CN113649003A - Ion-modified red mud-based heterojunction photocatalyst and preparation method and application thereof - Google Patents
Ion-modified red mud-based heterojunction photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000004108 freeze drying Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000000084 colloidal system Substances 0.000 claims abstract description 9
- 238000007710 freezing Methods 0.000 claims abstract description 6
- 230000008014 freezing Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 29
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 230000015556 catabolic process Effects 0.000 claims description 11
- 238000006731 degradation reaction Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- 238000010306 acid treatment Methods 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 description 58
- 238000006243 chemical reaction Methods 0.000 description 24
- 238000012360 testing method Methods 0.000 description 24
- 238000003756 stirring Methods 0.000 description 21
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 17
- 238000001179 sorption measurement Methods 0.000 description 16
- 230000001699 photocatalysis Effects 0.000 description 10
- 230000000593 degrading effect Effects 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 230000003247 decreasing effect Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 230000020477 pH reduction Effects 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 8
- 229910052724 xenon Inorganic materials 0.000 description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 8
- 239000002910 solid waste Substances 0.000 description 7
- 239000010865 sewage Substances 0.000 description 5
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910021281 Co3O4In Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention provides an ion-modified red mud-based heterojunction photocatalyst as well as a preparation method and application thereof, wherein the method comprises the following steps: step 1, sequentially acidifying and drying red mud to obtain acid-activated red mud; step 2, according to the formula (4-8): (4-8): (2-5) uniformly mixing the acid-activated red mud, hexadecyl trimethyl ammonium bromide and cobalt nitrate in deionized water to obtain a turbid liquid; and 3, firstly adding a sodium silicate solution into the turbid liquid to obtain a mixed system, then adjusting the pH value of the mixed system to 2-4 to obtain a colloid, firstly freezing the colloid, then freeze-drying to obtain a mixture, and finally roasting the mixture at 800 ℃ to obtain the ion-modified red mud-based heterojunction photocatalyst.
Description
Technical Field
The invention relates to the field of photocatalytic degradation of organic pollutants and resource utilization of solid wastes, in particular to an ion-modified red mud-based heterojunction photocatalyst and a preparation method and application thereof.
Background
How to utilize red mud is always a problem which is widely concerned, because red mud is a material with extremely high utilization value, and contains a large amount of ferric oxide, the ferric oxide is a photocatalyst and has good electron transmission efficiency, so how to utilize ferric oxide is the key point of attention of technologists.
Along with the stricter and stricter environmental protection, the problem of sewage pollution is urgently needed to be solved, and the method for treating sewage by using the photocatalyst is a simple and efficient method, so that resources can be saved, the environment is protected, the photocatalyst can be efficiently recycled, and the resources can be saved. Photocatalysis utilizes light excitation to generate photoproduction electrons and holes, then the electrons are transferred to form a certain active group to react with organic pollutants, and then the active group is degraded, so that a water body is purified, resources are saved, and the method is an efficient pollution-free treatment mode in the aspect of sewage treatment. Therefore, a large amount of ferric oxide in the red mud is utilized to form a heterojunction photocatalytic material, and the problems that sewage treatment is difficult and organic pollutants in sewage are degraded in a catalytic manner are solved urgently.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the ion-modified red mud-based heterojunction photocatalyst as well as the preparation method and the application thereof, so that the problem of mass accumulation of solid wastes is solved, the solid wastes are changed into valuable, and the effect of recycling is achieved.
The invention is realized by the following technical scheme:
a preparation method of an ion-modified red mud-based heterojunction photocatalyst comprises the following steps:
step 1, sequentially carrying out acid treatment and drying on red mud to obtain acid-treated red mud;
step 2, according to the formula (4-8): (4-8): (2-5) uniformly mixing the acid-activated red mud, hexadecyl trimethyl ammonium bromide and cobalt nitrate in deionized water to obtain a turbid liquid;
and 3, adding a sodium silicate solution into the turbid liquid to obtain a mixed system, then adjusting the pH value of the mixed system to 2-4 to obtain a colloidal body, freezing the colloidal body, then adopting a freeze drying technology to obtain a porous block body, and finally roasting the porous block body at the temperature of 500-800 ℃ to obtain the ion-modified red mud-based heterojunction photocatalyst.
Preferably, the red mud in the step 1 is obtained according to the following processes:
drying the untreated red mud, then sequentially grinding and sieving with a 150-mesh sieve to obtain the red mud.
Preferably, in the step 1, sulfuric acid with the concentration of 1-5mol/L is used for soaking the red mud, so that the acid treatment of the red mud is completed.
Preferably, the mass ratio of the sodium silicate added in the step 3 to the cobalt nitrate in the step 2 is (11.368-17.052): (2-5).
Preferably, step 3 uses 1mol/L hydrochloric acid to adjust the pH of the mixed system.
Preferably, step 3 freeze-dries the gel after freezing for 5-8 h.
Preferably, step 3, adding a sodium silicate solution into the turbid solution, and stirring for 2-4h to obtain a mixed system.
Preferably, step 3 fires the porous block at said temperature for 5-7 hours.
An ion-modified red mud-based heterojunction photocatalyst obtained by the preparation method of the ion-modified red mud-based heterojunction photocatalyst.
The application of the ion-modified red mud-based heterojunction photocatalyst in the degradation of methylene blue.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a preparation method of an ion-modified red mud-based heterojunction photocatalyst, which comprises the steps of firstly carrying out acid treatment on red mud to enable Fe in the red mud2O3The content of the cobalt nitrate is increased, the content of other alkaline oxides is reduced, a certain amount of red mud is treated by utilizing hexadecyl trimethyl ammonium bromide to activate the surface of the red mud, so that the cobalt nitrate can be uniformly mixed with a certain amount of red mud to obtain turbid liquid, then sodium silicate solution is added, and a colloid body can be formed by adjusting the pH of the mixed system to be strong acid, wherein Fe (OH) in the colloid body3The surface of the material is loaded with a large amount of cobalt nitrate, the cobalt nitrate is frozen at low temperature, the freezing and drying technology is further adopted to sublimate the solidified moisture in the material to obtain a block body with a porous structure, and the block body is roasted to form Fe2O3And Co3O4The heterojunction structure of (1). Fe2O3/Co3O4The heterojunction can degrade methylene blue. Solves the problem of mass accumulation of the solid waste red mud, changes the solid waste red mud into valuable, and realizes the resource utilization of the solid waste red mud.
Fe of the invention2O3/Co3O4The heterojunction can perform sufficient light absorption when degrading methylene blue, so as to generate more photo-generated electrons and holes, and the methylene blue can be degraded by more than 90%. The invention can achieve the purpose of treating wastes with wastes by utilizing solid wastes such as red mud.
Drawings
FIG. 1 is a UV-Vis spectrum of the material obtained in example 1 after two half-hour photoreaction degradations.
FIG. 2 is an X-ray diffraction pattern of the material obtained in example 1.
FIG. 3 is a physical diagram of the material obtained in example 1.
The specific implementation mode is as follows:
the present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention relates to a preparation method of an ion-modified red mud-based heterojunction photocatalyst, which comprises the following steps:
the method comprises the following steps: drying the red mud in an oven at 60-80 ℃ for 24-48 hours, grinding, sieving with a 150-mesh sieve, then acidifying in 5-15mL of 1-5mol/L sulfuric acid solution, and drying to obtain the acid-activated red mud. After acidification, Fe in red mud2O3The content of (b) is increased and the content of other basic oxides is decreased.
Step two: 4-8g of cetyltrimethylammonium bromide was dissolved in 100-300 mL of deionized water to give solution A.
Step three: then 2-5g of cobalt nitrate is dissolved in the solution A, and the solution B is obtained after stirring for 20 min.
Step four: and then adding 4-8g of acid activated red mud into the solution B, and then uniformly stirring for 20min generally to form a turbid solution C, so that cobalt nitrate and the red mud can be uniformly mixed and stirred.
Step five: then adding 20mL of sodium silicate solution with the concentration of 2-4mol/L into the turbid liquid C, stirring for 2-4 hours, adjusting the pH to 2-4 by using 1mol/L hydrochloric acid to form colloid, wherein Fe (OH) is contained in the colloid3The surface of (a) is loaded with a large amount of cobalt nitrate. It was then transferred to a freezer for 6 hours.
Step six: then the frozen colloid is put into a freeze drying box for freeze drying for 5 to 8 hours. When the material is dried, water on the surface of the material can be separated from the gaps to form a porous structure.
Step seven: then the formed porous material is put into a muffle furnace to be baked at the temperature of 500-800 DEG CAnd firing for 5-7 hours to finally form the red mud-based heterojunction photocatalytic material. Will increase the Fe of the material after acidification2O3The amount of other basic oxides decreases and Fe is formed after firing in a muffle furnace2O3/Co3O4A heterojunction structure.
The steps for degrading the methylene blue solution are as follows:
adding 100mL of methylene blue solution with the concentration of 0.04g/L into a test tube, then adding 0.4g of the material into the test tube for adsorption, carrying out a dark reaction adsorption experiment for 30min, then carrying out a reaction process in a light reaction stage, carrying out photocatalytic degradation by using a 300W xenon lamp as a light source, sampling for 3mL every 30min, centrifuging the sampled sample, testing by using ultraviolet-visible spectrophotometry, and calculating the photocatalytic degradation condition of the material according to the obtained curve.
Example 1:
the invention relates to a preparation method of an ion-modified red mud-based heterojunction photocatalyst, which comprises the following steps:
the method comprises the following steps: drying the red mud in an oven at 60 ℃ for 24 hours, grinding, sieving by a 150-mesh sieve, then acidifying in 5mL of sulfuric acid solution with the concentration of 1mol/L, and drying to obtain the acid-activated red mud. The material after acidification can lead Fe in the red mud2O3The content of (b) is increased and the content of other basic oxides is decreased.
Step two: 4g of cetyltrimethylammonium bromide was dissolved in 100mL of deionized water to obtain solution A.
Step three: then, 2g of cobalt nitrate was dissolved in the solution A, and the solution B was obtained by stirring for 20 min.
Step four: and then adding 4g of acid activated red mud into the solution B, and then uniformly stirring for 20min to form a turbid solution C, so that the cobalt nitrate and the red mud can be uniformly mixed and stirred.
Step five: then, 20mL of a 3mol/L sodium silicate solution was added to the turbid solution C, followed by stirring for 2 hoursAdjusting the pH to 2 with 1mol/L hydrochloric acid to form a colloid, Fe (OH)3The surface of (a) is loaded with a large amount of cobalt nitrate. It was then transferred to a freezer for 6 hours.
Step six: the frozen gel was then dried in a freeze drying oven for 6 hours. Water on the surface of the material separates from the gaps during drying, forming a porous structure.
Step seven: and then placing the formed porous material into a muffle furnace to be roasted for 5 hours at 500 ℃, and finally forming the red mud-based heterojunction photocatalytic material. Will increase the Fe of the material after acidification2O3The amount of other basic oxides decreases and a heterojunction structure is formed after firing in a muffle furnace.
It can be seen from FIG. 2 that the resulting material contains a large amount of Fe2O3And Co3O4In which a small amount of basic oxide is present, the resulting structure is hardly affected.
As can be seen in fig. 3, the material appears red overall.
The steps for degrading the methylene blue solution are as follows:
adding 100mL of methylene blue solution with the concentration of 0.04g/L into a test tube, then adding 0.4g of the material into the test tube for adsorption, carrying out a dark reaction adsorption experiment for 30min, then carrying out a reaction process in a light reaction stage, carrying out photocatalytic degradation by using a 300W xenon lamp as a light source, sampling for 3mL every 30min, centrifuging the sampled sample, testing by using ultraviolet-visible spectrophotometry, and calculating the photocatalytic degradation condition of the material according to the obtained curve. The calculated degradation rate of methylene blue of the material was 90%, and it can be seen in particular from fig. 1 that after degradation after two and a half hours, it can be found that the methylene blue is almost completely degraded.
Example 2:
the invention relates to a preparation method of an ion-modified red mud-based heterojunction photocatalyst, which comprises the following steps:
the method comprises the following steps: drying the red mud in an oven at 60 ℃ for 24 hours, grinding, sieving by a 150-mesh sieve, then acidifying in 5mL of sulfuric acid solution with the concentration of 2mol/L, and drying to obtain the acid-activated red mud. The material after acidification can lead Fe in the red mud2O3The content of (b) is increased and the content of other basic oxides is decreased.
Step two: 4g of cetyltrimethylammonium bromide was dissolved in 150mL of deionized water to obtain solution A.
Step three: then, 3g of cobalt nitrate was dissolved in the solution A, and the solution B was obtained by stirring for 20 min.
Step four: and then adding 5g of acid activated red mud into the solution B, and then uniformly stirring for 20min to form a turbid solution C, so that the cobalt nitrate and the red mud can be uniformly mixed and stirred.
Step five: then, 20mL of a 3mol/L sodium silicate solution was added to the turbid liquid C, followed by stirring for 2 hours, adjusting the pH to 4 with 1mol/L hydrochloric acid to form a gelatinous body, Fe (OH)3The surface of (a) is loaded with a large amount of cobalt nitrate. It was then transferred to a freezer for 6 hours.
Step six: the frozen gel was then dried in a freeze drying oven for 6 hours. Water on the surface of the material separates from the gaps during drying, forming a porous structure.
Step seven: and then placing the formed porous material into a muffle furnace to be roasted for 5 hours at the temperature of 550 ℃, and finally forming the red mud-based heterojunction photocatalytic material. Will increase the Fe of the material after acidification2O3The amount of other basic oxides decreases and a heterojunction structure is formed after firing in a muffle furnace.
The steps for degrading the methylene blue solution are as follows:
adding 100mL of methylene blue solution with the concentration of 0.04g/L into a test tube, then adding 0.4g of the material into the test tube for adsorption, carrying out a dark reaction adsorption experiment for 30min, then carrying out a reaction process in a light reaction stage, carrying out photocatalytic degradation by using a 300W xenon lamp as a light source, sampling for 3mL every 30min, centrifuging the sampled sample, testing by using ultraviolet-visible spectrophotometry, and calculating the photocatalytic degradation condition of the material according to the obtained curve. The degradation rate of methylene blue was calculated to be 92%.
Example 3:
the invention relates to a preparation method of an ion-modified red mud-based heterojunction photocatalyst, which comprises the following steps:
the method comprises the following steps: drying the red mud in an oven at 60 ℃ for 48 hours, grinding, sieving with a 150-mesh sieve, acidifying in 5mL of 3mol/L sulfuric acid solution, and drying to obtain the acid-activated red mud. The material after acidification can lead Fe in the red mud2O3The content of (b) is increased and the content of other basic oxides is decreased.
Step two: 6g of cetyltrimethylammonium bromide was dissolved in 100mL of deionized water to obtain solution A.
Step three: then, 5g of cobalt nitrate was dissolved in the solution A, and the solution B was obtained by stirring for 20 min.
Step four: then 6g of acid activated red mud is added into the solution B, and then the solution B is uniformly stirred for 20min to form a turbid solution C, so that cobalt nitrate and the red mud can be uniformly mixed and stirred.
Step five: then, 20mL of a 4mol/L sodium silicate solution was added to the turbid liquid C, followed by stirring for 3 hours, adjusting the pH to 3 with 1mol/L hydrochloric acid to form a gelatinous body, Fe (OH)3The surface of (a) is loaded with a large amount of cobalt nitrate. It was then transferred to a freezer for 6 hours.
Step six: the frozen gel was then dried in a freeze drying oven for 5 hours. Water on the surface of the material separates from the gaps during drying, forming a porous structure.
Step seven: and then placing the formed porous material into a muffle furnace to be roasted for 5 hours at the temperature of 600 ℃, and finally forming the red mud-based heterojunction photocatalytic material. Will increase the Fe of the material after acidification2O3The amount of other basic oxides decreases and a heterojunction structure is formed after firing in a muffle furnace.
The steps for degrading the methylene blue solution are as follows:
adding 100mL of methylene blue solution with the concentration of 0.04g/L into a test tube, then adding 0.4g of the material into the test tube for adsorption, carrying out a dark reaction adsorption experiment for 30min, then carrying out a reaction process in a light reaction stage, carrying out photocatalytic degradation by using a 300W xenon lamp as a light source, sampling for 3mL every 30min, centrifuging the sampled sample, testing by using ultraviolet-visible spectrophotometry, and calculating the photocatalytic degradation condition of the material according to the obtained curve. The degradation rate of methylene blue was calculated to be 85%.
Example 4:
the invention relates to a preparation method of an ion-modified red mud-based heterojunction photocatalyst, which comprises the following steps:
the method comprises the following steps: drying the red mud in an oven at 60 ℃ for 48 hours, grinding, sieving with a 150-mesh sieve, acidifying in 10mL of 3mol/L sulfuric acid solution, and drying to obtain the acid-activated red mud. The material after acidification can lead Fe in the red mud2O3The content of (b) is increased and the content of other basic oxides is decreased.
Step two: 6g of cetyltrimethylammonium bromide was dissolved in 150mL of deionized water to obtain solution A.
Step three: then, 5g of cobalt nitrate was dissolved in the solution A, and the solution B was obtained by stirring for 20 min.
Step four: then 6g of acid activated red mud is added into the solution B, and then the solution B is uniformly stirred for 20min to form a turbid solution C, so that cobalt nitrate and the red mud can be uniformly mixed and stirred.
Step five: then, 20mL of a 3mol/L sodium silicate solution was added to the turbid liquid C, followed by stirring for 3 hours, adjusting the pH to 2 with 1mol/L hydrochloric acid to form a gelatinous body, Fe (OH)3The surface of (a) is loaded with a large amount of cobalt nitrate. Then transfer itFreezing for 6 hours in a freezer.
Step six: the frozen gel was then dried in a freeze drying oven for 8 hours. Water on the surface of the material separates from the gaps during drying, forming a porous structure.
Step seven: and then placing the formed porous material into a muffle furnace to be roasted for 5 hours at 650 ℃, and finally forming the red mud-based heterojunction photocatalytic material. Will increase the Fe of the material after acidification2O3The amount of other basic oxides decreases and a heterojunction structure is formed after firing in a muffle furnace.
The steps for degrading the methylene blue solution are as follows:
adding 100mL of methylene blue solution with the concentration of 0.04g/L into a test tube, then adding 0.4g of the material into the test tube for adsorption, carrying out a dark reaction adsorption experiment for 30min, then carrying out a reaction process in a light reaction stage, carrying out photocatalytic degradation by using a 300W xenon lamp as a light source, sampling for 3mL every 30min, centrifuging the sampled sample, testing by using ultraviolet-visible spectrophotometry, and calculating the photocatalytic degradation condition of the material according to the obtained curve. The degradation rate of methylene blue was calculated to be 80%.
Example 5:
the invention relates to a preparation method of an ion-modified red mud-based heterojunction photocatalyst, which comprises the following steps:
the method comprises the following steps: drying the red mud in an oven at 70 ℃ for 24 hours, grinding, sieving by a 150-mesh sieve, then acidifying in 10mL of sulfuric acid solution with the concentration of 4mol/L, and drying to obtain the acid-activated red mud. The material after acidification can lead Fe in the red mud2O3The content of (b) is increased and the content of other basic oxides is decreased.
Step two: 6g of cetyltrimethylammonium bromide was dissolved in 200mL of deionized water to obtain solution A.
Step three: then 4g of cobalt nitrate was dissolved in the solution A, and the solution B was obtained by stirring for 20 min.
Step four: then 8g of acid activated red mud is added into the solution B, and then the solution B is uniformly stirred for 20min to form a turbid solution C, so that cobalt nitrate and the red mud can be uniformly mixed and stirred.
Step five: then, 20mL of a 4mol/L sodium silicate solution was added to the turbid liquid C, followed by stirring for 2 hours, adjusting the pH to 4 with 1mol/L hydrochloric acid to form a gelatinous body, Fe (OH)3The surface of (a) is loaded with a large amount of cobalt nitrate. It was then transferred to a freezer for 6 hours.
Step six: the frozen gel was then dried in a freeze drying oven for 7 hours. Water on the surface of the material separates from the gaps during drying, forming a porous structure.
Step seven: and then placing the formed porous material into a muffle furnace to be roasted for 6 hours at 700 ℃, and finally forming the red mud-based heterojunction photocatalytic material. Will increase the Fe of the material after acidification2O3The amount of other basic oxides decreases and a heterojunction structure is formed after firing in a muffle furnace.
The steps for degrading the methylene blue solution are as follows:
adding 100mL of methylene blue solution with the concentration of 0.04g/L into a test tube, then adding 0.4g of the material into the test tube for adsorption, carrying out a dark reaction adsorption experiment for 30min, then carrying out a reaction process in a light reaction stage, carrying out photocatalytic degradation by using a 300W xenon lamp as a light source, sampling for 3mL every 30min, centrifuging the sampled sample, testing by using ultraviolet-visible spectrophotometry, and calculating the photocatalytic degradation condition of the material according to the obtained curve. The degradation rate of methylene blue was calculated to be 86%.
Example 6:
the invention relates to a preparation method of an ion-modified red mud-based heterojunction photocatalyst, which comprises the following steps:
the method comprises the following steps: drying red mud in an oven at 70 ℃ for 48 hours, grinding, sieving with a 150-mesh sieve, and concentrating in 15mLAcidifying in a sulfuric acid solution with the degree of 5mol/L, and drying to obtain the acid-activated red mud. The material after acidification can lead Fe in the red mud2O3The content of (b) is increased and the content of other basic oxides is decreased.
Step two: 8g of cetyltrimethylammonium bromide was dissolved in 250mL of deionized water to obtain solution A.
Step three: then, 5g of cobalt nitrate was dissolved in the solution A, and the solution B was obtained by stirring for 20 min.
Step four: and then adding 7g of acid activated red mud into the solution B, and then uniformly stirring for 20min generally to form a turbid solution C, so that the cobalt nitrate and the red mud can be uniformly mixed and stirred.
Step five: then, 20mL of a 4mol/L sodium silicate solution was added to the turbid liquid C, followed by stirring for 4 hours, adjusting the pH to 3 with 1mol/L hydrochloric acid to form a gelatinous body, Fe (OH)3The surface of (a) is loaded with a large amount of cobalt nitrate. It was then transferred to a freezer for 6 hours.
Step six: the frozen gel was then dried in a freeze drying oven for 7 hours. Water on the surface of the material separates from the gaps during drying, forming a porous structure.
Step seven: and then placing the formed porous material into a muffle furnace to be roasted for 5 hours at 800 ℃, and finally forming the red mud-based heterojunction photocatalytic material. Will increase the Fe of the material after acidification2O3The amount of other basic oxides decreases and a heterojunction structure is formed after firing in a muffle furnace.
The steps for degrading the methylene blue solution are as follows:
adding 100mL of methylene blue solution with the concentration of 0.04g/L into a test tube, then adding 0.4g of the material into the test tube for adsorption, carrying out a dark reaction adsorption experiment for 30min, then carrying out a reaction process in a light reaction stage, carrying out photocatalytic degradation by using a 300W xenon lamp as a light source, sampling for 3mL every 30min, centrifuging the sampled sample, testing by using ultraviolet-visible spectrophotometry, and calculating the photocatalytic degradation condition of the material according to the obtained curve. The degradation rate of methylene blue was calculated to be 76%.
Example 7:
the invention relates to a preparation method of an ion-modified red mud-based heterojunction photocatalyst, which comprises the following steps:
the method comprises the following steps: drying the red mud in an oven at 80 ℃ for 48 hours, grinding, sieving by a 150-mesh sieve, then acidifying in 5mL of sulfuric acid solution with the concentration of 3mol/L, and drying to obtain the acid-activated red mud. The material after acidification can lead Fe in the red mud2O3The content of (b) is increased and the content of other basic oxides is decreased.
Step two: 4g of cetyltrimethylammonium bromide was dissolved in 300mL of deionized water to obtain solution A.
Step three: then, 5g of cobalt nitrate was dissolved in the solution A, and the solution B was obtained by stirring for 20 min.
Step four: then 8g of acid activated red mud is added into the solution B, and then the solution B is uniformly stirred for 20min to form a turbid solution C, so that cobalt nitrate and the red mud can be uniformly mixed and stirred.
Step five: then, 20mL of a 3mol/L sodium silicate solution was added to the turbid liquid C, followed by stirring for 2 hours, adjusting the pH to 2 with 1mol/L hydrochloric acid to form a gelatinous body, Fe (OH)3The surface of (a) is loaded with a large amount of cobalt nitrate. It was then transferred to a freezer for 6 hours.
Step six: the frozen gel was then dried in a freeze drying oven for 6 hours. Water on the surface of the material separates from the gaps during drying, forming a porous structure.
Step seven: and then placing the formed porous material into a muffle furnace to be roasted for 7 hours at the temperature of 550 ℃, and finally forming the red mud-based heterojunction photocatalytic material. Will increase the Fe of the material after acidification2O3The amount of other basic oxides decreases and a heterojunction structure is formed after firing in a muffle furnace.
The steps for degrading the methylene blue solution are as follows:
adding 100mL of methylene blue solution with the concentration of 0.04g/L into a test tube, then adding 0.4g of the material into the test tube for adsorption, carrying out a dark reaction adsorption experiment for 30min, then carrying out a reaction process in a light reaction stage, carrying out photocatalytic degradation by using a 300W xenon lamp as a light source, sampling for 3mL every 30min, centrifuging the sampled sample, testing by using ultraviolet-visible spectrophotometry, and calculating the photocatalytic degradation condition of the material according to the obtained curve. The degradation rate of methylene blue was calculated to be 78%.
Claims (10)
1. The preparation method of the ion-modified red mud-based heterojunction photocatalyst is characterized by comprising the following steps of:
step 1, sequentially carrying out acid treatment and drying on red mud to obtain acid-treated red mud;
step 2, according to the formula (4-8): (4-8): (2-5) uniformly mixing the acid-activated red mud, hexadecyl trimethyl ammonium bromide and cobalt nitrate in deionized water to obtain a turbid liquid;
and 3, adding a sodium silicate solution into the turbid liquid to obtain a mixed system, then adjusting the pH value of the mixed system to 2-4 to obtain a colloidal body, freezing the colloidal body, then adopting a freeze drying technology to obtain a porous block body, and finally roasting the porous block body at the temperature of 500-800 ℃ to obtain the ion-modified red mud-based heterojunction photocatalyst.
2. The preparation method of the ion-modified red mud-based heterojunction photocatalyst according to claim 1, wherein the red mud in the step 1 is obtained by the following processes:
drying the untreated red mud, then sequentially grinding and sieving with a 150-mesh sieve to obtain the red mud.
3. The preparation method of the ion-modified red mud-based heterojunction photocatalyst according to claim 1, wherein in the step 1, sulfuric acid with a concentration of 1-5mol/L is used for soaking the red mud to complete acid treatment of the red mud.
4. The preparation method of the ion-modified red mud-based heterojunction photocatalyst according to claim 1, wherein the mass ratio of the sodium silicate added in the step 3 to the cobalt nitrate in the step 2 is (11.368-17.052): (2-5).
5. The preparation method of the ion-modified red mud-based heterojunction photocatalyst according to claim 1, wherein 1mol/L hydrochloric acid is used in the step 3 to adjust the pH of the mixed system.
6. The method for preparing the ion-modified red mud-based heterojunction photocatalyst according to claim 1, wherein the colloid after freezing is freeze-dried for 5-8h in the step 3.
7. The preparation method of the ion-modified red mud-based heterojunction photocatalyst according to claim 1, wherein the sodium silicate solution is added into the turbid solution in the step 3, and the mixture is stirred for 2-4 hours to obtain a mixed system.
8. The preparation method of the ion-modified red mud-based heterojunction photocatalyst according to claim 1, wherein in the step 3, the porous block is calcined at the temperature for 5-7 h.
9. An ion-modified red mud-based heterojunction photocatalyst obtained by the method for preparing the ion-modified red mud-based heterojunction photocatalyst according to any one of claims 1 to 8.
10. The application of the ion-modified red mud-based heterojunction photocatalyst as defined in claim 9 in the degradation of methylene blue.
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