CN107020091B - Ag with visible light response4(GeO4) Photocatalyst and preparation method and application thereof - Google Patents
Ag with visible light response4(GeO4) Photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 46
- 229910005833 GeO4 Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 230000001699 photocatalysis Effects 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- FNIHDXPFFIOGKL-UHFFFAOYSA-N disodium;dioxido(oxo)germane Chemical compound [Na+].[Na+].[O-][Ge]([O-])=O FNIHDXPFFIOGKL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 230000000593 degrading effect Effects 0.000 claims abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 2
- 239000003651 drinking water Substances 0.000 claims description 2
- 235000020188 drinking water Nutrition 0.000 claims description 2
- 239000002352 surface water Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 8
- 238000011160 research Methods 0.000 abstract description 7
- 230000004298 light response Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 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 abstract 1
- 239000000047 product Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 239000000975 dye Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000007792 addition Methods 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910005831 GeO3 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
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- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical class C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
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- 231100000956 nontoxicity Toxicity 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
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
-
- B01J35/39—
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses Ag with visible light response4(GeO4) The preparation method of the photocatalyst comprises the following steps: (1) slowly dripping the sodium germanate solution into the silver nitrate solution under the stirring state, and continuously stirring to form a precursor solution; (2) transferring the precursor solution into a reaction kettle, reacting for 10-14h at the temperature of 110-4(GeO4) A photocatalyst. Ag prepared by the invention4(GeO4) The photocatalyst has visible light response, has higher photocatalytic activity after being formed, and is relatively suitable for degrading organic pollutants and decomposing water to produce oxygen in the actual application of the field of photocatalysis. The experimental research shows that Ag4(GeO4) The photocatalytic material shows better photocatalytic performance, and the photocatalyst prepared by photocatalytic water decomposition and oxygen production can decompose water and produce oxygen in an amount of 200umol/g under the irradiation of visible light for 1 hour. 98% of the methylene blue organic dye can be degraded in 20 minutes.
Description
Technical Field
The invention relates to the technical field of preparation of photocatalytic materials, in particular to Ag with visible light response4(GeO4) Light (es)A catalyst, a preparation method and application thereof.
Background
The use of semiconductor photocatalysts to convert low-density solar energy which is difficult to collect into high-density electrical energy and chemical energy which are easy to use has become one of the most active research fields in the world in recent years. Especially, the unique advantages exhibited in the aspects of decomposing water by photocatalysis and treating environment by photo-oxidative degradation of pollutants attract the wide attention of scientists in various countries in the world, so that the wide theoretical and experimental research on the advantages has very important strategic and practical significance.
Of all the problems restricting the practical application of the photocatalytic technology, the most important is to improve the utilization efficiency of the photocatalyst to the light energy. Ultraviolet light accounts for 3-4% of all energy in the solar spectrum, and visible light accounts for more than 40%, so that research and development of visible light response photocatalyst is a research focus for improving the solar energy utilization efficiency, and has important theoretical and practical significance.
Among various photocatalyst materials, titanium dioxide has the advantages of low price, no toxicity, strong oxidation capacity, good stability and the like, and is one of the most researched and widely applied semiconductor photocatalysts at present. 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. Currently, research on visible light driven novel photocatalysts is mainly focused on two aspects: on one hand, the traditional titanium dioxide photocatalytic material is modified to realize the effective work of the material under visible light, such as metal ion doping, non-metal ion doping, ion implantation and the like; on the other hand, various novel visible light response photocatalytic materials are designed and developed, such as bismuth-based photocatalyst and Cu-based photocatalyst2O catalysts, etc., are also important research directions. Therefore, it is of great importance to develop new photocatalytic materials with strong absorption in the visible light region and strong photocatalytic activity.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, it is an object of the present invention to provide a method for manufacturing a semiconductor deviceAg with visible light response4(GeO4) A photocatalyst and a preparation method and application thereof. The photocatalyst has strong absorption in a visible light region and strong photocatalytic activity, and comprises the steps of photocatalytic water decomposition to produce oxygen and photocatalytic degradation of organic dye methylene blue.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided an Ag having a visible light response4(GeO4) The preparation method of the photocatalyst comprises the following steps:
(1) slowly dripping the sodium germanate solution into the silver nitrate solution under the stirring state, and continuously stirring to form a precursor solution;
(2) transferring the precursor solution into a reaction kettle, reacting for 10-14h at the temperature of 110-4(GeO4) A photocatalyst.
Preferably, in the step (1), the concentration of the sodium germanate solution is 0.06-0.07 mol/L; preferably 0.0625 mol/L. The concentration of the silver nitrate solution is 0.2-0.3 mol/L; preferably 0.25 mol/L.
Preferably, in the step (1), the volume ratio of the sodium germanate solution to the silver nitrate solution is 1: 1. The addition of sodium germanate and silver nitrate can affect the Ag prepared4(GeO4) The invention discloses a photocatalyst with a structure composition, which optimizes and inspects the addition of sodium germanate and silver nitrate, and finds that the molar ratio of the sodium germanate to the silver nitrate is (0.06-0.07): (0.2-0.3) is preferably added, so that the target product can be generated to the maximum extent; when the sodium germanate and the silver nitrate are added according to the molar ratio of 1:4, Ag4(GeO4) The yield of the photocatalyst is highest.
Preferably, in the step (1), the stirring is continued for 20-40 min; preferably 30 min. The contact condition of reactants can be improved through stirring, the thermodynamic and kinetic conditions of the reaction are improved, and the reaction can be smoothly carried out. The stirring time is optimized, and the result shows that if the stirring time is too short, the contact of reactants is insufficient; if the stirring time is too long, on one hand, the synthesis time is prolonged, and the production cost is increased, and on the other hand, the crystal structure of the reaction product may be influenced by the too long stirring time. Through multiple comparison tests, the stirring time is preferably 20-40 min.
Preferably, in the step (2), the reaction temperature is 120 ℃ and the reaction time is 12 h. The crystal phase structure of the product can be changed by carrying out heat treatment on the precursor, and the crystal phase structure of the product is closely related to the photocatalytic activity of the product. The invention carries out optimization investigation on the temperature of heat treatment, and the result shows that the reaction temperature is lower than 110 ℃ or higher than 130 ℃ and a pure-phase product with the crystal phase structure of the invention cannot be generated.
Preferably, in the step (2), the reaction kettle is a polytetrafluoroethylene reaction kettle.
Ag prepared by the method4(GeO4) Photocatalysts are also the scope of the present invention.
In a second aspect of the present invention, there is provided the above Ag4(GeO4) The application of the photocatalyst in the photocatalytic decomposition of water to produce oxygen.
In a third aspect of the present invention, there is provided the above Ag4(GeO4) Application of the photocatalyst in degrading organic pollutants in air, waste water, surface water or drinking water.
The invention has the beneficial effects that:
(1) ag prepared by the invention4(GeO4) The photocatalyst has visible light response, has higher photocatalytic activity after being formed, and is relatively suitable for degrading organic pollutants and decomposing water to produce oxygen in the actual application of the field of photocatalysis. The experimental research shows that Ag4(GeO4) The photocatalytic material shows better photocatalytic performance, and the photocatalyst prepared by photocatalytic water decomposition and oxygen production can decompose water and produce oxygen in an amount of 200umol/g under the irradiation of visible light for 1 hour. 98% of the methylene blue organic dye can be degraded in 20 minutes.
(2) Ag of the present invention4(GeO4) The preparation and synthesis method of the photocatalyst has simple conditions, firstly takes sodium germanate and silver nitrate as raw materials to form a precursor, and then forms Ag with stable thermodynamics by heat treatment reaction crystallization4(GeO4) The photocatalyst has mild reaction conditions, is more suitable for large-scale production and practical application, and has 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 shows Ag according to the present invention4(GeO4) X-ray images of (a).
FIG. 2 is a light absorption spectrum of the product of the present invention.
FIG. 3 is an SEM image of a product of the invention.
FIG. 4 shows the formation of a photocatalyst with silver oxide and C3N4The method is used for degrading an organic dye methylene blue contrast map by visible light photocatalysis; in the figure, 1: c3N4，2：Ag2O，3：Ag4(GeO4)。
FIG. 5 is a graph showing the oxygen yield of water produced by photocatalytic decomposition using a photocatalyst formed by the product of the example of the present invention.
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.
As described in the background, a novel light having a strong absorption in the visible light region and a strong photocatalytic activity has been developedThe catalytic material has very important significance. Based on the Ag, the invention provides the Ag with visible light response4(GeO4) A photocatalyst.
In one embodiment of the present application, there is provided an Ag having a visible light response4(GeO4) The preparation method of the photocatalyst comprises the following steps:
(1) slowly dripping the sodium germanate solution into the silver nitrate solution under the stirring state, and continuously stirring to form a precursor solution;
(2) transferring the precursor solution into a reaction kettle, reacting for 10-14h at the temperature of 110-4(GeO4) A photocatalyst.
Preferably, in the step (1), the concentration of the sodium germanate solution is 0.06-0.07 mol/L; preferably 0.0625 mol/L. The concentration of the silver nitrate solution is 0.2-0.3 mol/L; preferably 0.25 mol/L.
Preferably, in the step (1), the volume ratio of the sodium germanate solution to the silver nitrate solution is 1: 1. The addition of sodium germanate and silver nitrate can affect the Ag prepared4(GeO4) The invention discloses a photocatalyst with a structure composition, which optimizes and inspects the addition of sodium germanate and silver nitrate, and finds that the molar ratio of the sodium germanate to the silver nitrate is (0.06-0.07): (0.2-0.3) is preferably added, so that the target product can be generated to the maximum extent; when the sodium germanate and the silver nitrate are added according to the molar ratio of 1:4, Ag4(GeO4) The yield of the photocatalyst is highest.
Preferably, in the step (1), the stirring is continued for 20-40 min; preferably 30 min. The contact condition of reactants can be improved through stirring, the thermodynamic and kinetic conditions of the reaction are improved, and the reaction can be smoothly carried out. The stirring time is optimized, and the result shows that if the stirring time is too short, the contact of reactants is insufficient; if the stirring time is too long, on one hand, the synthesis time is prolonged, and the production cost is increased, and on the other hand, the crystal structure of the reaction product may be influenced by the too long stirring time. Through multiple comparison tests, the stirring time is preferably 20-40 min.
Preferably, in the step (2), the reaction temperature is 120 ℃ and the reaction time is 12 h. The crystal phase structure of the product can be changed by carrying out heat treatment on the precursor, and the crystal phase structure of the product is closely related to the photocatalytic activity of the product. The invention carries out optimization investigation on the temperature of heat treatment, and the result shows that the reaction temperature is lower than 110 ℃ or higher than 130 ℃ and a pure-phase product with the crystal phase structure of the invention cannot be generated.
Preferably, in the step (2), the reaction kettle is a polytetrafluoroethylene reaction kettle.
In one embodiment of the present application, the Ag having a visible light response4(GeO4) The preparation method of the photocatalyst comprises the following steps:
(1) first 2.5 mmoles of sodium germanate (Na)2GeO3) And 10 mmol of silver nitrate were dissolved in 40 ml of deionized water, respectively.
(2) Stirring for half an hour to form a precursor solution.
(3) The resulting mixed solution was charged into a 100ml polytetrafluoroethylene reaction vessel and reacted at 120 ℃ for 12 hours.
(4) After the reaction is finished, naturally cooling, filtering and drying to obtain Ag4(GeO4) A photocatalyst.
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: ag4(GeO4) Preparation of the photocatalyst
The method comprises the following specific steps:
2.5 mmole of sodium germanate (Na)2GeO3) And 10 mmol of silver nitrate were dissolved in 40 ml of deionized water, respectively. And slowly dripping the sodium germanate solution into the silver nitrate solution under the stirring state, and stirring for half an hour to form a precursor solution. The resulting mixed solution was charged into 100ml of polytetramethyleneAnd reacting for 12 hours at 120 ℃ in a fluorine reaction kettle. After the reaction is finished, naturally cooling, filtering and drying to obtain Ag4(GeO4) A photocatalyst.
FIG. 1 shows the crystalline Ag prepared in this example4(GeO4) As can be seen from fig. 1, the product showed good crystallinity after 12 hours of hydrothermal treatment and contained Ag as a component4(GeO4) And no obvious hetero-peak appears.
FIG. 2 is a spectrum of light absorption of the final product obtained in this example, and it can be seen from FIG. 2 that the product has strong absorption in the visible light region.
FIG. 3 is a SEM photograph of the product obtained in this example, and it can be seen from FIG. 3 that Ag is obtained4(GeO4) The product is a foam-like structure formed by assembling small nanorods.
Application example 1: photocatalytic degradation of organic dyes test
1. The test method comprises the following steps:
the photocatalytic degradation organic dye test is carried out in a common 100mL glass beaker at normal temperature and pressure. The light source is a 300W xenon lamp with a filter, so that the wavelength of the light source is more than 420 nm. Methylene blue was used to evaluate the photocatalytic activity of the samples. 50mg of Ag prepared in example 1 was weighed4(GeO4) The sample was dispersed in 50ml of methylene blue B solution (20 mg/L). And (3) before the photocatalytic reaction test, magnetically stirring in the dark for 30min to ensure that methylene blue achieves adsorption balance on the surface of the catalyst, sampling 3ml every 10min after light is introduced, carrying out centrifugal separation, and taking supernatant and measuring absorbance by using an ultraviolet visible spectrophotometer.
2. And (3) test results:
the result of photocatalytic degradation of organic dye methylene blue is shown in fig. 4, and it can be seen from fig. 4 that when the photocatalyst is tested by photocatalytic degradation of organic dye methylene blue under visible light, the photocatalyst can degrade 98% of methylene blue B within 20 minutes, and the photocatalytic activity of the photocatalyst is higher than that of silver oxide and C3N4。
Application example 2: photocatalytic decomposition of water for oxygen test
1. The test method comprises the following steps:
the oxygen test of the water produced by photocatalytic decomposition is carried out in a glass container system closed by connecting circulating cooling water (5 ℃), and the vacuum condition is-97 KPa. The light source irradiated at the top is a 300W xenon lamp provided with a filter, so that the wavelength of the light source is more than 420 nm. And testing every 0.5h after light is transmitted, and converting the peak area value measured by a gas chromatograph into the yield of oxygen.
2. And (3) test results:
the oxygen production test by photocatalytic water decomposition is shown in FIG. 5, and it can be seen from the graph that the efficiency of oxygen production by photocatalytic water decomposition for 1 hour is 200. mu. mol/g under visible light.
Comparative example 1:
the molar ratio of the sodium germanate and silver nitrate additions in example 1 was adjusted to 1: 2, the rest of the procedure is the same as in example 1.
Comparative example 2:
the molar ratio of the sodium germanate and silver nitrate additions in example 1 was adjusted to 1: 6, the rest of the same procedure as in example 1.
The products prepared in comparative example 1 and comparative example 2 were subjected to X-ray diffraction analysis and light absorption analysis, respectively, and as a result, it was found that the products prepared in comparative example 1 and comparative example 2 were inferior in crystallinity and exhibited significant hetero peaks, as compared with the product prepared in example 1; in addition, the absorption capacity in the visible region is significantly lower than that of the product prepared in example 1.
Comparative example 3:
the same procedure as in example 1 was repeated except that the reaction temperature of the precursor mixed solution was adjusted to 100 ℃.
Comparative example 4:
the reaction temperature of the precursor mixed solution was adjusted to 140 ℃, and the rest of the operation was the same as in example 1.
The products prepared in comparative examples 3 and 4 were subjected to X-ray diffraction analysis, and it was found that neither comparative example 3 nor comparative example 4 could produce a pure phase product having a crystal phase structure of example 1 of the present invention.
The products prepared in comparative examples 1-4 were subjected to photocatalytic degradation of organic dyes and photocatalytic decomposition of water to produce oxygen, respectively, using the methods of application example 1 and application example 2. As a result, it was found that the products prepared in comparative examples 1 to 4 had significantly lower ability to photocatalytically degrade organic dyes than the products prepared in example 1 (the products of comparative examples 1 to 4 had an ability to degrade methylene blue B up to 90% in 20 minutes); its photocatalytic water splitting ability to produce oxygen was also significantly lower than the products prepared in example 1 (the highest efficiency of the products of comparative examples 1-4 to split water to produce oxygen in 1 hour was 140. mu. mol/g).
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 (9)
1. Ag with visible light response4(GeO4) The preparation method of the photocatalyst is characterized by comprising the following steps:
(1) slowly dripping the sodium germanate solution into the silver nitrate solution under the stirring state, and continuously stirring to form a precursor solution;
(2) transferring the precursor solution into a reaction kettle, reacting for 10-14h at the temperature of 110-4(GeO4) A photocatalyst;
wherein, in the step (1), the concentration of the sodium germanate solution is 0.06-0.07 mol/L; the concentration of the silver nitrate solution is 0.2-0.3 mol/L; the volume ratio of the sodium germanate solution to the silver nitrate solution is 1: 1.
2. The preparation method according to claim 1, wherein in the step (1), the concentration of the sodium germanate solution is 0.0625 mol/L; the concentration of the silver nitrate solution is 0.25 mol/L.
3. The method according to claim 1, wherein in the step (1), the stirring is continued for 20 to 40 min.
4. The process according to claim 3, wherein in the step (1), the stirring is continued for 30 min.
5. The method according to claim 1, wherein the reaction temperature in the step (2) is 120 ℃ and the reaction time is 12 hours.
6. The production method according to claim 1, wherein in the step (2), the reaction vessel is a polytetrafluoroethylene reaction vessel.
7. Ag produced by the production method according to any one of claims 1 to 64(GeO4) A photocatalyst.
8. Ag according to claim 74(GeO4) The application of the photocatalyst in the photocatalytic decomposition of water to produce oxygen.
9. Ag according to claim 74(GeO4) Application of the photocatalyst in degrading organic pollutants in air, waste water, surface water or drinking water.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989488A (en) * | 2012-12-20 | 2013-03-27 | 中国石油大学(华东) | Silver iodide photocatalyst, preparation method and application thereof |
| CN103586024A (en) * | 2013-11-22 | 2014-02-19 | 武汉理工大学 | Preparation method for hollow ball or spheroidal Ag2ZnGeO4 photocatalyst |
| CN105964250A (en) * | 2016-06-08 | 2016-09-28 | 山东大学 | Ag10Si4O13 photocatalyst with visible-light response and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989488A (en) * | 2012-12-20 | 2013-03-27 | 中国石油大学(华东) | Silver iodide photocatalyst, preparation method and application thereof |
| CN103586024A (en) * | 2013-11-22 | 2014-02-19 | 武汉理工大学 | Preparation method for hollow ball or spheroidal Ag2ZnGeO4 photocatalyst |
| CN105964250A (en) * | 2016-06-08 | 2016-09-28 | 山东大学 | Ag10Si4O13 photocatalyst with visible-light response and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
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| Darstellung und Kristallstruktur von Silberorthogermanat, Ag4Ge04;C. Linke et al.;《 Zeitschrift für Kristallographie》;19951231;第850-855页 * |
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