CN107456983B - Ag/AgCl/TiO2Composite photocatalytic material and preparation method and application thereof - Google Patents
Ag/AgCl/TiO2Composite photocatalytic material and preparation method and application thereof Download PDFInfo
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- 229910021607 Silver chloride Inorganic materials 0.000 title claims abstract description 98
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 title claims abstract description 98
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 138
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 53
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002131 composite material Substances 0.000 claims abstract description 35
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- 238000000034 method Methods 0.000 claims abstract description 28
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000011068 loading method Methods 0.000 claims abstract description 22
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 4
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- WXJHMNWFWIJJMN-UHFFFAOYSA-N 1-methyl-3-octyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCN1C[NH+](C)C=C1 WXJHMNWFWIJJMN-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- HSIKGXXCQDBVPG-UHFFFAOYSA-N [Cl].C(CCCCCCC)N1CN(C=C1)C Chemical compound [Cl].C(CCCCCCC)N1CN(C=C1)C HSIKGXXCQDBVPG-UHFFFAOYSA-N 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
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- 238000001354 calcination Methods 0.000 claims description 2
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- 239000000243 solution Substances 0.000 claims 2
- 239000012266 salt solution Substances 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000975 co-precipitation Methods 0.000 abstract description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 7
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- OXFBEEDAZHXDHB-UHFFFAOYSA-M 3-methyl-1-octylimidazolium chloride Chemical compound [Cl-].CCCCCCCCN1C=C[N+](C)=C1 OXFBEEDAZHXDHB-UHFFFAOYSA-M 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- 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
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B01J35/33—
Abstract
The invention discloses Ag/AgCl/TiO2The composite photocatalytic material is prepared by using titanium dioxide as a base material and loading AgCl and Ag particles on the surface of the base material. Firstly, synthesizing a titanium dioxide precursor by a solvothermal method, then obtaining anatase-phase titanium dioxide by high-temperature calcination, finally taking the titanium dioxide as a carrier, silver nitrate as a silver source and 1-octyl-3-methylimidazolium chloride or hydrochloric acid solution as a chlorine source, wherein an AgCl loading mode can be divided into a hydrothermal coprecipitation method and an immersion precipitation method, and obtaining a product Ag/AgCl/TiO by reduction treatment by illumination2. The preparation method is simple and feasible to operate, and the synthesized Ag/AgCl/TiO2The microsphere has stronger photocatalytic activity and excellent performance in the aspect of photocatalytic degradation of ethylene, benzene and other volatile organic pollutants.
Description
Technical Field
The invention relates to the technical field of air pollution treatment and preparation of photocatalytic materials, in particular to Ag/AgCl/TiO2A composite photocatalytic material and a preparation method and application thereof.
Background
With the current increasingly serious environmental pollution problem, air pollution has seriously affected human physical and mental health, and the research of photocatalyst on treating air pollution has become the key point and focus of catalytic scientific research. In the field of photocatalysis, titanium dioxide has become one of the most important semiconductor photocatalysts due to the advantages of excellent photocatalytic performance, good chemical stability, safety, no toxicity, low cost and the like, and has attracted wide attention of scientists in a plurality of fields such as hydrogen production by photolysis of water, solar cells, air and sewage treatment and the like. Therefore, the research of deep theory combination experiments on the artificial neural network has very important strategic and practical significance.
However, the titanium dioxide has a wide band gap and only responds to ultraviolet light, which greatly influences the commercial prospect of the titanium dioxide in the degradation of organic pollutants by utilizing solar light. On the basis that precious metal (Au, Ag) nanoparticles attract a lot of attention due to the characteristic that the surface plasma resonance effect enhances the visible light absorption of photocatalytic materials, the inventor of the application discovers that Ag/AgX (X ═ Cl, Br, I) surface plasma photocatalysts prepared by an ion exchange-photo reduction method have high visible light catalytic performance in the fields of organic dye degradation, heavy metal ion reduction, bacterial inactivation and the like, and due to the excellent performance of silver/silver halide light visible photocatalysts, people gradually catch fire for the researches on precious metal modification and silver halide load modification of titanium dioxide. However, TiO loading by Ag/AgX (X ═ Cl, Br, I) is currently being attempted2The research on the surface plasma photocatalyst mainly focuses on improving the photocatalytic performance of visible light, degrading organic dye (CN104941615A), applying the surface plasma photocatalyst as a catalytic sterilization material (CN105148888A) and the like, and no surface plasma photocatalyst is availableTiO loaded by Ag/AgX2The research report of the surface plasma photocatalyst on the degradation of gas-phase organic pollutants.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide Ag/AgCl/TiO2A composite photocatalytic material and a preparation method and application thereof. Ag/AgCl/TiO of the invention2The composite photocatalytic material is especially suitable for degrading ethylene, benzene and other volatile organic pollutants.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, there is provided an Ag/AgCl/TiO2The preparation method of the composite photocatalytic material comprises the following steps:
loading AgCl on the surface of spherical titanium dioxide by taking the spherical titanium dioxide as a carrier, silver nitrate as a silver source and 1-octyl-3-methylimidazole chlorine salt or hydrochloric acid solution as a chlorine source; reducing silver ions in AgCl on the surface of the spherical titanium dioxide into simple substance silver by photoinduced reduction to obtain Ag/AgCl/TiO2A composite photocatalytic material.
In the preparation method, the method for loading AgCl on the surface of the spherical titanium dioxide comprises the following steps: hydrothermal coprecipitation and impregnation coprecipitation.
The method for loading AgCl by the hydrothermal coprecipitation method comprises the following steps:
(1) adding 1-octyl-3-methylimidazole chloride, titanium dioxide and PVP into deionized water, fully stirring for 1.5-2.5h, dropwise adding a silver nitrate solution, and continuously stirring for 0.5-1.5 h;
(2) transferring the solution obtained after the stirring in the step (1) to a high-pressure reaction kettle, and reacting for 20-40min at the temperature of 150-; cooling to room temperature after reaction, filtering, washing and drying the precipitate, and grinding to obtain AgCl/TiO2。
The method for loading AgCl by the impregnation coprecipitation method comprises the following steps:
(1) adding titanium dioxide into deionized water, performing ultrasonic dispersion, then dropwise adding a silver nitrate solution, fully stirring for 1.5-2.5h, filtering out a supernatant after stirring, then adding deionized water, dropwise adding a hydrochloric acid solution, and continuously stirring for 0.5-1.5 h;
(2) after stirring, filtering, washing, drying and grinding the precipitate to obtain AgCl/TiO2。
In the above preparation method, the preparation method of the spherical titanium dioxide comprises: mixing tetrabutyl titanate and ammonium acetate in a volume ratio of 1: (25-35), and uniformly stirring for 0.5-1.5h to obtain emulsion; transferring the emulsion into a reaction kettle, reacting at 140 ℃ and 160 ℃ for 10-14h, cooling to room temperature after reaction, separating and drying the precipitate to obtain TiO2A precursor;
adding TiO into the mixture2Calcining the precursor at the temperature of 450-550 ℃ for 1.5-2.5h to obtain the spherical TiO of anatase phase2。
Ag/AgCl/TiO prepared by the preparation method2Composite photocatalytic materials are also within the scope of the present invention.
The Ag/AgCl/TiO2In the composite photocatalytic material, the loading capacity of Ag/AgCl is 1-10%; preferably 6% (theoretically, Ag/TiO)2Is 6%).
The load capacity of Ag/AgCl can influence the catalytic performance of the composite photocatalytic material, and the efficiency of the composite photocatalytic material for degrading ethylene is gradually improved along with the increase of the load capacity of Ag/AgCl within a certain range; however, the Ag/AgCl loading is not suitable to be too large, and the efficiency of ethylene degradation is reduced along with the increase of the Ag/AgCl loading when the Ag/AgCl loading exceeds a certain range. Experiments show that the Ag/AgCl loading is preferably 1-10%, and the Ag/AgCl loading is 6%, so that the performance of the composite material is optimal.
In a second aspect of the present invention, there is provided the above Ag/AgCl/TiO2The application of the composite photocatalytic material in degrading volatile organic pollutants.
The volatile organic contaminants include: ethylene, benzene and other volatile organic contaminants.
The invention has the beneficial effects that:
(1) Ag/AgCl/TiO prepared by the invention2The composite photocatalytic material shows excellent photocatalytic degradation activity, can degrade organic dye, is especially suitable for degrading ethylene, benzene and other volatile organic pollutants, and has good photocatalytic degradation effectExperimental research shows that the Ag/AgCl/TiO of the invention2The composite photocatalytic material can degrade 99 percent of ethylene in about 60 minutes and 99 percent of benzene in about 3 hours under the irradiation of full light (320nm-2500 nm). The efficiency of photo-oxidative degradation of ethylene under full light is higher than that of commercial TiO2(P25) is about four times faster.
(2) The invention is in TiO2After Ag/AgCl is loaded, the TiO loaded with Ag/AgCl is verified by degradation experiments of ethylene, chloroethylene, ethanol and benzene2The performance of the titanium dioxide is obviously improved compared with that of pure titanium dioxide.
(3) The Ag/AgCl/TiO of the invention2The preparation and synthesis method of the composite photocatalytic material has simple conditions and higher commercial application prospect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is an X-ray powder diffraction pattern of a sample prepared in example 1 of the present invention and a standard card corresponding to each sample;
FIG. 2 is an SEM (scanning electron microscope) image of a sample prepared in example 1 of the present invention;
FIG. 3 is a light absorption spectrum of a sample prepared in example 1 of the present invention;
FIG. 4 shows a sample prepared in example 1 of the present invention and commercial TiO2(P25) comparison for photocatalytic degradation of ethylene;
FIG. 5 shows the samples obtained in examples 2 to 3 of the present invention and commercial TiO2(P25) comparison for photocatalytic degradation of ethylene;
FIG. 6 shows a sample prepared in example 2 of the present invention and commercial TiO2(P25) for photocatalytic degradation of benzene comparison.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Description of terms:
the volatile organic pollutants in the invention are organic pollutants with a boiling point of 50-260 ℃ and a saturated vapor pressure of more than 133.3Pa at room temperature, and comprise hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, polycyclic aromatic hydrocarbons and the like.
As described in the background, prior art research on photocatalytic pollution remediation has been directed primarily to liquid phase systems (i.e., wastewater treatment), and less has been done on gas phase pollutant degradation. Based on the Ag/AgCl/TiO, the invention provides2A composite photocatalytic material, a preparation method thereof and application thereof in catalytic degradation of gas-phase pollutants.
In one embodiment of the present application, there is provided an Ag/AgCl/TiO2The preparation method of the composite photocatalytic material comprises the following steps:
loading AgCl on the surface of spherical titanium dioxide by taking the spherical titanium dioxide as a carrier, silver nitrate as a silver source and 1-octyl-3-methylimidazole chlorine salt or hydrochloric acid solution as a chlorine source; reducing silver ions in AgCl on the surface of the spherical titanium dioxide into simple substance silver by photoinduced reduction to obtain Ag/AgCl/TiO2A composite photocatalytic material.
Preferably, the method of supporting AgCl on the surface of the spherical titanium dioxide may employ a hydrothermal coprecipitation method or an impregnation coprecipitation method.
The method for loading AgCl by the hydrothermal coprecipitation method comprises the following steps:
(1) adding 1-octyl-3-methylimidazole chloride, titanium dioxide and PVP into deionized water, fully stirring for 1.5-2.5h, dropwise adding a silver nitrate solution, and continuously stirring for 0.5-1.5 h;
(2) transferring the solution obtained after the stirring in the step (1) to a high-pressure reaction kettle, and reacting for 20-40min at the temperature of 150-; cooling to room temperature after reaction, filtering, washing and drying the precipitate, and grinding to obtain AgCl/TiO2。
The method for loading AgCl by the impregnation coprecipitation method comprises the following steps:
(1) adding titanium dioxide into deionized water, performing ultrasonic dispersion, then dropwise adding a silver nitrate solution, fully stirring for 1.5-2.5h, filtering out a supernatant after stirring, then adding deionized water, dropwise adding a hydrochloric acid solution, and continuously stirring for 0.5-1.5 h;
(2) after stirring, filtering, washing, drying and grinding the precipitate to obtain AgCl/TiO2。
Ag/AgCl/TiO prepared by the method2The composite photocatalytic material has the advantages of uniform granularity, excellent performance and good chemical stability.
In another embodiment of the present application, there is also provided Ag/AgCl/TiO prepared by the above method2The composite photocatalytic material is applied to catalytic degradation of volatile organic pollutants.
Experimental research shows that the Ag/AgCl/TiO of the invention2The composite photocatalytic material can degrade 99 percent of ethylene in about 60 minutes and 99 percent of benzene in about 3 hours under the irradiation of full light (320nm-2500 nm). The efficiency of photo-oxidative degradation of ethylene under full light is higher than that of commercial TiO2(P25) is about four times faster.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples of the present invention are all conventional in the art and commercially available.
Example 1: Ag/AgCl/TiO2Preparation of composite photocatalytic material
The method comprises the following specific steps:
(1) preparation of TiO by solvothermal method2Precursor:
90ml of glacial acetic acid are initially taken in a measuring cylinder and poured into a 150ml beaker, 3.0ml of tetrabutyl titanate are added dropwise to the glacial acetic acid with a pipette, and stirring is continued for 60 minutes. After stirring, the obtained white emulsion was transferred to a 120ml Teflon-lined autoclave, which was then placed in a 150 ℃ temperature-controlled oven for 12 hours. Taking out the reaction kettle after the reaction is finished, naturally cooling to room temperature, finally cleaning the precipitate with absolute ethyl alcohol for 2-3 times in the suction filtration process, and drying at 60-70 ℃ to obtain TiO2And (3) precursor powder.
(2) Preparation of anatase phase TiO2：
Firstly, TiO with a certain mass is added2Pouring precursor powder into a crucible, then selecting air atmosphere to calcine for 2 hours at 500 ℃ in a muffle furnace, setting the heating rate at 5 ℃ per minute, naturally cooling, taking out a sample and fully grinding to obtain anatase phase TiO2And (3) powder.
(3) Preparation of Ag/AgCl/TiO by hydrothermal coprecipitation-photoreduction2The composite photocatalytic material is as follows:
90ml of deionized water were initially taken in a graduated cylinder and poured into a 150ml beaker, 0.084g of 1-octyl-3-methylimidazolium chloride salt and subsequently 0.4g of TiO were added2The powder and 0.1g PVP were stirred well for 2 hours, then 3ml of 0.1mol/L silver nitrate solution was added dropwise, and stirring was continued for another 1 hour. After the stirring, the obtained solution was transferred to a 120ml teflon-lined autoclave, and then the autoclave was placed in an oven at 160 ℃ to react for 30 minutes. Taking out the reaction kettle after the reaction is finished, naturally cooling to room temperature, finally cleaning the precipitate for 2-3 times by using ionized water in the suction filtration process, drying at 60-70 ℃, and grinding to obtain AgCl/TiO2. Carrying out photoinduced reduction in the degradation process to reduce silver ions in AgCl on the surface of titanium dioxide into simple substance silver to obtain Ag/AgCl/TiO2。
Ag/AgCl/TiO prepared by the method2The X-ray diffraction pattern of the compound is shown in FIG. 1, and it can be seen from FIG. 1 that TiO was synthesized2Is pure anatase phase titanium dioxide (JCPDS No.21-1272) and does not have itThe peak of other phase (rutile, brookite) appears, and the Ag/AgCl/TiO is obtained after hydrothermal coprecipitation-illumination reduction2The product obviously shows diffraction peaks of silver chloride (JCPDSno.31-1238) and elementary silver (JCPDS No.65-2871), which are in one-to-one correspondence with PDF standard cards, which indicates that the loading is successful, and no mixed peak of other substances is introduced.
Ag/AgCl/TiO prepared by the method2The SEM image of (A) is shown in FIG. 2, and the Ag/AgCl/TiO obtained from FIG. 22The silver chloride is spherical, the size of the silver chloride is about 2-3 microns, and the silver chloride is loaded on the spherical surface.
Ag/AgCl/TiO prepared by the method2The ultraviolet-visible diffuse reflection absorption spectrum of (D) is shown in FIG. 3. As can be seen from FIG. 3, P25 and TiO2Substantially no absorption in the visible region, and in TiO2After AgCl is deposited on the surface, it can be seen that the absorption edge is shifted in the long-wavelength direction and the absorption of visible light is also significantly enhanced. Ag/AgCl/TiO2The visible light absorption is obviously enhanced because the silver ions on the AgCl surface are reduced into partial silver simple substance under illumination and are caused by the surface plasma resonance effect of the silver nano particles.
Example 2: Ag/AgCl/TiO2Preparation of composite photocatalytic material
The method comprises the following specific steps:
(1) preparation of TiO by solvothermal method2Precursor:
90ml of glacial acetic acid are initially taken in a measuring cylinder and poured into a 150ml beaker, 3.0ml of tetrabutyl titanate are added dropwise to the glacial acetic acid with a pipette, and stirring is continued for 60 minutes. After stirring, the obtained white emulsion was transferred to a 120ml Teflon-lined autoclave, which was then placed in a 150 ℃ temperature-controlled oven for 12 hours. Taking out the reaction kettle after the reaction is finished, naturally cooling to room temperature, finally cleaning the precipitate with absolute ethyl alcohol for 2-3 times in the suction filtration process, and drying at 60-70 ℃ to obtain TiO2And (3) precursor powder.
(2) Preparation of anatase phase TiO2：
Firstly, TiO with a certain mass is added2The precursor powder is poured into a crucible. Then, an air atmosphere is selectedCalcining at 500 deg.C for 2 hr in muffle furnace at a heating rate of 5 deg.C per minute, naturally cooling, taking out sample, and grinding to obtain anatase phase TiO2And (3) powder.
(3) Preparation of Ag/AgCl/TiO by immersion precipitation-photoreduction2The composite photocatalytic material is as follows:
firstly, 100ml of deionized water is measured by a measuring cylinder and poured into a 150ml beaker, and 0.2g of TiO is added into the beaker2Powder, sonicate for 20 minutes. After the completion of the sonication, 185. mu.l of 0.1mol/L silver nitrate solution was added dropwise to the beaker using a pipette gun, and the mixture was stirred sufficiently for 2 hours. After the stirring was completed, the supernatant was filtered off, followed by addition of 100ml of deionized water. 2ml of a 0.2mol/L hydrochloric acid solution was added dropwise thereto, and the mixture was stirred for 1 hour. After stirring, washing the precipitate with ionized water for 2-3 times in the suction filtration process, drying at 60-70 deg.C, and grinding to obtain AgCl/TiO2. Carrying out photoinduced reduction in the degradation process to reduce silver ions in AgCl on the surface of titanium dioxide into simple substance silver to obtain 1 percent of Ag/AgCl/TiO2(theoretically, Ag/TiO)2Is 1%).
Example 3: Ag/AgCl/TiO with different loading amounts2Preparation of composite photocatalytic material
5％Ag/AgCl/TiO2And 10% Ag/AgCl/TiO2The preparation method is the same as that of example 2, except that: the amounts of the silver nitrate solution and the hydrochloric acid solution added were 5 times and 10 times the amounts added in example 2.
Application example 1: photocatalytic activity test
1. The test method comprises the following steps:
the photocatalytic degradation activity test was carried out in a system of quartz glass containers (volume: 400ml) closed with circulating cooling water (5 ℃/25 ℃). The light source used for top illumination was a 300W xenon lamp, and the photocatalytic activity of the samples was evaluated using ethylene and benzene.
0.3g of sample (Ag/AgCl/TiO prepared in example 1-example 3) was weighed2Composite photocatalytic material) is uniformly dispersed at the bottom of the container; as commercial TiO2(P25) as a control. Before the photocatalytic reaction test, the gas is magnetically stirred for 2 hours in the dark to reach the surface of the catalystAnd (3) carrying out adsorption balance, manually sampling 30 mul every 10 minutes or 30 minutes after light is transmitted, and testing by using an Shimadzu gas chromatograph. Wherein the initial volume of ethylene is 2ml, the initial volume of benzene liquid is 5 mul, and the ordinate of degradation curve is C/C0C denotes the initial concentration of the injected gas, C0Representing the real-time concentration of gas in the vessel during sampling.
2. And (3) test results:
example 1 spherical Ag/AgCl/TiO prepared by hydrothermal coprecipitation-photoreduction2The concentration degradation curve of the photocatalyst for photodegradation of ethylene is shown in FIG. 4. from FIG. 4, it can be seen that the photocatalyst can almost completely degrade ethylene in about 60 minutes under all light, and the photocatalytic activity is obviously higher than that of commercial TiO2(P25), approximately four times the degradation rate of P25.
Examples 2-3 Ag/AgCl/TiO prepared using immersion precipitation-photoreduction2The concentration degradation curve of the photocatalyst for photodegradation of ethylene is shown in FIG. 5, and it can be seen from FIG. 5 that the degradation speed of the photocatalyst is gradually increased with the increase of the content of the impregnated AgCl, and the content of 10% Ag/AgCl/TiO at full light2Can degrade 99 percent of ethylene in about 150 minutes and commercial TiO2(P25) is markedly enhanced in comparison with its photocatalytic activity.
To prove that ethylene is coated with Ag/AgCl/TiO2Photo-degraded rather than naturally degraded or air-leaked, we made two comparative tests:
(1) placing the container filled with the photocatalyst and the ethylene in the dark, and stirring for testing;
(2) the containers containing only ethylene were placed under a 300W xenon lamp for light testing.
From the degradation curves of FIGS. 4 and 5, it was found that the ethylene concentration hardly changed, thereby confirming that ethylene was degraded in the test because of Ag/AgCl/TiO prepared according to the present invention2Acts as a photocatalyst and not for other reasons.
FIG. 6 is a graph showing Ag/AgCl/TiO prepared by immersion precipitation-photoreduction in example 22The photocatalyst is used for the concentration degradation curve of photodegradation benzene gas.
Also, the same applies toTo prove that benzene is Ag/AgCl/TiO2Photo-degraded rather than naturally degraded or air-leaked, we made two comparative tests: (1) we put the vessel containing the photocatalyst and benzene in the dark and stir for testing; (2) the container containing only benzene is placed under a 300W xenon lamp for illumination test; from the degradation curve of FIG. 6, it was found that the benzene concentration was hardly changed, thereby confirming that the benzene degradation in the test was due to Ag/AgCl/TiO2Acts as a photocatalyst and not for other reasons. As can be seen from FIG. 6, 1% Ag/AgCl/TiO at all light2Can degrade 99 percent of benzene and commercial TiO in about 170 minutes2(P25) is markedly enhanced in comparison with its photocatalytic activity.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (6)
1. Ag/AgCl/TiO for degrading volatile organic pollutants2The preparation method of the composite photocatalytic material is characterized by comprising the following steps:
loading AgCl on the surface of spherical titanium dioxide by taking spherical titanium dioxide as a carrier, silver nitrate as a silver source and 1-octyl-3-methylimidazole chlorine salt solution as a chlorine source; reducing silver ions in AgCl on the surface of the spherical titanium dioxide into simple substance silver by photoinduced reduction to obtain Ag/AgCl/TiO2A composite photocatalytic material;
the method for loading the AgCl comprises the following steps:
(1) adding 1-octyl-3-methylimidazole chloride, titanium dioxide and PVP into deionized water, fully stirring for 1.5-2.5h, dropwise adding a silver nitrate solution, and continuously stirring for 0.5-1.5 h;
(2) transferring the solution obtained after the stirring in the step (1) to a high-pressure reaction kettle, and reacting for 20-40min at the temperature of 150-; cooling to room temperature after reaction, filtering, washing and drying the precipitate, and grinding to obtain AgCl/TiO2；
The spherical dioxygenThe preparation method of the titanium oxide comprises the following steps: mixing tetrabutyl titanate and ammonium acetate in a volume ratio of 1: (25-35), and uniformly stirring for 0.5-1.5h to obtain emulsion; transferring the emulsion into a reaction kettle, reacting at 140 ℃ and 160 ℃ for 10-14h, cooling to room temperature after reaction, separating and drying the precipitate to obtain TiO2A precursor;
adding TiO into the mixture2Calcining the precursor at the temperature of 450-550 ℃ for 1.5-2.5h to obtain the spherical TiO of anatase phase2。
2. Ag/AgCl/TiO for degrading volatile organic pollutants prepared by the method of claim 12A composite photocatalytic material.
3. Ag/AgCl/TiO for degrading volatile organic pollutants according to claim 22The composite photocatalytic material is characterized in that the Ag/AgCl/TiO2The loading capacity of Ag/AgCl in the composite photocatalytic material is 1-10%.
4. Ag/AgCl/TiO for degrading volatile organic pollutants according to claim 22The composite photocatalytic material is characterized in that the Ag/AgCl/TiO2The loading capacity of Ag/AgCl in the composite photocatalytic material is 6%.
5. Ag/AgCl/TiO for degrading volatile organic pollutants as claimed in claim 22The application of the composite photocatalytic material in degrading volatile organic pollutants.
6. Use according to claim 5, wherein the volatile organic contaminants comprise: ethylene, benzene, or other volatile organic contaminants.
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| CN115397585A (en) * | 2020-07-21 | 2022-11-25 | 刘峰 | Super-atomic material, sol, preparation method and application thereof |
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| CN112570024B (en) * | 2020-12-28 | 2022-09-02 | 青岛科技大学 | Ag/AgCl/IL/FeOOH/AC photocatalytic material and preparation and application thereof |
| CN113198480B (en) * | 2021-04-27 | 2023-04-28 | 上海应用技术大学 | La/Co@TiO 2 Nanosphere catalyst and preparation method and application thereof |
| CN114011442A (en) * | 2021-10-29 | 2022-02-08 | 盐城工学院 | Self-dispersion reactive Ag/AgCl/TiO2Preparation method and product and application thereof |
| CN114210349A (en) * | 2021-11-18 | 2022-03-22 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of composite visible-light-driven photocatalyst and composite visible-light-driven photocatalyst |
| CN114425330B (en) * | 2022-01-14 | 2023-07-28 | 山东大学 | Double noble metal loaded nano titanium dioxide and preparation method and application thereof |
| CN115414964B (en) * | 2022-08-26 | 2024-03-22 | 陕西科技大学 | Polymer modified gangue composite Ag-based photocatalyst and preparation method thereof |
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