CN110652990B - Preparation method of heterojunction-containing supported clay nano photocatalytic material - Google Patents
Preparation method of heterojunction-containing supported clay nano photocatalytic material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 40
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 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 16
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
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- 238000002156 mixing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
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- 229910052724 xenon Inorganic materials 0.000 claims description 3
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- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 claims description 2
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- 238000003911 water pollution Methods 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention belongs to the technical field of nano photocatalytic materials, and provides a preparation method of a heterojunction-containing clay-loaded nano photocatalytic material. Prepared by AgCl, agX and clay according to a certain proportion; x in AgX is Br or I; the clay is bentonite, diatomite or attapulgite. Firstly, adding the dry clay into NaCl solution, and dropwise adding AgNO while stirring 3 Obtaining a binary AgCl/clay catalyst through solution; slowly dripping KI (NaBr) solution, continuously stirring, centrifugally separating the solution, washing with deionized water and drying to obtain the photocatalytic material AgX-AgCl/clay. Silver halide and silver chloride have matched energy level levels, and a silver halide-silver chloride heterojunction is constructed and loaded on the clay of the mineral soil material, so that the defects of easy agglomeration, photo-corrosion and easy decomposition of silver chloride are effectively inhibited, and the stability and the photo-catalytic activity of the silver chloride under illumination are improved. The preparation method is simple, has low cost, and can degrade organic pollutants under the catalysis of visible light.
Description
Technical Field
The invention belongs to the technical field of nano photocatalytic materials, and particularly relates to a preparation method of a heterojunction-containing clay-loaded nano photocatalytic material.
Background
With the continuous development of industrialization and modernization, the problem of water pollution is getting more and more serious. Compared with the traditional water pollution treatment method, the photocatalysis method is green and environment-friendly and has no secondary pollution. The photocatalyst material with good performance is the key for treating water body pollution by a photocatalysis method. At present, most of photocatalysts have photocatalytic activity only under ultraviolet light, and have the defects of narrow photoresponse range, low quantum efficiency and the like. In order to broaden the photoresponse range, various methods have been tried to prepare novel visible light photocatalytic materials. In recent years, agX is increasingly applied to the field of preparation of photocatalysts due to its unique photosensitivity. In a patent of silver halide/silicon titanium aerogel ternary composite photocatalyst and a preparation method thereof (application number 201610658028.3) applied by institute of science and academy of sciences in Shandong province, a multilevel semiconductor composite photocatalyst is prepared by using a silicon titanium aerogel block material as a carrier of silver halide nanoparticles; in a preparation method of a silver halide heterostructure photocatalyst (application number 201210540641.7), the Huainan academy of academic sciences reports that silver halide is loaded on a silicon dioxide carrier through a deposition-precipitation method, and the formed heterojunction nano composite material well improves the photocatalytic activity of the silver halide.
In summary, in the prior art, a multistage load-type material is mainly prepared by coupling AgX and a semiconductor, so that the application of various semiconductor materials increases the industrialization cost and is not beneficial to industrial popularization; and the silver halide is easy to corrode by light, easy to agglomerate, poor in stability and difficult to recover. Therefore, the problem can be better solved by preparing the supported photocatalyst by loading AgX on a carrier with good adsorbability and large specific surface area. The bentonite, the diatomite, the attapulgite and other clays are used as mineral materials with low price and rich raw materials, so that on one hand, the immobilization of active components of the catalyst can be realized, the problems of poor agglomeration stability and difficult recovery of AgX are solved, and on the other hand, photo-generated electrons can be captured by utilizing the interlayer cation capture capacity of the bentonite, the recombination of electrons and holes is inhibited, and the free radical oxidation reaction of the holes is strengthened; on the other hand, the bentonite, the diatomite, the attapulgite and other clays have larger surface areas and better adsorptivity, can adsorb pollutant molecules on the surface of the catalyst, increase the effective contact area of the catalyst and the pollutant molecules directly, and improve the activity of the catalyst. The contact between AgX and organic mineral soil can effectively reduce the contact potential barrier between the photocatalytic material and organic pollutant molecules, and improve the photocatalytic degradation efficiency of organic matters. At present, the application of the AgX and clay heterojunction-containing supported nano material in the aspect of photocatalysis is not reported.
Disclosure of Invention
The invention aims to provide a preparation method and application of a heterojunction-containing supported clay nano photocatalytic material, wherein the heterojunction-containing supported nano photocatalytic material is a novel photocatalyst material formed by forming a heterojunction between silver halide AgX (Br, I) -silver chloride (AgCl) and loading the heterojunction-containing supported nano photocatalytic material on bentonite (diatomite and attapulgite). The material can degrade organic pollutants by photocatalysis under visible light.
The invention is realized by the following technical scheme: a heterojunction-containing clay-loaded nano photocatalytic material is prepared from the following raw materials in percentage by weight: agCl:5.0% -40%; agX:4.0% -16.0%; clay: 54.0% -91.0%; wherein: x in AgX is Br or I; the clay is bentonite, diatomite or attapulgite.
The preparation method of the heterojunction-containing supported clay nano photocatalytic material comprises the following steps:
(1) Preparation of AgCl/Clay: weighing clay according to a certain proportion, mixing the clay in NaCl solution, and dripping AgNO under the stirring state 3 Stirring the solution at room temperature for 4-6 hours, and washing AgCl/clay with deionized water until the pH value of a washing solution is 6-7;
(2) The preparation of the heterojunction-containing supported nano photocatalytic material AgX-AgCl/clay comprises the following steps: dropwise adding a KI or NaBr solution into the prepared AgCl/clay solution; stirring for 10-20 min, centrifugally separating the obtained solution, washing with deionized water until the pH value of the water washing liquid is 6-7, and drying in a drying box to obtain the nano photocatalytic material AgX-AgCl/clay; wherein: KI or NaBr with AgNO 3 The weight ratio of (A) to (B) is as follows: 0.01 to 0.5:0.1 to 1.0.
NaCl and AgNO in step (1) 3 The weight ratio of (A) to (B) is as follows:1.0-2.0: 0.1-1.0. The specific preparation method of AgCl/clay in the step (1) comprises the following steps:
A. 1.0g of dry clay was weighed and uniformly dispersed in 50mL of deionized water, and 50mL of 0.3M NaCl solution was added dropwise with stirring, followed by 100mL of 0.05M AgNO 3 Solutions, i.e. NaCl and AgNO 3 The weight ratio is 1.4;
B. mixing the solution containing clay and NaCl with AgNO 3 After the solution was mixed, stirring was continued at room temperature for 5 hours.
AgNO 3 The dropping speed of (2) to (10) drops per second.
In the step (2), the dropping speed of the KI or NaBr solution is 2-10 drops per second; the concentration of KI or NaBr solution is 0.01-0.05M; KI and AgNO 3 The mass ratio of the components is 0.331: 0.796; naBr and AgNO 3 The mass ratio of (A) to (B) is 0.205: 0.796. The stirring time in the step (2) is 15 min; the drying temperature set by the drying box in the step (2) is 60-80 ℃.
Taking methylene blue, phenol or methyl p-hydroxybenzoate with the concentration of 20 mg/L as a substrate, taking 0.1g of a heterojunction-containing clay-loaded nano photocatalytic material, and filtering ultraviolet light by using an optical filter with a light source of a 300W xenon lamp, wherein the reaction time is 40-120 min.
The supported nanometer photocatalytic material AgX-AgCl/clay containing the heterojunction is used as a photocatalyst, is particularly suitable for being used as a photocatalyst for degrading organic matters in the field of environmental protection, shows strong photocatalytic performance in the aspect of degrading phenol substances such as p-hydroxybenzoate, organic dyes and phenol, and has a wide application range.
AgCl has excellent photocatalytic activity, but the photo-generated electron hole recombination rate is higher, so that the utilization rate of photo-generated carriers is not high, and photo-decomposition and photo-corrosion are easy to occur, so that the stability is poor; the AgI (AgBr) and AgCl form a heterojunction structure, so that the transfer of photoproduction electrons of the composite material is accelerated, and the compounding of photoproduction electron-hole pairs is inhibited, thereby enhancing the photocatalytic performance of the composite material, inhibiting the photolysis and corrosion of the AgCl and effectively improving the stability of the composite material. The AgX (Br, I) -AgCl/clay has a relatively obvious adsorption effect on organic pollutants in a dark reaction stage, because the AgX (Br, I) and the AgCl change the surface appearance of clay bentonite (diatomite and attapulgite), and the specific surface area of the clay is increased, so that the adsorption capacity of the clay is enhanced.
The clay is a reaction carrier and can further increase the adsorption performance of the material, and AgI (AgBr) is formed on the surface of AgCl by KI (NaBr) solution through ion exchange, so that the photocatalytic performance and stability of AgCl are effectively enhanced.
According to the invention, agCl is loaded on the surface of clay, and the activity of the catalyst is effectively distributed by utilizing the developed pore structure of the clay, so that the defect that AgCl is easy to agglomerate is effectively inhibited. The flow of photoproduction electrons can be effectively accelerated by utilizing a heterojunction structure formed between AgX (Br, I) and AgCl, and the separation of electrons and cavities is promoted, so that the photocatalytic activity is improved, the existence of AgX (Br, I) also effectively inhibits the photo-corrosion and decomposition of AgCl, the stability of AgCl under illumination is ensured, and the absorption of the AgCl on visible light is effectively improved.
The preparation process of the supported nanometer photocatalytic material AgX (Br, I) -AgCl/clay containing the heterojunction is simple, and in addition, the composite catalyst can also reduce the consumption of noble metal silver, and has the advantages of low cost and short preparation time.
The heterojunction-containing supported nano photocatalytic material AgX (Br, I) -AgCl/clay provided by the invention has the advantages of wide photoresponse range, high quantum efficiency and the like, and can be applied to the field of environmental protection, particularly to photocatalytic degradation of organic pollutants in water.
Drawings
FIG. 1 is a graph of the degradation kinetics of methylene blue.
FIG. 2 is an SEM image of AgI-AgCl/bentonite.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1: a heterojunction-containing supported bentonite nano photocatalytic material is specifically prepared by the following steps:
(1) Preparation of AgCl/bentonite: weighing 1.0g of dry bentonite, uniformly dispersing in 50mL of deionized water, dropwise adding 50mL of NaCl solution with the concentration of 0.3M under the stirring state, and dropwise adding 100mL of AgNO with the concentration of 0.05M 3 Stirring the solution at room temperature for 5 hours to prepare a photocatalyst AgCl/bentonite, and washing the solution by deionized water until the pH value of a washing solution is 6-7;
(2) Preparation of AgX (Br, I) -AgCl/bentonite: to the AgCl/bentonite suspension prepared in (1) was added dropwise 10 mL of a 0.02M KI (NaBr) solution. Stirring for 15min, centrifuging, washing with deionized water to pH 6-7, and heating to 60-80 deg.c. Drying in a drying box to obtain a composite photocatalytic material sample;
(3) Methylene blue degradation experiment: a xenon lamp with a light source of 300W; 0.1g of the supported nano photocatalytic material containing the heterojunction is weighed and put into 100mL of methylene blue solution, and the result of a photocatalytic degradation experiment shows that after the material is illuminated for 40min, the degradation rate of the methylene blue can reach 90%.
Example 2: this example differs from example 1 in that the NaCl solution added in step (1) has a concentration of 0.28M, followed by dropwise addition of AgNO 3 The concentration of the solution was 0.049M; the concentration of the KI (NaBr) solution dropwise added in the step (2) is 0.015M, and other steps are the same as those in the example 1; in the experiment for degrading methylene blue, the difference from the step (3) of example 1 is that the degradation rate of methylene blue by the photocatalyst sample prepared in this example is 92%.
Example 3: this example differs from example 1 in that the NaCl solution added in step (1) has a concentration of 0.26M, followed by dropwise addition of AgNO 3 The concentration of the solution was 0.048M; the concentration of the KI (NaBr) solution dropwise added in the step (2) is 0.017M, and other steps are the same as those in the embodiment 1; in the experiment for degrading methylene blue, the difference from the step (3) of example 1 is that the degradation rate of methylene blue by the photocatalyst sample prepared in this example is 94%.
Example 4: this example differs from example 1 in the concentration of NaCl solution added in step (1)0.24M, then AgNO added dropwise 3 The concentration of the solution was 0.047M; the concentration of the KI (NaBr) solution added dropwise in the step (2) is 0.018M, and other steps are the same as those in the example 1; in the experiment for degrading methylene blue, the difference from the step (3) of example 1 is that the degradation rate of methylene blue by the photocatalyst sample prepared in this example is 99%.
Example 5: this example differs from example 1 in that the NaCl solution added in step (1) has a concentration of 0.235M, followed by dropwise addition of AgNO 3 The concentration of the solution was 0.0465M; the concentration of the KI (NaBr) solution dripped in the step (2) is 0.019M, and other steps are the same as those in the embodiment 1; in the experiment for degrading methylene blue, the difference from the step (3) of example 1 is that the degradation rate of methylene blue by the photocatalyst sample prepared in this example is 100%.
And (3) explanation of effect detection:
FIG. 1 is a degradation kinetic diagram of the supported nano photocatalytic material AgX (Br, I) -AgCl/bentonite containing heterojunction obtained in examples 1 to 5 on methylene blue in visible light catalytic degradation. As can be seen from the figure, the methylene blue with the initial concentration of 20 mg/L can be completely degraded within 40min by the photocatalytic material prepared in the invention, and the photocatalytic material has excellent photocatalytic performance.
Example 6: this example is different from example 5 in that methyl parahydroxybenzoate was selected in step (3) to evaluate the photocatalytic activity of the catalyst prepared in example 5, and the degradation rate of methyl parahydroxybenzoate was 98%.
Example 7: this example is different from example 5 in that phenol was selected in step (3) to evaluate the photocatalytic activity of the catalyst prepared in example 5, and the light irradiation time period was changed to 120min, and the degradation rate of phenol was 68%.
Claims (8)
1. A heterojunction-containing clay-supported nano photocatalytic material is characterized in that: the composite material is prepared from the following raw materials in percentage by weight: agCl:5% -40%; agX:4 to 16 percent; clay: 54 to 91 percent; wherein: x in AgX is Br or I; the clay is bentonite, diatomite or attapulgite;
the preparation method comprises the following steps:
(1) AgCl/clay: weighing clay according to a certain proportion, mixing the clay in NaCl solution, and dripping AgNO under the stirring state 3 Stirring the solution at room temperature for 4-6 hours, and washing AgCl/clay with deionized water until the pH value of a washing solution is 6-7;
(2) Preparation of the heterojunction-containing supported nano photocatalytic material AgX-AgCl/clay: dropwise adding a KI or NaBr solution into the prepared AgCl/clay solution; stirring for 10-20 min, centrifuging the obtained solution, washing with deionized water until the pH value of the washing liquid is 6-7, and drying in a drying box to obtain the nano photocatalytic material AgX-AgCl/clay; wherein: KI or NaBr with AgNO 3 The mass ratio of the components is as follows: 0.01 to 0.5:0.1 to 1.0.
2. The photocatalyst material containing heterojunction loading clay nanometer according to claim 1, wherein: naCl and AgNO in step (1) 3 The mass ratio of the components is as follows: 1.0-2.0: 0.1-1.0.
3. The photocatalyst material containing heterojunction loading clay nanometer as claimed in claim 1, wherein: the specific preparation method of AgCl/clay in the step (1) comprises the following steps:
A. 1.0g of dry clay was weighed out and uniformly dispersed in 50mL of deionized water, and 50mL of a 0.3M NaCl solution was added dropwise with stirring, followed by 100mL of 0.05M AgNO 3 A solution;
B. mixing the solution containing clay and NaCl with AgNO 3 After the solution was mixed, stirring was continued at room temperature for 5 hours.
4. The photocatalyst material containing heterojunction loading clay nanometer according to claim 3, wherein: agNO 3 The dropping rate of (2) to (10) drops per second.
5. The photocatalyst material containing heterojunction loading clay nanometer according to claim 4, wherein: step (a)2) The dripping speed of the KI or NaBr solution is 2 to 10 drops per second; the concentration of KI or NaBr solution is 0.01-0.05M; KI and AgNO 3 The mass ratio of (1) is 0.331: 0.796; naBr and AgNO 3 The mass ratio of (A) to (B) is 0.205: 0.796.
6. The photocatalyst material containing heterojunction loading clay nanometer as claimed in claim 1, wherein: the stirring time in the step (2) is 15 min; the drying temperature set by the drying box in the step (2) is 60-80 ℃.
7. The use of the nano photocatalytic material AgX-AgCl/clay containing heterojunction loading clay as claimed in claim 1 in degrading p-hydroxybenzoate, organic dye and phenolic substance.
8. The application of the heterojunction-containing clay-supported nano photocatalytic material in degrading organic matters, according to claim 7, is characterized in that: the specific application method comprises the following steps: methylene blue with the concentration of 20 mg/L, phenol or methyl p-hydroxybenzoate are used as substrates, 0.1g of heterojunction-containing clay-loaded nano photocatalytic material is taken, a xenon lamp with the light source of 300W is used as the light source, ultraviolet light is filtered out by a light filter, and the reaction time is 40-120 min.
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