CN110201722B - Silver phosphate composite photocatalyst for treating rose bengal B in high-salinity wastewater and preparation method and application thereof - Google Patents
Silver phosphate composite photocatalyst for treating rose bengal B in high-salinity wastewater and preparation method and application thereof Download PDFInfo
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- 229910000161 silver phosphate Inorganic materials 0.000 title claims abstract description 181
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 title claims abstract description 166
- 229940019931 silver phosphate Drugs 0.000 title claims abstract description 166
- 239000002131 composite material Substances 0.000 title claims abstract description 138
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 82
- 239000002351 wastewater Substances 0.000 title claims abstract description 56
- VQHHOXOLUXRQFQ-UHFFFAOYSA-L dipotassium;4,5,6,7-tetrachloro-2',4',5',7'-tetraiodo-3-oxospiro[2-benzofuran-1,9'-xanthene]-3',6'-diolate Chemical compound [K+].[K+].O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C([O-])C(I)=C1OC1=C(I)C([O-])=C(I)C=C21 VQHHOXOLUXRQFQ-UHFFFAOYSA-L 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229920000767 polyaniline Polymers 0.000 claims abstract description 124
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims description 30
- 238000006731 degradation reaction Methods 0.000 claims description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
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- 230000015556 catabolic process Effects 0.000 claims description 16
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- 229910021642 ultra pure water Inorganic materials 0.000 claims description 11
- 239000012498 ultrapure water Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 6
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 15
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
-
- 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
Abstract
The invention discloses a silver phosphate composite photocatalyst for treating rose bengal B in high-salinity wastewater, and a preparation method and application thereof. The preparation method comprises the steps of preparing silver phosphate/polyaniline composite material solution and preparing the catalyst with chromium-doped strontium titanate solution. The silver phosphate composite photocatalyst has the advantages of low cost, good photocatalytic performance, good stability, environmental protection and the like, the preparation method has the advantages of simple process, easily available raw materials, easy operation, controllable preparation conditions, greenness, no pollution and the like, and the catalyst can effectively degrade and remove pollutants in wastewater, particularly has a good removal effect on rose bengal B in high-salinity wastewater, and has high use value and good application prospect.
Description
Technical Field
The invention belongs to the technical field of semiconductor material photocatalysis application and environmental protection, and relates to a silver phosphate composite photocatalyst for treating rose bengal B in high-salt wastewater, and a preparation method and application thereof.
Background
The discharge amount of high-salinity wastewater is large, the content of toxic and harmful organic matters is high, and great threat is caused to the environment. The discharge treatment of the wastewater reaching the standard is difficult to realize by adopting the traditional biological and physical and chemical treatment technology, and the development of a more efficient, economic and applicable treatment technology of the high-salinity wastewater is urgently needed to protect the water environment and realize the sustainable development of the industry in China. Solar energy is a clean and renewable energy source, and is concerned about solving the energy crisis, but how to effectively utilize solar energy and realize sustainable development is undoubtedly a problem which needs to be solved urgently in all countries at present. The semiconductor photocatalysis technology is a low-cost, environment-friendly and sustainable treatment technology, has great potential in the wastewater industry, and the advanced oxidation technology is widely applied to the aspect of removing persistent organic matters and microorganisms in water. The technology mainly utilizes the effects that electrons jump from a valence band to a conduction band position under the excitation of light by a semiconductor, so that photogenerated electrons are formed in the conduction band, photogenerated holes are formed in the valence band, organic pollutants are decomposed by the reduction-oxidation reaction of photogenerated electron-hole pairs, bacteria are killed, heavy metal ions are reduced, peculiar smell is eliminated, and the like.
Currently, the research of photocatalytic materials has been rapidly spread around the world and made a great deal of progress, but there still exist some problems, the root cause of which is that the recombination of photogenerated electron-hole pairs is much faster than the process of capture-transfer, and thus the effective improvement of the separation of photogenerated carriers is of great importance. The effective improvement of the separation efficiency of the photon-generated carriers depends on factors such as the electronic structure, the light absorption characteristic, the particle size, the surface area, the surface modification, the reaction condition, the photosensitizer and the like of the photocatalyst, and the formation of the nano heterojunction is one of important methods for inhibiting the recombination of photon-generated electron-hole pairs. A heterojunction is an interface region formed by two different semiconductors coming into contact. The nano heterojunction utilizes the valence band hole of the narrow-band semiconductor and the conduction band electron of the wide-band semiconductor to react, promotes photoinduced charge separation, improves photoelectric conversion efficiency, and prolongs the life cycle of current carriers. The general heterojunction structure enables photogenerated electrons and holes to be respectively gathered on a conduction band and a valence band with lower energy, and the life cycle of carriers can be effectively prolonged. The Z-type heterojunction is a special heterojunction, can widen the photoresponse range and improve the redox capability of the whole system, thereby having better photocatalytic activity.
The silver phosphate material has excellent visible light catalytic activity as a catalyst, however, the silver phosphate material has serious light corrosivity in the actual photocatalysis process, and a good degradation effect is difficult to obtain. Therefore, the existing researchers provide the silver phosphate/polyaniline composite material, the degradation effect of the silver phosphate on pollutants is enhanced by modifying polyaniline on the silver phosphate, and the problems of insufficient light stability and the like still exist. Obviously, how to further improve the light stability of the silver phosphate material is a technical problem to be solved urgently in the field. In addition, the chromium-doped strontium titanate material is used as a catalyst, which can only absorb ultraviolet sunlight and cannot effectively utilize sunlight in a visible light band, which severely limits the wide application of the chromium-doped strontium titanate material. Therefore, how to obtain the silver phosphate composite photocatalyst with low cost, good photocatalytic performance, good stability and environmental protection has very important significance for effectively treating high-salinity wastewater, particularly rose bengal B high-salinity wastewater.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides the silver phosphate composite photocatalyst for treating the rose bengal B in the high-salt wastewater, which has the advantages of low cost, good photocatalytic performance, good stability and environmental protection, and also provides a preparation method of the silver phosphate composite photocatalyst, which has the advantages of simple process, easily obtained raw materials, easy operation, controllable preparation conditions, environmental friendliness and no pollution, and application of the silver phosphate composite photocatalyst in treating the rose bengal B in the high-salt wastewater.
In order to solve the technical problems, the invention adopts the technical scheme that:
a silver phosphate composite photocatalyst for treating rose bengal B in high-salt wastewater comprises a silver phosphate/polyaniline composite material, wherein chromium-doped strontium titanate is loaded on the silver phosphate/polyaniline composite material; the silver phosphate/polyaniline composite material takes polyaniline silver phosphate as a carrier, and the polyaniline is loaded with the silver phosphate.
The silver phosphate composite photocatalyst is further improved, wherein the mass ratio of the silver phosphate/polyaniline composite material to the chromium-doped strontium titanate in the silver phosphate composite photocatalyst is 100: 1-7; the mass ratio of the silver phosphate to the polyaniline in the silver phosphate/polyaniline composite material is 100: 1-7.
As a general technical concept, the invention also provides a preparation method of the silver phosphate composite photocatalyst for treating rose bengal B in high-salt wastewater, which comprises the following steps:
s1, mixing the silver phosphate/polyaniline composite material with water, carrying out ultrasonic treatment, adding polyvinylpyrrolidone, and stirring to obtain a silver phosphate/polyaniline composite material solution;
s2, mixing chromium-doped strontium titanate with water, carrying out ultrasonic treatment, dropwise adding the obtained chromium-doped strontium titanate solution into the silver phosphate/polyaniline composite material solution obtained in the step S1, carrying out reaction under the condition of keeping out of the sun, centrifuging, washing, and drying to obtain the silver phosphate composite photocatalyst.
The preparation method is further improved, wherein the mass ratio of the silver phosphate/polyaniline composite material to the polyvinylpyrrolidone is 1: 1-1.5; the mass ratio of the silver phosphate/polyaniline composite material to the chromium-doped strontium titanate is 100: 1-7.
In the preparation method, the preparation method of the silver phosphate/polyaniline composite material is further improved, and comprises the following steps:
(1) mixing polyaniline with N-N dimethyl amide, and performing ultrasonic treatment to obtain a polyaniline solution;
(2) mixing AgNO3Dropwise adding the solution into the polyaniline solution obtained in the step (1), and stirring under the condition of keeping out of the sun to obtain AgNO3A polyaniline solution;
(3) mixing Na2HPO4·12H2Dropwise adding O solution into AgNO obtained in the step (2)3Stirring in a polyaniline solution under a dark condition, washing, and drying to obtain a silver phosphate/polyaniline composite material;
the preparation method of the chromium-doped strontium titanate comprises the following steps:
(a) will [ (CH)3)2CHO]4Ti、Sr(Ac)2、Cr(NO3)3·9H2Mixing O and glycol, and stirring until the solution becomes powder;
(b) and (b) mixing the powder obtained in the step (a) with a sodium hydroxide solution, stirring, reacting in a reaction kettle, centrifuging, washing and drying to obtain the chromium-doped strontium titanate.
In the preparation method, the mass-to-volume ratio of the polyaniline to the N-N dimethyl amide in the step (1) is 0.42 g-2.94 g: 1L; the ultrasonic treatment time is 1-3 h;
in the step (2), the AgNO3AgNO in solution3The mass ratio of the polyaniline to the polyaniline in the polyaniline solution is 100: 0.81-5.75; the stirring time is 10-20 h;
in the step (3), the Na2HPO4·12H2Na in O solution2HPO4·12H2O and the AgNO3AgNO in polyaniline solution3The molar ratio of (A) to (B) is 1: 3; the stirring time is 1-6 h; the drying is carried out under vacuum conditions; the drying temperature is 50-75 ℃;
in the step (a), the [ (CH)3)2CHO]4Ti、Sr(Ac)2、Cr(NO3)3·9H2The molar ratio of O is 20: 19: 1; the stirring is carried out at the temperature of 120-160 ℃;
in the step (b), the mass-volume ratio of the powder to the sodium hydroxide solution is 7-17 g: 1L; the concentration of the sodium hydroxide solution is 2-6 mol/L; the stirring time is 20 min-60 min; the temperature of the reaction is 180 ℃; the reaction time is 30-40 h; the washing is to wash the solid substances obtained by centrifugation for 2 to 3 times respectively by adopting ethanol and ultrapure water; the drying is carried out under vacuum conditions; the drying temperature is 50-75 ℃.
In the above preparation method, further improvement is provided, in the step S1, the time of the ultrasonic treatment is 10min to 30 min; the stirring time is 10min to 30 min;
in the step S2, the reaction time is 4-8 h; the washing is to wash the solid substances obtained by centrifugation for 2 to 3 times respectively by adopting ethanol and ultrapure water; the drying is carried out under vacuum conditions; the drying temperature is 50-75 ℃.
As a general technical concept, the invention also provides an application of the silver phosphate composite photocatalyst or the silver phosphate composite photocatalyst prepared by the preparation method in treatment of rose bengal B high-salinity wastewater.
The application is further improved, and comprises the following steps: mixing the silver phosphate composite photocatalyst with the rose bengal B high-salt wastewater, and performing degradation reaction under the illumination condition to finish degradation of the rose bengal B in the high-salt wastewater; the addition amount of the silver phosphate composite photocatalyst is 0.5g of silver phosphate composite photocatalyst added into each liter of rose bengal B high-salt wastewater.
In the application, the concentration of the rose bengal B high-salinity wastewater is further improved to be 20 mg/L; the light source of the degradation reaction is a 300W xenon lamp; the time of the degradation reaction is 10 min-20 min.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a silver phosphate composite photocatalyst for treating rose bengal B in high-salinity wastewater, which comprises a silver phosphate/polyaniline composite material (Ag)3PO4/PANI), the silver phosphate/polyaniline composite material is loaded with chromium-doped strontium titanate (Cr: SrTiO)3) The silver phosphate/polyaniline composite material takes polyaniline silver phosphate as a carrier, and the polyaniline is loaded with the silver phosphate. In the invention, the silver phosphate/polyaniline composite material is used as a carrier, wherein the visible light quantum efficiency of the silver phosphate is up to 90 percent, and the silver phosphate/polyaniline composite material has the advantages ofThe composite material has excellent visible light catalytic activity and good matching property with an energy band structure of chromium-doped strontium titanate, so that the chromium-doped strontium titanate is loaded on the silver phosphate/polyaniline composite material, and the silver phosphate and the chromium-doped strontium titanate successfully construct a Z-type heterojunction, so that the constructed Z-type heterojunction can improve the light stability, can effectively promote the separation of photo-generated electron-hole pairs, prolongs the service life of charge carriers, and obtains more active free radicals, thereby improving the photocatalytic performance of the material; meanwhile, polyaniline is compounded with silver phosphate and chromium-doped strontium titanate, and by utilizing the conjugated structure and good conductivity of polyaniline, the migration efficiency of silver phosphate and chromium-doped strontium titanate charge carriers can be improved, and the separation of photo-generated charge carriers is promoted, so that the recombination of photo-generated electron-hole pairs is inhibited, and the photocatalytic performance is further improved. In addition, the polyaniline has excellent stability, and the polyaniline is compounded with silver phosphate and chromium-doped strontium titanate, so that the light stability of the silver phosphate composite photocatalyst can be further improved, and the recycling performance of the material is improved. In addition, the polyaniline, the silver phosphate and the chromium-doped strontium titanate used in the invention have low cost and less toxic and harmful effects on the environment, so that the silver phosphate composite photocatalyst formed by compounding the polyaniline, the silver phosphate and the chromium-doped strontium titanate has low cost and is environment-friendly. Therefore, the silver phosphate composite photocatalyst has the advantages of low cost, good photocatalytic performance, good stability, environmental protection and the like, can effectively degrade and remove pollutants in wastewater, particularly has a good removing effect on rose bengal B in high-salinity wastewater, and has high use value and good application prospect.
(2) In the silver phosphate composite photocatalyst, the mass ratio of the silver phosphate/polyaniline composite material to the chromium-doped strontium titanate is 100: 1-7, and the mass ratio of the silver phosphate to the polyaniline in the silver phosphate/polyaniline composite material is 100: 1-7, so that the silver phosphate composite photocatalyst has higher photocatalytic activity and better light stability.
(3) The invention also provides a preparation method of the silver phosphate composite photocatalyst, which takes the silver phosphate/polyaniline composite material, polyvinylpyrrolidone and chromium-doped strontium titanate as raw materials, and the silver phosphate/polyaniline composite material, the polyvinylpyrrolidone and the chromium-doped strontium titanate are mixed and react to prepare the silver phosphate composite photocatalyst with good stability and excellent photocatalytic performance. The preparation method has the advantages of simple process, easily obtained raw materials, low cost and the like, is environment-friendly, does not generate toxic and harmful byproducts, is suitable for large-scale preparation, and meets the requirement of actual production.
(4) The silver phosphate composite photocatalyst can be used for treating rose bengal B high-salt wastewater, can realize effective degradation of rose bengal B in the high-salt wastewater by mixing the silver phosphate composite photocatalyst with the rose bengal B high-salt wastewater and carrying out degradation reaction under the illumination condition, has the advantages of simple application process, low treatment cost, high treatment efficiency, good degradation effect and the like, and has very important significance for effectively treating the rose bengal B in the high-salt wastewater.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is a flow chart of a preparation process of a silver phosphate composite photocatalyst for treating rose bengal B from high-salinity wastewater in example 1 of the present invention.
Fig. 2 is an SEM image of the silver phosphate composite photocatalyst prepared in example 1 of the present invention.
FIG. 3 is a TEM image of a silver phosphate composite photocatalyst prepared in example 1 of the present invention.
Fig. 4 is a graph of the degradation effect of different silver phosphate composite photocatalysts on rose bengal B high-salt wastewater in example 5 of the present invention.
Fig. 5 is a graph of the effect of the silver phosphate composite photocatalyst on the cyclic degradation of rose bengal B high-salt wastewater in example 6 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
In the following examples of the present invention, unless otherwise specified, materials and instruments used are commercially available, processes used are conventional, apparatuses used are conventional, and the obtained data are average values of three or more repeated experiments.
Example 1
A silver phosphate composite photocatalyst for treating rose bengal B in high-salinity wastewater comprises a silver phosphate/polyaniline composite material, wherein chromium-doped strontium titanate is loaded on the silver phosphate/polyaniline composite material, the silver phosphate/polyaniline composite material takes polyaniline silver phosphate as a carrier, and the polyaniline is loaded with silver phosphate.
In the embodiment, the mass ratio of the silver phosphate/polyaniline composite material to the chromium-doped strontium titanate in the silver phosphate composite photocatalyst is 100: 3; the mass ratio of the silver phosphate to the polyaniline in the silver phosphate/polyaniline composite material is 100: 5.
The preparation method of the silver phosphate composite photocatalyst according to the embodiment is shown in fig. 1, and includes the following steps:
(1) preparing a silver phosphate/polyaniline composite material:
(1.1) weighing 0.0628g of Polyaniline (PANI) in 30mL of N-N dimethyl amide (DMF), and carrying out ultrasonic treatment for 3h to obtain a polyaniline solution.
(1.2) weighing 1.53g AgNO3Dissolving in 30mL of ultrapure water to obtain AgNO3Dropwise adding the solution into the polyaniline solution obtained in the step (1.1), and continuously stirring for 12 hours in the dark to obtain AgNO3Polyaniline solution.
(1.3) weighing 1.074g of Na2HPO4·12H2O was dissolved in 30mL of ultrapure water to obtain Na2HPO4·12H2Dropwise adding O solution into AgNO obtained in step (1.1)3Stirring in a dark place for 4 hours in a polyaniline solution, centrifuging a mixture obtained by stirring to perform solid-liquid separation, washing with ethanol and ultrapure water for 2 times respectively, and drying at 60 ℃ under a vacuum condition to obtain a silver phosphate/polyaniline composite material, which is marked as Ag3PO4/PANI。
(2) Preparation of chromium-doped strontium titanate:
(2.1) 3.895g of Sr (Ac) were weighed respectively2And 0.4g Cr (NO)3)3·9H2O was added to 60mL of ethylene glycol, and after completely dissolving, stirring was continued for 30min, and 5.92mL of [ (CH)3)2CHO]4And stirring the Ti solution for 30min, transferring the Ti solution into an oil bath at the temperature of 150 ℃, and continuously stirring until the solution becomes a gel powder state to obtain precursor powder.
(2.2) weighing 0.9g of precursor powder obtained in the step (2.1) and 60mL of NaOH solution with the concentration of 5mol/L, mixing and stirring for 40min, transferring the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining with the volume of 100mL, reacting for 36h at 180 ℃, centrifuging the reaction product solution, washing solid substances obtained by centrifuging respectively 2 times by using ethanol and ultrapure water, and drying in vacuum at 60 ℃ to obtain chromium-doped strontium titanate which is recorded as Cr: SrTiO3。
(3) Preparing a silver phosphate composite photocatalyst:
(3.1) weighing 0.3g of the silver phosphate/polyaniline composite material prepared in the step (1) in 30mL of ultrapure water, carrying out ultrasonic treatment for 30min, adding 0.2g of polyvinylpyrrolidone, and stirring for 30min to obtain a silver phosphate/polyaniline composite material solution.
(3.2) weighing 0.009g of chromium-doped strontium titanate prepared in the step (2) in 30mL of ultrapure water, carrying out ultrasonic treatment for 30min, dropwise adding the obtained chromium-doped strontium titanate solution into the silver phosphate/polyaniline composite material solution obtained in the step (3.1), carrying out a light-shielding reaction for 4h, centrifuging, washing solid substances obtained by centrifuging for 2 times by using ethanol and ultrapure water respectively, and carrying out vacuum drying at 60 ℃ to obtain a silver phosphate composite photocatalyst recorded as Ag3PO4/PANI/3％Cr∶SrTiO3。
Fig. 2 is an SEM image of the silver phosphate composite photocatalyst prepared in example 1 of the present invention. As can be seen from FIG. 2, the silver phosphate in the silver phosphate composite photocatalyst of the invention is irregular small spherical polyhedral nanoparticles with a particle size of 0.2-1.2 μm, and the polyaniline exhibits chaotic and agglomerated shapes and Ag3PO4Closely adhered to the PANI, the particle size of the silver phosphate/polyaniline composite material thus formed was 10-20 μm. In fig. 2, the chromium-doped strontium titanate is not clearly identified in the figure due to its low content.
To is coming toFurther confirming that the silver phosphate composite photocatalyst has been successfully prepared, a transmission electron microscope image of the silver phosphate composite photocatalyst is provided, as shown in fig. 3. FIG. 3 is a TEM image of a silver phosphate composite photocatalyst prepared in example 1 of the present invention. As can be seen from FIG. 3, Ag3PO4And Cr SrTiO3With good connection therebetween. Ag3PO4Has a interplanar spacing of 0.245nm, corresponding to Ag3PO4(JCPDS card No.06-0505) with the interplanar distance of the (211) plane. Cr SrTiO3Has an interplanar spacing of 0.231nm, which is comparable to SrTiO3(JCPDS card No.35-0734) has a uniform interplanar spacing in the (110) plane. Therefore, the silver phosphate composite photocatalyst is successfully prepared.
Example 2
The silver phosphate composite photocatalyst for treating rose bengal B in high-salt wastewater is basically the same as the silver phosphate composite photocatalyst in example 1, and the differences are only that: in the silver phosphate composite photocatalyst of example 2, the mass ratio of the silver phosphate/polyaniline composite material to the chromium-doped strontium titanate is 100: 1.
The preparation method of the silver phosphate composite photocatalyst for treating rose bengal B in high-salt wastewater is basically the same as that in example 1, and the differences are only that: the amount of chromium-doped strontium titanate used in example 2 was 0.003 g.
The silver phosphate composite photocatalyst prepared in example 2 is marked as Ag3PO4/PANI/1％Cr∶SrTiO3。
Example 3
The silver phosphate composite photocatalyst for treating rose bengal B in high-salt wastewater is basically the same as the silver phosphate composite photocatalyst in example 1, and the differences are only that: the mass ratio of the silver phosphate/polyaniline composite material to the chromium-doped strontium titanate in the silver phosphate composite photocatalyst of example 3 is 100: 5.
The preparation method of the silver phosphate composite photocatalyst for treating rose bengal B in high-salt wastewater is basically the same as that in example 1, and the differences are only that: the amount of chromium-doped strontium titanate used in example 3 was 0.015 g.
The silver phosphate composite photocatalyst prepared in example 3, noted as Ag3PO4/PANI/5％Cr∶SrTiO3。
Example 4
The silver phosphate composite photocatalyst for treating rose bengal B in high-salt wastewater is basically the same as the silver phosphate composite photocatalyst in example 1, and the differences are only that: the mass ratio of the silver phosphate/polyaniline composite material to the chromium-doped strontium titanate in the silver phosphate composite photocatalyst of example 4 is 100: 7.
The preparation method of the silver phosphate composite photocatalyst for treating rose bengal B in high-salt wastewater is basically the same as that in example 1, and the differences are only that: the amount of chromium-doped strontium titanate used in example 4 was 0.021 g.
The silver phosphate composite photocatalyst prepared in example 4 is marked as Ag3PO4/PANI/7％Cr∶SrTiO3。
Example 5
The application of the silver phosphate composite photocatalyst in treatment of rose bengal B high-salt wastewater, specifically relates to treatment of rose bengal B in high-salt wastewater by using the silver phosphate composite photocatalyst, and comprises the following steps:
the silver phosphate composite photocatalyst (Ag) prepared in example 1-4 was used3PO4/PANI/1％Cr∶SrTiO3、Ag3PO4/PANI/3％Cr∶SrTiO3、Ag3PO4/PANI/5％Cr∶SrTiO3、Ag3PO4/PANI/7％Cr∶SrTiO3) Silver phosphate (Ag)3PO4) Chromium-doped strontium titanate (Cr: SrTiO)3) Silver phosphate/polyaniline composite material (Ag)3PO4/PANI), respectively 50mg, adding into 100mL of 20mg/L rose bengal B high-salt wastewater, stirring in dark for 30min to obtain uniform mixture and reach adsorption-desorption balance, and placing in 300W xenon lamp (lambda)>420nm) for 10min under the irradiation condition to finish the degradation of the rose bengal B in the high-salinity wastewater.
FIG. 4 shows that different silver phosphate composite photocatalysts in example 5 of the present invention have a high rose bengal B activityThe degradation effect of the salt wastewater is shown. As can be seen from FIG. 4, the silver phosphate composite photocatalyst prepared by the method can realize efficient and thorough degradation of rose bengal B in high-salt wastewater, wherein the silver phosphate composite photocatalyst (Ag) is3PO4/PANI/1％Cr∶SrTiO3、Ag3PO4/PANI/3％Cr∶SrTiO3、Ag3PO4/PANI/5％Cr∶SrTiO3、Ag3PO4/PANI/7％Cr∶SrTiO3) The removal rates of the rose bengal B high-salt wastewater within 10min are respectively about 100%, 98.68% and 94.10%, and the removal rate of Ag is3PO4/PANI/3％Cr∶SrTiO3The highest degradation rate, silver phosphate (Ag)3PO4) Chromium-doped strontium titanate (Cr: SrTiO)3) Silver phosphate/polyaniline composite material (Ag)3PO4/PANI) has the removal rate of 54.09%, 10.94% and 98.07% respectively for the rose bengal B high-salinity wastewater within 10min, which shows that the silver phosphate composite photocatalyst has excellent photocatalytic performance.
Example 6
Investigating the stability of the silver phosphate composite photocatalyst, in particular to the method for circularly treating rose bengal B high-salt wastewater by the silver phosphate composite photocatalyst, which comprises the following steps:
(1) the silver phosphate composite photocatalyst (Ag) prepared in example 1 was used3PO4(PANI/3% Cr: SrTiO), silver phosphate (Ag)3PO4) Silver phosphate/polyaniline composite material (Ag)3PO4/PANI), respectively adding 50mg into 100mL of 20mg/L rose bengal B high-salt wastewater, stirring for 30min under dark condition to achieve adsorption-desorption equilibrium, and mixing under 300W xenon lamp (lambda)>420nm) for 10min under the irradiation condition to finish the degradation of the rose bengal B in the high-salinity wastewater.
(2) After the degradation reaction in the step (1) is finished, filtering, recovering the catalyst, and regenerating the catalyst; and (3) continuously treating the rose bengal B high-salt wastewater by using the regenerated catalyst according to the method in the step (1), and repeating the treatment for 5 times.
FIG. 5 shows silver phosphate composite photocatalyst in example 6 of the present inventionThe effect of the reagent on the cyclic degradation of the rose bengal B high-salinity wastewater is shown. As can be seen from FIG. 5, after 5 cycles of the experiment, silver phosphate (Ag)3PO4) Silver phosphate/polyaniline composite material (Ag)3PO4/PANI) and silver phosphate composite photocatalyst (Ag)3PO4/PANI/3％Cr∶SrTiO3) The degradation efficiency is 41.67%, 80.22% and 92.24% respectively. Compared with the first time, the degradation efficiency is respectively reduced by 21.20%, 19.46% and 7.76%. Silver phosphate composite photocatalyst (Ag)3PO4/PANI/3％Cr∶SrTiO3) Has higher photocatalytic stability.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (8)
1. The application of the silver phosphate composite photocatalyst in treatment of rose bengal B high-salt wastewater is characterized by comprising the following steps: mixing the silver phosphate composite photocatalyst with the rose bengal B high-salt wastewater, and performing degradation reaction under the illumination condition to finish degradation of the rose bengal B in the high-salt wastewater; the addition amount of the silver phosphate composite photocatalyst is 0.5g of silver phosphate composite photocatalyst added into each liter of rose bengal B high-salt wastewater; the concentration of the rose bengal B high-salinity wastewater is 20 mg/L;
the silver phosphate composite photocatalyst comprises a silver phosphate/polyaniline composite material, wherein chromium-doped strontium titanate is loaded on the silver phosphate/polyaniline composite material; the silver phosphate/polyaniline composite material takes polyaniline silver phosphate as a carrier, and the polyaniline is loaded with the silver phosphate; the mass ratio of the silver phosphate/polyaniline composite material to the chromium-doped strontium titanate in the silver phosphate composite photocatalyst is 100: 1-3.
2. The use according to claim 1, wherein the light source for the degradation reaction is a 300W xenon lamp; the time of the degradation reaction is 10 min-20 min.
3. The application of the silver phosphate/polyaniline composite material as claimed in claim 1, wherein the mass ratio of the silver phosphate to the polyaniline in the silver phosphate/polyaniline composite material is 100: 1-7.
4. The use of claim 3, wherein the preparation method of the silver phosphate composite photocatalyst comprises the following steps:
s1, mixing the silver phosphate/polyaniline composite material with water, carrying out ultrasonic treatment, adding polyvinylpyrrolidone, and stirring to obtain a silver phosphate/polyaniline composite material solution;
s2, mixing chromium-doped strontium titanate with water, carrying out ultrasonic treatment, dropwise adding the obtained chromium-doped strontium titanate solution into the silver phosphate/polyaniline composite material solution obtained in the step S1, carrying out reaction under the condition of keeping out of the sun, centrifuging, washing, and drying to obtain a silver phosphate composite photocatalyst; the mass ratio of the silver phosphate/polyaniline composite material to the chromium-doped strontium titanate is 100: 1-3.
5. The application of the silver phosphate/polyaniline composite material as claimed in claim 4, wherein the mass ratio of the silver phosphate/polyaniline composite material to the polyvinylpyrrolidone is 1: 1-1.5.
6. The use according to claim 5, wherein the preparation method of the silver phosphate/polyaniline composite material comprises the following steps:
(1) mixing polyaniline with N-N dimethyl amide, and performing ultrasonic treatment to obtain a polyaniline solution;
(2) mixing AgNO3Dropwise adding the solution into the polyaniline solution obtained in the step (1), and stirring under the condition of keeping out of the sun to obtain AgNO3A polyaniline solution;
(3) mixing Na2HPO4·12H2Dropwise adding O solution into AgNO obtained in the step (2)3Stirring in polyaniline solution under the condition of keeping out of the sun,washing and drying to obtain the silver phosphate/polyaniline composite material;
the preparation method of the chromium-doped strontium titanate comprises the following steps:
(a) will [ (CH)3)2CHO]4Ti、Sr(Ac)2、Cr(NO3)3·9H2Mixing O and glycol, and stirring until the solution becomes powder;
(b) and (b) mixing the powder obtained in the step (a) with a sodium hydroxide solution, stirring, reacting in a reaction kettle, centrifuging, washing and drying to obtain the chromium-doped strontium titanate.
7. The use according to claim 6, wherein in the step (1), the mass-to-volume ratio of the polyaniline to the N-N dimethyl amide is 0.42 g-2.94 g: 1L; the ultrasonic treatment time is 1-3 h;
in the step (2), the AgNO3AgNO in solution3The mass ratio of the polyaniline to the polyaniline in the polyaniline solution is 100: 0.81-5.75; the stirring time is 10-20 h;
in the step (3), the Na2HPO4·12H2Na in O solution2HPO4·12H2O and the AgNO3AgNO in polyaniline solution3The molar ratio of (A) to (B) is 1: 3; the stirring time is 1-6 h; the drying is carried out under vacuum conditions; the drying temperature is 50-75 ℃;
in the step (a), the [ (CH)3)2CHO]4Ti、Sr(Ac)2、Cr(NO3)3·9H2The molar ratio of O is 20: 19: 1; the stirring is carried out at the temperature of 120-160 ℃;
in the step (b), the mass-volume ratio of the powder to the sodium hydroxide solution is 7-17 g: 1L; the concentration of the sodium hydroxide solution is 2-6 mol/L; the stirring time is 20 min-60 min; the temperature of the reaction is 180 ℃; the reaction time is 30-40 h; the washing is to wash the solid substances obtained by centrifugation for 2 to 3 times respectively by adopting ethanol and ultrapure water; the drying is carried out under vacuum conditions; the drying temperature is 50-75 ℃.
8. The use according to any one of claims 4 to 7, wherein in the step S1, the time of the ultrasonic treatment is 10min to 30 min; the stirring time is 10min to 30 min;
in the step S2, the reaction time is 4-8 h; the washing is to wash the solid substances obtained by centrifugation for 2 to 3 times respectively by adopting ethanol and ultrapure water; the drying is carried out under vacuum conditions; the drying temperature is 50-75 ℃.
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