CN113813959A - Preparation method of silver zirconate/titanium dioxide composite photocatalyst, product and application thereof - Google Patents
Preparation method of silver zirconate/titanium dioxide composite photocatalyst, product and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000004332 silver Substances 0.000 title claims abstract description 43
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 43
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 67
- 239000011259 mixed solution Substances 0.000 claims abstract description 52
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 20
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims abstract description 16
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 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 abstract description 6
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 22
- 230000015556 catabolic process Effects 0.000 abstract description 20
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- 101710134784 Agnoprotein Proteins 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000000418 atomic force spectrum Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005206 flow analysis Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012088 reference solution Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2101/38—Organic compounds containing nitrogen
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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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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a preparation method of a silver zirconate/titanium dioxide composite photocatalyst, a product and application thereof, wherein the preparation method comprises the step of mixing nano TiO2With AgNO3Mixing the solutions, carrying out ultrasonic treatment, and stirring for 20-30 min in a dark condition to obtain a mixed solution A; ZrOCl2·8H2Dropwise adding the solution O into the mixed solution A while stirring, and dropwise adding a concentrated ammonia solution to make the pH of the solution system be 10-12 to obtain a mixed solution B; carrying out hydrothermal reaction on the mixed solution B at 160-180 ℃ for 20-24 h, taking out the mixed solution, centrifuging and washing the mixed solution, and obtaining a precipitateDrying and grinding to obtain light brown Ag2ZrO3/TiO2And (3) calcining the powder at 400-500 ℃ for 10-12 hours to obtain the white silver zirconate/titanium dioxide composite photocatalyst. Preferred Ag in the present invention2ZrO3With TiO2When the molar ratio of (1: 2) is higher than that of the compound photocatalyst, the photocatalytic performance of the compound photocatalyst is best, the degradation rate of the compound photocatalyst to a methylene blue solution reaches 93.26% within 60 minutes, the dynamic curve value K reaches 0.03749, and the compound photocatalyst is good in stability.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a silver zirconate/titanium dioxide composite photocatalyst, a product and application thereof.
Background
The research on a novel and environment-friendly sewage degradation technology becomes a main task of many researchers, the photocatalysis method is simple and convenient to operate, green and environment-friendly, has sustainability, can degrade various organic pollutants into carbon dioxide and water or organic substances with small toxicity, is high in efficiency and free of secondary pollution, and the photocatalysis technology is widely applied due to the benefits.
The development of the photocatalytic technology is rapid, but in the process, a plurality of problems still exist to be solved. The band gap of the photocatalyst is wide, so that a light source cannot be fully utilized, and the effect of treating wastewater is not ideal; a composite reaction is easy to occur in the process of photoreaction, and the combination of electrons and holes is unstable, so that the photocatalytic degradation rate is reduced; the photo-corrosion phenomenon is also liable to occur.
Zirconium oxide (ZrO)2) And zirconium-based catalysts, which have the characteristics of inert chemistry, higher oxidation potential, lower production cost and the like, have been widely used in the research of decontamination of water and air. However, because of ZrO2The band gap of (A) is 5-6 eV, thereby limiting ZrO2The use in the ultraviolet region results in the use of only 4% of the solar spectrum.
Therefore, in order to increase the absorptivity of solar energy, the band gap is narrowed to increase ZrO2The visible light absorption capability of (a) is a technical problem to be solved urgently in the field.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of the silver zirconate/titanium dioxide composite photocatalyst.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a silver zirconate/titanium dioxide composite photocatalyst comprises the following steps,
mixing nanometer TiO2With AgNO3Mixing the solutions, carrying out ultrasonic treatment, and stirring for 20-30 min in a dark condition to obtain a mixed solution A;
ZrOCl2·8H2Dropwise adding the solution O into the mixed solution A while stirring, and dropwise adding a concentrated ammonia solution to make the pH of the solution system be 10-12 to obtain a mixed solution B;
hydrothermal reaction of the mixed solution B at 160-180 DEG CTaking out the mixture for 20-24 h, centrifuging and washing the mixture, drying and grinding the obtained precipitate to obtain light brown Ag2ZrO3/TiO2And (3) calcining the powder at 400-500 ℃ for 10-12 hours to obtain the white silver zirconate/titanium dioxide composite photocatalyst.
As a preferable scheme of the preparation method of the silver zirconate/titanium dioxide composite photocatalyst, the preparation method comprises the following steps: the silver zirconate/titanium dioxide composite photocatalyst is prepared from Ag2ZrO3With TiO2The molar ratio of (A) to (B) is 1-4: 1-6.
As a preferable scheme of the preparation method of the silver zirconate/titanium dioxide composite photocatalyst, the preparation method comprises the following steps: ag2ZrO3With TiO2The molar ratio of (A) to (B) is 1: 2-4.
As a preferable scheme of the preparation method of the silver zirconate/titanium dioxide composite photocatalyst, the preparation method comprises the following steps: ag2ZrO3With TiO2In a molar ratio of 1: 2.
As a preferable scheme of the preparation method of the silver zirconate/titanium dioxide composite photocatalyst, the preparation method comprises the following steps: the nano TiO2The particle size is 25-30 nm.
As a preferable scheme of the preparation method of the silver zirconate/titanium dioxide composite photocatalyst, the preparation method comprises the following steps: the AgNO3The concentration of the solution was 0.1 mol/L.
As a preferable scheme of the preparation method of the silver zirconate/titanium dioxide composite photocatalyst, the preparation method comprises the following steps: said ZrOCl2·8H2The concentration of the O solution is 0.1 mol/L.
As a preferable scheme of the preparation method of the silver zirconate/titanium dioxide composite photocatalyst, the preparation method comprises the following steps: ZrOCl2·8H2Adding O solution dropwise into the mixed solution A, wherein ZrOCl2·8H2AgNO in O solution and mixed liquor A3The volume ratio of the solution was 1: 2.
The invention further aims to overcome the defects in the prior art and provide a product prepared by the preparation method of the silver zirconate/titanium dioxide composite photocatalyst.
The invention also aims to overcome the defects in the prior art and provide the application of the silver zirconate/titanium dioxide composite photocatalyst in photocatalytic degradation of methylene blue.
The invention has the beneficial effects that:
(1) the invention provides a preparation method of a silver zirconate/titanium dioxide composite photocatalyst and Ag prepared by the preparation method2ZrO3/TiO2The composite photocatalyst has better visible light absorption performance, and is preferably Ag2ZrO3With TiO2When the molar ratio of the compound photocatalyst is 1:2, the synergistic effect of the photocatalytic performance of the compound photocatalyst is optimal, the degradation rate of the methylene blue solution in 60 minutes reaches 93.26%, the dynamic curve value K reaches 0.03749, and the stability is good.
(2) The performance of the silver zirconate/titanium dioxide composite photocatalyst is improved mainly due to Ag2ZrO3With nano TiO2Effective compounding of (2) reduces TiO2The band gap effectively separates photoproduction electrons from holes, reduces the recombination rate of the electrons and the holes, and improves the TiO2The photocatalytic performance of the photocatalyst has the main effect that the influence of functional groups is h+>·O2 ->·OH。
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a graph of the degradation rate of the silver zirconate/titanium dioxide composite photocatalyst prepared by compounding in different proportions in the embodiment of the invention.
FIG. 2 is a graph of the dynamic force curves of composite samples of different proportions in an embodiment of the present invention.
FIG. 3 shows the present inventionEXAMPLES Ag2ZrO3With Ag2ZrO3/TiO2XED pattern of composite samples.
FIG. 4 shows an example of Ag2ZrO3/TiO2SEM image of the sample.
FIG. 5 shows an example of Ag2ZrO3/TiO2EDS map of (a).
FIG. 6 shows TiO of an embodiment of the present invention2、Ag2ZrO3With Ag2ZrO3/TiO2Graph of photocurrent results.
FIG. 7 is a spectrum of UV-visible absorption of a composite sample according to an embodiment of the present invention.
FIG. 8 shows Ag after adding different capture agents according to the present invention2ZrO3/TiO2Degradation rate curve of (d).
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The invention relates to an experimental reagent
Preparing Ag by adopting hydrothermal-calcining method2ZrO3And Ag2ZrO3/TiO2The water used in the experimental process of the composite photocatalyst is deionized water, and the chemical agents used for preparation are as followsTable 1.
TABLE 1
And (3) crystal form analysis:
ag to be prepared2ZrO3And Ag2ZrO3/TiO2The crystal structure of the composite sample is determined by an X-ray diffractometer.
And (3) observing physical appearance:
the surface topography and particle size of the sample can be observed by scanning electron microscopy. Ag2ZrO3/TiO2The composite powder is detected by scanning electron pictures with different magnification factors, and the composite form of the photocatalytic material can be directly observed.
X-ray energy spectroscopy (EDS) analysis:
ag to be prepared2ZrO3/TiO2And (3) determining the types of chemical components and the content of each element of the composite sample by using an X-ray energy spectrometer. The size of the characteristic wave in the EDS spectrum is determined by the characteristic energy released during the energy level transition, and each element has its unique characteristic wavelength.
Ultraviolet and visible light diffuse reflection spectrum analysis:
using ultraviolet diffuse reflection instrument to compound Ag2ZrO3/TiO2The visible light absorption performance of the photocatalyst is measured, and the measuring wavelength range is 200-800 nm.
And (3) testing photocurrent:
respectively weighing 0.05g of nano TiO2、Ag2ZrO3、Ag2ZrO3/TiO2Adding the composite powder into an absolute ethyl alcohol solution to prepare 3mL of mixed solution for later use; each set was prepared as 3 clean glass slides, placed in a petri dish, the reaction was dropped onto the glass slides, and placed in an oven for slight drying.
The research on the silver zirconate photocatalysis principle comprises the following steps:
in order to explore the degradation process of the photocatalystThe effect specific gravity of the functional group is that Ag is added2ZrO3/TiO2And (3) respectively adding tert-butyl alcohol, p-benzoquinone and disodium ethylene diamine tetraacetate (EDTA-2Na) into the MB solution of the composite photocatalyst, repeating the test step of degrading MB, and measuring the absorbance of the MB solution.
Example 1
The embodiment provides a preparation method of a silver zirconate/titanium dioxide composite photocatalyst, which comprises the following steps,
(1) 40mL (0.1mol/L) of AgNO is measured3The solution was poured into a dark brown volumetric flask and 0.1597g of nano TiO were weighed2With AgNO3Mixing the solutions, performing ultrasonic treatment for 30min, and magnetically stirring for 30min in a dark condition to obtain a mixed solution A.
(2) 20ml (0.1mol/L) of ZrOCl2·8H2And dropwise adding the O solution into the mixed solution while stirring for 30min, and then dropwise adding a concentrated ammonia solution to keep the pH value of the solution at 11 to obtain a mixed solution B.
(3) Putting the mixed solution into a 160 ℃ oven for hydrothermal reaction for 24 hours, taking out the mixed solution, centrifuging and washing the mixed solution for three times, putting the obtained precipitate into a 60 ℃ oven for drying and grinding to obtain light brown Ag2ZrO3/TiO2Calcining the powder at 400 deg.C for 12 hr to obtain white Ag2ZrO3/TiO2And (3) powder.
Example 2
The embodiment provides a preparation method of a silver zirconate/titanium dioxide composite photocatalyst, which comprises the following steps,
(1) 40mL (0.1mol/L) of AgNO is measured3The solution was poured into a dark brown volumetric flask and 0.3194g of nano TiO were weighed2With AgNO3Mixing the solutions, performing ultrasonic treatment for 30min, and magnetically stirring for 30min in a dark condition to obtain a mixed solution A.
(2) 20ml (0.1mol/L) of ZrOCl2·8H2And dropwise adding the O solution into the mixed solution while stirring for 30min, and then dropwise adding a concentrated ammonia solution to keep the pH value of the solution at 11 to obtain a mixed solution B.
(3) Placing the mixture at 160 deg.CHydrothermal reaction in oven for 24 hr, taking out, centrifuging, washing for three times, oven drying the precipitate at 60 deg.C, and grinding to obtain light brown Ag2ZrO3/TiO2Calcining the powder at 400 deg.C for 12 hr to obtain white Ag2ZrO3/TiO2And (3) powder.
Example 3
The embodiment provides a preparation method of a silver zirconate/titanium dioxide composite photocatalyst, which comprises the following steps,
(1) 40mL (0.1mol/L) of AgNO is measured3The solution is poured into a dark brown volumetric flask, and 0.6389g of nano TiO is weighed2With AgNO3Mixing the solutions, performing ultrasonic treatment for 30min, and magnetically stirring for 30min in a dark condition to obtain a mixed solution A.
(2) 20ml (0.1mol/L) of ZrOCl2·8H2And dropwise adding the O solution into the mixed solution while stirring for 30min, and then dropwise adding a concentrated ammonia solution to keep the pH value of the solution at 11 to obtain a mixed solution B.
(3) Putting the mixed solution into a 160 ℃ oven for hydrothermal reaction for 24 hours, taking out the mixed solution, centrifuging and washing the mixed solution for three times, putting the obtained precipitate into a 60 ℃ oven for drying and grinding to obtain light brown Ag2ZrO3/TiO2Calcining the powder at 400 deg.C for 12 hr to obtain white Ag2ZrO3/TiO2And (3) powder.
Example 4
The embodiment provides a preparation method of a silver zirconate/titanium dioxide composite photocatalyst, which comprises the following steps,
(1) 40mL (0.1mol/L) of AgNO is measured3The solution was poured into a dark brown volumetric flask and 0.9484g of nano TiO were weighed2With AgNO3Mixing the solutions, performing ultrasonic treatment for 30min, and magnetically stirring for 30min in a dark condition to obtain a mixed solution A.
(2) 20ml (0.1mol/L) of ZrOCl2·8H2Adding O solution dropwise into the mixed solution while stirring for 30min, and adding concentrated ammonia solution dropwise to maintain pH of the solution at 11 to obtain mixed solutionB。
(3) Putting the mixed solution into a 160 ℃ oven for hydrothermal reaction for 24 hours, taking out the mixed solution, centrifuging and washing the mixed solution for three times, putting the obtained precipitate into a 60 ℃ oven for drying and grinding to obtain light brown Ag2ZrO3/TiO2Calcining the powder at 400 deg.C for 12 hr to obtain white Ag2ZrO3/TiO2And (3) powder.
Example 5
The embodiment provides a preparation method of a silver zirconate/titanium dioxide composite photocatalyst, which comprises the following steps,
(1) 40mL (0.1mol/L) of AgNO is measured3The solution was poured into a dark brown volumetric flask and 0.0798g of nano TiO were weighed2With AgNO3Mixing the solutions, performing ultrasonic treatment for 30min, and magnetically stirring for 30min in a dark condition to obtain a mixed solution A.
(2) 20ml (0.1mol/L) of ZrOCl2·8H2And dropwise adding the O solution into the mixed solution while stirring for 30min, and then dropwise adding a concentrated ammonia solution to keep the pH value of the solution at 11 to obtain a mixed solution B.
(3) Putting the mixed solution into a 160 ℃ oven for hydrothermal reaction for 24 hours, taking out the mixed solution, centrifuging and washing the mixed solution for three times, putting the obtained precipitate into a 60 ℃ oven for drying and grinding to obtain light brown Ag2ZrO3/TiO2Calcining the powder at 400 deg.C for 12 hr to obtain white Ag2ZrO3/TiO2And (3) powder.
Example 6
The embodiment provides a preparation method of a silver zirconate/titanium dioxide composite photocatalyst, which comprises the following steps,
(1) 40mL (0.1mol/L) of AgNO is measured3The solution was poured into a dark brown volumetric flask and 0.0399g of nano TiO were weighed2With AgNO3Mixing the solutions, performing ultrasonic treatment for 30min, and magnetically stirring for 30min in a dark condition to obtain a mixed solution A.
(2) 20ml (0.1mol/L) of ZrOCl2·8H2Adding O solution dropwise into the mixed solution while stirring for 30min, and mixingThen, concentrated ammonia solution is added dropwise to keep the pH value of the solution at 11, so as to prepare mixed solution B.
(3) Putting the mixed solution into a 160 ℃ oven for hydrothermal reaction for 24 hours, taking out the mixed solution, centrifuging and washing the mixed solution for three times, putting the obtained precipitate into a 60 ℃ oven for drying and grinding to obtain light brown Ag2ZrO3/TiO2Calcining the powder at 400 deg.C for 12 hr to obtain white Ag2ZrO3/TiO2And (3) powder.
Example 7
Preparation of silver zirconate
20ml of 0.1mol/L ZrOCl2·8H2The O solution is added dropwise with 40mL of 0.1mol/L AgNO3Mixing, and magnetically stirring for 30min in dark condition. A concentrated ammonia solution was then added dropwise to maintain the pH of the solution at 11. The mixture was transferred to a 100mL reaction vessel, compressed in a stainless steel container, and placed in an oven at 160 ℃ for 24 hours. Taking out, centrifuging and washing the mixed solution for three times, drying the obtained precipitate in an oven at 60 ℃ and grinding to obtain brown Ag2ZrO3Calcining the powder at 400 deg.C for 12 hr to obtain white Ag2ZrO3And (3) powder.
Testing the photocatalytic performance:
degradation of methylene blue solution
The concentration of the degraded MB solution was determined with a UV1600 series UV-vis spectrophotometer.
Preparing 10mg/L MB solution, adding 0.1g Ag into 100ml MB solution2ZrO3And stirring the powder on a magnetic stirrer in the dark for 30 minutes to achieve the adsorption-desorption balance of the photocatalyst on the MB solution.
And (3) placing the reaction liquid under a xenon lamp, simulating visible light, carrying out photocatalytic degradation, and keeping constant-speed stirring in the illumination process. From 0 minutes, 3mL of the suspension was taken out every 10 minutes, and centrifuged by a high-speed centrifuge at 1000X 10r/min for 5 minutes.
After centrifugation, the supernatant was taken out, and the absorbance of the supernatant was measured by an ultraviolet-visible spectrophotometer using deionized water as a reference solution at an MB absorption wavelength λ of 664nm for 60 minutes, and the test was completed.
The degradation rate obtained from the measured absorbance was plotted in a graph according to the formula (2-1) and analyzed. And drawing a kinetic curve graph according to the formula (2-2).
η＝(C0-Ct)/C0×100％ (2-1)
K＝ln(C0/Ct) (2-2)
In the above formula: c0、CtThe absorbance values at the maximum absorption peak (λ max ═ 664nm) of the MB solution at reaction time 0 minute and reaction time t, respectively.
Ag was added to the samples of examples 1 to 6 at different ratios (1:1, 1:2, 1:4, 1:6, 2:1, 4:1)2ZrO3/TiO2The composite samples, each added to 100ml of MB solution, were measured for their respective degradation curves and kinetic curves.
The photocatalytic efficiency of the synthesized groups of samples was studied by photodegradation of MB solution, as shown in FIG. 1, which shows TiO2And Ag2ZrO3And 6 group Ag2ZrO3/TiO2And (3) degrading the 10mg/LMB solution within 60min by using the composite photocatalysts with different molar ratios under the irradiation of visible light.
Since the organic dye also has the ability to capture visible light, photodegradation of the MB solution with and without photocatalyst was also performed to deny the possibility of photosensitized degradation.
As is evident from FIG. 1, either Ag alone2ZrO3Or is Ag2ZrO3/TiO2The composite and the degradation rate are all compared with TiO2Much higher, the degradation rate of TiO2 is only 36.5%, and single Ag2ZrO3The degradation rate of the photocatalyst was 89.78%.
The method comprises the following steps of 1: ag compounded at 2 mol ratio2ZrO3/TiO2The sample has the best degradation degree of MB solution, and the degradation rate can reachTo 93.26%.
Fig. 2 shows the dynamic curve values for samples compounded at different ratios, where the ratio K is the largest at 1:2 (K-0.03739). Illustrates Ag2ZrO3Photocatalytic performance ratio of TiO2Good, Ag2ZrO3With TiO2The photocatalytic performance can be further improved after the composition.
Example 8
(1) The obtained Ag2ZrO3/TiO21:2 composite sample, calcined Ag2ZrO3The crystallinity and purity of the sample were measured by X-ray diffractometer, respectively.
Fig. 3 shows that there are good peaks at 28 °, 33 ° and 47 ° 2 θ, and the peak at 33 ° has the greatest intensity, indicating that the Ag synthesized2ZrO3/TiO2The sample had crystalline properties.
The diffraction pattern shows that it does not correspond to the diffraction pattern of silver oxide (AgO) nor to that of zirconium oxide (ZrO2), but it does not correspond to Na2ZrO3There is a certain similarity. Since Ag replaces Na and Ag2ZrO3There will be a certain deviation of the characteristic peaks of (a).
The Ag is obtained by a hydrothermal-calcining method experiment2ZrO3The XRD pattern of the Ag is similar to that of AgZ-MA synthesized by microwave assistance in the literature, and the Ag is proved2ZrO3The synthesis purity of the product is relatively high.
(2) SEM analysis
From FIG. 4, it can be seen that Ag is contained in the composite sample2ZrO3Particle coating nano TiO2The result of the strong adsorption binding is the same as that of the XRD test, which shows that the purity of the photocatalyst is higher, and the hydrothermal-calcining method is adopted to prepare Ag2ZrO3/TiO2Composite photocatalysts have been successful.
(3) EDS analysis
The element composition of the composite photocatalyst is studied by EDS analysis, and as can be seen from figure 5, the composite photocatalyst contains oxygen, silver, zirconium and titanium, and no other elements are observed, so that the result indicates that the composite purity of the photocatalyst is high.
In Table 2, the chemical elements account for the catalyst, and the atomic weight of Ag accounts for 46.17%, the atomic weight of O accounts for 43.58%, while the atomic weight of Ti accounts for only 8.10%, and the lowest Zr accounts for only 2.15%. The experimental result shows that Ag2ZrO3/TiO2The preparation of (1) was successful.
TABLE 2 Ag2ZrO3/TiO2Chemical element ratio
(4) Photoelectric flow analysis
The photocatalyst rapidly increases the response value of the current when being irradiated by light and rapidly decreases the response value of the current when not being irradiated by light, as shown in fig. 6, in three groups of samples, Ag2ZrO3/TiO2The current response value of the composite sample is highest, and Ag is the second2ZrO3，TiO2Indicates the Ag prepared2ZrO3/TiO2The composite photocatalyst has the best photosensitive performance.
(5) UV-VisDRS assay
FIG. 7 is Ag2ZrO3/TiO2And the ultraviolet and visible light diffuse reflection spectrogram of the composite photocatalyst within the wavelength range of 200-800 nm. TiO22Has strong light absorption reaction in the wavelength range of 200-380 nm, and is consistent with the numerical value in the literature.
But Ag2ZrO3And Ag2ZrO3/TiO2The composite material has good response to visible light, and the wide absorption edge is positioned at 465 nm. For pure TiO2Absorption wavelength threshold of 384nm, similar to TiO2Intrinsic band gap (3.2eV), and pure Ag2ZrO3The band gap energy of (2.8 eV).
As shown in FIG. 7, the absorbance values of Zr and TiAg are lower than that of pure TiO2, which indicates that the forbidden bandwidths of Zr and TiAg are small, and the energy required for photoelectron transition is less, so that Ag2ZrO3/TiO2 has good light absorption performance.
Example 9
Ag2ZrO3/TiO2Results of radical analysis
After addition of different capture agents, Ag2ZrO3/TiO2The degradation rate of the composite sample to the MB solution was different, and Ag was observed in the absence of any trapping agent after 60 minutes of reaction, as shown in FIG. 82ZrO3/TiO2The degradation rate of the catalyst to MB is 93.26%; when tert-butyl alcohol is added to capture hydroxyl and OH, the degradation rate is 93.13%; after p-Benzoquinone (BQ) is added to capture superoxide radical (. O2-), the degradation rate is 74.97%;
when the ethylene diamine tetraacetic acid (EDTA-2Na) is added to capture the hole (h +), the degradation rate is reduced to 49.58%, which shows that the group playing the main degradation role in the photocatalyst has the least influence on the hydroxyl radical OH and the superoxide radical O2 -Maximum is the cavity h+。
The invention provides a preparation method of a silver zirconate/titanium dioxide composite photocatalyst and Ag prepared by the preparation method2ZrO3/TiO2The composite photocatalyst has better visible light absorption performance, and is preferably Ag2ZrO3With TiO2When the molar ratio of (1: 2) is higher than that of the compound photocatalyst, the photocatalytic performance of the compound photocatalyst is best, the degradation rate of the compound photocatalyst to a methylene blue solution reaches 93.26% within 60 minutes, the dynamic curve value K reaches 0.03749, and the compound photocatalyst is good in stability.
The performance of the silver zirconate/titanium dioxide composite photocatalyst is improved mainly due to Ag2ZrO3With nano TiO2Effective compounding of (2) reduces TiO2The band gap effectively separates photoproduction electrons from holes, reduces the recombination rate of the electrons and the holes, and improves the TiO2The photocatalytic performance of the photocatalyst has the main effect that the influence of functional groups is h+>·O2 ->·OH。
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a silver zirconate/titanium dioxide composite photocatalyst is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
mixing nanometer TiO2With AgNO3Mixing the solutions, carrying out ultrasonic treatment, and stirring for 20-30 min in a dark condition to obtain a mixed solution A;
ZrOCl2·8H2Dropwise adding the solution O into the mixed solution A while stirring, and dropwise adding a concentrated ammonia solution to make the pH of the solution system be 10-12 to obtain a mixed solution B;
carrying out hydrothermal reaction on the mixed solution B at 160-180 ℃ for 20-24 h, taking out the mixed solution, centrifuging and washing the mixed solution, drying and grinding the obtained precipitate to obtain light brown Ag2ZrO3/TiO2And (3) calcining the powder at 400-500 ℃ for 10-12 hours to obtain the white silver zirconate/titanium dioxide composite photocatalyst.
2. The method for preparing the silver zirconate/titanium dioxide composite photocatalyst as claimed in claim 1, wherein: the silver zirconate/titanium dioxide composite photocatalyst is prepared from Ag2ZrO3With TiO2The molar ratio of (A) to (B) is 1-4: 1-6.
3. The method for preparing the silver zirconate/titanium dioxide composite photocatalyst as claimed in claim 1 or 2, wherein: ag2ZrO3With TiO2The molar ratio of (A) to (B) is 1: 2-4.
4. The method for preparing the silver zirconate/titanium dioxide composite photocatalyst as claimed in claim 3, wherein: ag2ZrO3With TiO2In a molar ratio of 1: 2.
5. The method for preparing the silver zirconate/titanium dioxide composite photocatalyst as claimed in claim 1, wherein: the nano TiO2The particle size is 25-30 nm.
6. The method for preparing the silver zirconate/titanium dioxide composite photocatalyst as claimed in claim 1, wherein: the AgNO3The concentration of the solution was 0.1 mol/L.
7. The method for preparing the silver zirconate/titanium dioxide composite photocatalyst as claimed in claim 1, wherein: said ZrOCl2·8H2The concentration of the O solution is 0.1 mol/L.
8. The method for preparing the silver zirconate/titanium dioxide composite photocatalyst as claimed in claim 1, wherein: ZrOCl2·8H2Adding O solution dropwise into the mixed solution A, wherein ZrOCl2·8H2AgNO in O solution and mixed liquor A3The volume ratio of the solution was 1: 2.
9. The product prepared by the preparation method of the silver zirconate/titanium dioxide composite photocatalyst as set forth in any one of claims 1 to 8.
10. Use of the product according to claim 9 for the photocatalytic degradation of methylene blue.
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