sand;
step two: stirring and washing the machine-made sand for 5.5 minutes by using a stirring and washing barrel, then placing the machine-made sand on a mesh screen for airing for 30 minutes, and then placing the machine-made sand in an oven for heating and drying; adding the dried machine-made sand into membrane attaching liquid, stirring for 6 minutes, pouring into a tray, placing in an oven, heating and drying to attach the nano montmorillonite to the surface of the machine-made sand, and obtaining the machine-made sand attached with a membrane;
step three: dividing the graphite-phase carbon nitride into two parts according to the weight, adding one part of the graphite-phase carbon nitride and cement into a stirrer, mixing and stirring for 2 minutes, adding the film-attached machine-made sand, and continuously stirring for 1.5 minutes to obtain a solid mixture;
step four: adding the other part of graphite-phase carbon nitride into deionized water for ultrasonic dispersion for 15 minutes to obtain graphite-phase carbon nitride dispersion liquid;
step five: and adding the graphite phase carbon nitride dispersion liquid into the solid mixture, and stirring for 2.5 minutes to prepare the photocatalytic cement mortar.
Measurement of photocatalytic efficiency:
according to the raw material ratio and the preparation method of the above examples 1-3 and comparative examples 1-4, cement mortar test pieces with the diameter of 31mm and the thickness of 9mm are respectively prepared. After the test piece is maintained for 7 days, measuring the photocatalytic efficiency;
the photocatalytic efficiency of the test piece was measured as follows:
the test uses NO with a gas concentration of 10ppm as the photocatalytic object. The concentration of NO was measured using a model GASTiger6000 complex gas analyzer. Placing a cement mortar test piece in a closed and light-transmitting experiment container, and placing a xenon lamp light source on the top of the experiment container, which is opposite to the cement mortar test piece;
firstly, gas is introduced into an experimental container until the concentration is 0.3ppm, then the reaction is stopped, and after standing and stabilizing for 40 minutes, the gas concentration is recorded as an initial value P0(ii) a Then, the light source is turned on, and the timing is started to obtain the gas concentrations P of four time nodes of the 30 th minute, the 60 th minute, the 90 th minute and the 120 th minute respectivelyiI =1,2,3, 4; photocatalytic efficiency viThe calculation formula of (2) is as follows: v. ofi=（P0-Pi）/ P0X 100%, the calculation results are shown in Table 1.
TABLE 1
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can make equivalent changes and modifications within the technical scope of the present invention disclosed by the present invention.
Claims (9)
1. The preparation method of the boron-carbon-nitrogen-containing photocatalytic cement mortar is characterized by comprising the following steps of: the photocatalytic cement mortar comprises the following raw materials in parts by weight: 4-10 parts of cement, 10-35 parts of machine-made sand, 0.004-0.02 part of boron-carbon-nitrogen, 0.005-0.014 part of nano montmorillonite and 2-6 parts of deionized water;
the preparation method of the boron-carbon nitrogen containing photocatalytic cement mortar comprises the following steps:
the method comprises the following steps: preparing membrane attaching liquid; adding nano montmorillonite with volume of V1Stirring the raw materials in the tap water for 25-50 minutes by a dispersion instrument at a rotating speed of 5500-9000 r/min to obtain a membrane-attaching solution; the V is1=（0.45~0.9）V2In which V is2The stacking volume of the machine-made sand;
step two: coating a film on the surface of the machine-made sand; stirring and washing the machine-made sand for 5-8 minutes by using a stirring and washing barrel, then airing the machine-made sand on a mesh screen for 25-40 minutes, and then placing the machine-made sand in an oven for heating and drying; adding the dried machine-made sand into membrane attaching liquid, stirring for 5-8 minutes, pouring into a tray, placing in an oven, heating and drying to attach the nano montmorillonite to the surface of the machine-made sand, and obtaining the machine-made sand by a film attaching machine;
step three: preparing a solid mixture; equally dividing boron, carbon and nitrogen into two parts according to weight, adding one part of boron, carbon and nitrogen and cement into a stirrer, mixing and stirring for 2-3.5 minutes, adding film-coated machine-made sand, and continuously stirring for 1-2 minutes to obtain a solid mixture;
step four: preparing boron carbon nitrogen dispersion liquid; adding another part of boron-carbon-nitrogen into deionized water for ultrasonic dispersion for 10-30 minutes to obtain a boron-carbon-nitrogen dispersion liquid;
step five: preparing photocatalytic cement mortar; and adding the boron-carbon-nitrogen dispersion liquid into the solid mixture, and stirring for 2-3.5 minutes to prepare the photocatalytic cement mortar.
2. The method of claim 1, wherein: and in the second step, the temperature of the oven is 65-110 ℃, and the time for heating and drying each time is 180-360 minutes.
3. The method of claim 1, wherein: and in the fourth step, the frequency of ultrasonic dispersion is 18-26 kHz.
4. The method of claim 1, wherein: the photocatalytic cement mortar comprises the following raw materials in parts by weight: 4.5-8 parts of cement, 13-25 parts of machine-made sand, 0.004-0.015 part of boron-carbon-nitrogen, 0.0053-0.011 part of nano montmorillonite and 2.2-4.8 parts of deionized water.
5. The method of claim 1, wherein: the photocatalytic cement mortar comprises the following raw materials in parts by weight: 5 parts of cement, 15 parts of machine-made sand, 0.005 part of boron carbon nitrogen, 0.006 part of nano montmorillonite and 2.5 parts of deionized water.
6. The method of claim 1, wherein: the grain size of the machine-made sand is 0.25-4.75 mm, and the grain size of the nano montmorillonite is 20-65 nm.
7. The method of claim 1, wherein: the cement is any one of ordinary portland cement, slag portland cement and fly ash portland cement.
8. The method of claim 1, wherein: the boron carbon nitride is nano boron carbon nitride with a three-dimensional layered porous structure.
9. The method of claim 1, wherein: the boron carbon nitride is a photocatalyst obtained by carbon doping of h-BN, and the specific method is that 2 parts by weight of boron source, 2-7 parts by weight of carbon source and 2-4 parts by weight of urea are adopted and prepared under the condition of 1250 ℃ in the atmosphere of ammonia gas; the boron source is boron oxide or boric acid; the carbon source is glucose or sucrose or fructose.
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