CN113731411A - Cu2MoS2O4/Ag2V4O11/g-C3N4Preparation method and application of ternary composite catalyst - Google Patents
Cu2MoS2O4/Ag2V4O11/g-C3N4Preparation method and application of ternary composite catalyst Download PDFInfo
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- 229910017656 Ag2V4O11 Inorganic materials 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 239000011206 ternary composite Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title abstract description 6
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 71
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 71
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000011218 binary composite Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 25
- 239000012153 distilled water Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003760 magnetic stirring Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 238000002835 absorbance Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000013032 photocatalytic reaction Methods 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- KUIXZSYWBHSYCN-UHFFFAOYSA-L remazol brilliant blue r Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=C2C(=O)C3=CC=CC=C3C(=O)C2=C1NC1=CC=CC(S(=O)(=O)CCOS([O-])(=O)=O)=C1 KUIXZSYWBHSYCN-UHFFFAOYSA-L 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
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- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims 1
- 239000003517 fume Substances 0.000 claims 1
- 229940107698 malachite green Drugs 0.000 claims 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims 1
- 229940043267 rhodamine b Drugs 0.000 claims 1
- 229910052979 sodium sulfide Inorganic materials 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 238000011068 loading method Methods 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum or polonium
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
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- B01J35/39—Photocatalytic properties
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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
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a Cu2MoS2O4/Ag2V4O11/g‑C3N4The preparation method and the application of the ternary composite catalyst are characterized in that the catalyst is composed of the following raw materials in parts by weight: cu2MoS2O4:1 to 10 parts of Ag2V4O11/g‑C3N4:10 parts. The preparation method comprises the following steps: (1) cu2MoS2O4Preparing; (2) ag2V4O11/g‑C3N4Preparing a binary composite material; (3) cu2MoS2O4/Ag2V4O11/g‑C3N4And (3) preparing the ternary composite catalytic material. The invention synthesizes Cu by a wet impregnation method2MoS2O4/Ag2V4O11/g‑C3N4The ternary photocatalyst has the advantages of convenient operation, low cost, good effect on organic wastewater and good prospect in actual production and commercial application.
Description
Technical Field
The invention relates to Cu2MoS2O4/Ag2V4O11/g-C3N4A preparation method and application of a ternary composite catalyst belong to the technical field of catalyst preparation and application.
Background
The generation of printing and dyeing wastewater is inevitable harm in the development process of modern industries such as textile, papermaking and the like. The printing and dyeing wastewater has strong toxicity and high chroma and is difficult to degrade under natural conditions, so the treatment process is always concerned by researchers. The photocatalysis technology is distinguished from various treatment technologies by environmental protection, low cost and no secondary pollution.
Graphite phase carbon nitride (g-C)3N4) The material is a semiconductor photocatalytic material with wide application, has cheap and easily obtained raw materials, low production cost, visible light activity and high chemical and thermal stability, and is used in the fields of photocatalytic water decomposition, organic pollutant degradation and the like. However, g-C3N4Wide forbidden band width (2.7 eV), small specific surface area and narrow visible light response range, thereby greatly limiting the photocatalysis of the materialAnd (4) performance. Thus, g-C is modified3N4To overcome the defects and improve the photocatalytic activity of the photocatalyst is g-C3N4One of the major points of the study.
Disclosure of Invention
The invention aims to provide Cu2MoS2O4/Ag2V4O11/g-C3N4Preparation method and application of ternary composite catalyst by using Cu2MoS2O4And Ag2V4O11Co-modification of g-C3N4To improve its photocatalytic efficiency.
In the present invention, Ag2V4O11Belongs to transition V group oxides, has narrow forbidden band width (only 1.45 eV), proper energy band structure and strong electron transfer rate, and is one of emerging photocatalytic materials. Cu2MoS2O4Is at Bi2MoS2O4In addition, Cu replaces Bi to form a oxysulfide, and the sulfuration can shorten the band gap of the semiconductor. Cu2MoS2O4The monomer has no photocatalytic activity, but can effectively improve the photocatalytic activity of a semiconductor after forming a heterojunction with another semiconductor.
The invention provides a Cu2MoS2O4/Ag2V4O11/g-C3N4The ternary composite catalyst consists of the following raw materials in parts by weight:
Cu2MoS2O4:1 to 10 parts by weight of a surfactant,
Ag2V4O11/g-C3N4:10 portions of Ag2V4O11：g-C3N4The mass ratio of (A) to (B) is 1-100: 100.
the present invention provides the above Cu2MoS2O4/Ag2V4O11/g-C3N4The preparation method of the three-way composite catalyst is characterized by comprising the following steps:
（1）Cu2MoS2O4system of (1)Preparing:
under magnetic stirring, 0.5-0.8 g of (NH)4）6Mo7O24·12H2Dissolving O in 60-150 mL of distilled water, and adding 3.8-5.4 g of Na2And S, continuously stirring until the color becomes clear yellow. Dropwise addition of HCl produced a brown substance and a pungent odor. When the pH value is adjusted to 6-8, stirring for 10-30 min, and adding 3.6-5.6 g of Cu (NO)3）2·3H2O, after being stirred uniformly, the mixture is condensed and refluxed for 9-12 h at the temperature of 60-80 ℃, the obtained sample is collected and washed for a plurality of times by water and absolute ethyl alcohol, and is dried for 10-24 h at the temperature of 50-80 ℃ and ground;
（2）Ag2V4O11/g-C3N4preparing a binary composite material:
mixing AgNO3Dissolving the mixture in 10-20 mL of distilled water to form a solution A with the concentration of 1-6 mmol/L. Under the conditions of heating and magnetic stirring, NH is added4VO3Dissolving the mixture in 30-60 mL of distilled water to form a light yellow clear solution, namely a solution B with the concentration of 0.5-2 mmol/L. And adding the solution A into the solution B to generate yellow floccules, wherein the solution A accounts for 0.8-1.2 parts, and the solution B accounts for 1 part.
With HNO3And adjusting the pH of the solution to be = 2.2-2.6, and then deepening the color of the solution to be orange yellow. And continuously stirring for 30-60 min under heating, so that the solution turns into brownish red. Adding 0.1-2 g g-C at room temperature3N4And carrying out ultrasonic treatment for 30-60 min, stirring for 10-24 h, carrying out hydrothermal reaction, washing the reaction product for several times by using distilled water and absolute ethyl alcohol respectively, and drying at 50-80 ℃ for 8-24 h. Ag in the product2V4O11：g-C3N4The mass ratio is 1-100: 100, respectively;
（3）Cu2MoS2O4/Ag2V4O11/g-C3N4preparing a three-way composite catalyst:
weighing 0.02-1.0 g of monomer Cu2MoS2O4And 0.4-1.0 g Ag2V4O11/g-C3N4And (3) placing the mixture into a beaker, adding 30-100 mL of solution, performing ultrasonic dispersion for 60-120 min, and stirring for 2-14 h. ObtainAnd centrifuging the obtained product at 8000-10000 r/min for 5-10 min, taking the precipitate, drying in an oven at 50-80 ℃ for 10-24 h, and grinding to obtain the ternary composite catalyst.
Cu as described above2MoS2O4/Ag2V4O11/g-C3N4The preparation method of the ternary composite catalyst comprises the steps of (2) heating the solution at 20-60 ℃ and performing hydrothermal reaction at 160-190 ℃.
Cu as described above2MoS2O4/Ag2V4O11/g-C3N4Preparation method of ternary composite catalyst, Cu in step (3)2MoS2O4And Ag2V4O11/g-C3N4The mass ratio of (A) to (B) is 1-10: 10.
Cu as described above2MoS2O4/Ag2V4O11/g-C3N4In the preparation method of the ternary composite catalyst, the solution used in the step (3) is distilled water, methanol or a distilled water/methanol mixture.
The present invention provides the above Cu2MoS2O4/Ag2V4O11/g-C3N4The application of the ternary composite catalyst in the catalytic degradation of organic dye under the condition of visible light.
Taking an organic dye reactive blue 19 as an example, preparing 250 mL of reactive blue 19 with the concentration of 20 mg/L, and then weighing 0.05-0.12 g of Cu2MoS2O4/Ag2V4O11/g-C3N4Adding the three-way catalyst into the active blue 19 solution, performing ultrasonic treatment for 10 min under a dark condition to uniformly disperse the catalyst, and then performing magnetic stirring in a dark box for 30 min to enable the solution to reach adsorption-desorption balance; then, a 300W xenon lamp is adopted, a 420 nm optical filter is added as a visible light source to carry out photocatalytic reaction, the total time of the photocatalytic reaction is 40 min, samples are taken every 10 min, after centrifugal separation, supernatant liquid is taken to measure the absorbance of the samples, and a corresponding concentration value is calculated according to the value of the absorbance; the removal rate of the reactive blue 19 is obtained according to the removal rate formula (1):
wherein: c0Is the initial concentration of reactive blue 19, mg.L-1；
CtIs the concentration of active blue 19 after time t, mg.L-1。
The removal rate range achieved by the method is 98-100%.
The invention has the beneficial effects that:
(1) the invention synthesizes Cu2MoS2O4And Ag with narrow band gap2V4O11And to modify g-C3N4Broadens the visible light response range, enhances the light absorption intensity and inhibits the photon-generated carrier recombination rate, thereby improving the g-C3N4The photocatalytic performance of (a).
(2) The preparation method is simple, convenient and low in cost, is easy to operate and has practical application significance.
(3) Cu in the invention2MoS2O4The loading of (A) effectively improves the binary Ag2V4O11/g-C3N4The crystallization condition of the catalyst further improves the photocatalytic performance.
(4) Cu synthesized by the invention2MoS2O4/Ag2V4O11/g-C3N4The three-way catalyst can degrade 20 mg/L of active blue 19 solution within 40 min, and the degradation rate can reach more than 99%.
Drawings
FIG. 1 is g-C prepared in example 13N4、Cu2MoS2O4、Ag2V4O11/g-C3N4And Cu2MoS2O4/Ag2V4O11/g-C3N4X-ray diffraction pattern of the three-way composite catalyst;
FIG. 2 is g-C prepared in example 13N4、Ag2V4O11/g-C3N4And Cu2MoS2O4/Ag2V4O11/g-C3N4Ultraviolet-visible diffuse reflection spectrogram of the ternary composite catalyst;
FIG. 3 is g-C prepared in example 13N4、Ag2V4O11/g-C3N4And Cu2MoS2O4/Ag2V4O11/g-C3N4A band gap diagram of the three-way composite catalyst;
FIG. 4 is g-C prepared in example 13N4、Ag2V4O11/g-C3N4And Cu2MoS2O4/Ag2V4O11/g-C3N4A fluorescence spectrogram of the three-way composite catalyst;
FIG. 5 is g-C prepared in example 13N4、Ag2V4O11/g-C3N4And Cu2MoS2O4/Ag2V4O11/g-C3N4The degradation effect of the three-way composite catalyst on 20 mg/L active blue 19 is shown.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
（1）Cu2MoS2O4the preparation of (1):
0.6621 g of (NH) were added under magnetic stirring4）6Mo7O24·12H2O in 80 mL distilled water, followed by 4.6 g Na2And S, continuously stirring until the color becomes clear yellow. Dropwise addition of HCl produced a brown substance and a pungent odor. When the pH was adjusted to 7, after stirring for 15 min, 4.6375 g of Cu (NO) was added3）2·3H2O, stirring to be uniform, condensing and refluxing for 10 hours at 70 ℃, collecting the obtained sample, washing the sample with water and absolute ethyl alcoholWashing for several times, drying at 60 deg.C for 12 hr, and grinding;
（2）Ag2V4O11/g-C3N4preparing a binary composite material:
mixing AgNO3Dissolving in 10 mL of distilled water to obtain a solution A; the NH concentration is 1.2 mmol/L, and the mixture is magnetically stirred at the temperature of 40 DEG C4VO3Dissolved in 50 mL of distilled water to form a pale yellow clear solution, identified as solution B, at a concentration of 2.4 mmol/L. Solution a was added to solution B to produce yellow flocs.
With HNO3The pH of the solution is adjusted to 2.45, and the solution color is deepened and becomes orange yellow. Continuously stirring under heating condition for 30 min; the solution turned a brownish red color. Adding 0.2955 g g-C at room temperature3N4Performing ultrasonic treatment for 60 min, and stirring for 11 h; carrying out hydrothermal reaction, washing the reaction product with distilled water and absolute ethyl alcohol for three times respectively, and drying at 60 ℃ for 14 h.
（3）Cu2MoS2O4/Ag2V4O11/g-C3N4Preparing a ternary composite catalytic material:
0.24 g of Cu was weighed2MoS2O4And 0.4 g of 20A/CN are mixed in 30 mL of water, the mixture is subjected to ultrasonic treatment for 60 min, the mixture is stirred for 12 h, the mixture is washed with water and absolute ethyl alcohol for several times, the obtained product is centrifugally separated for 6 min at 8000 r/min, precipitates are taken out, the dried product is dried for 12 h in an oven at 60 ℃, and the dried product is ground to obtain the ternary composite catalytic material.
Preparing 250 mL of active blue 19 with the concentration of 20 mg/L, and then weighing 0.05-0.12 g of Cu2MoS2O4/Ag2V4O11/g-C3N4Adding the three-way catalyst into the active blue 19 solution, performing ultrasonic treatment for 10 min under a dark condition to uniformly disperse the catalyst, and then performing magnetic stirring in a dark box for 30 min to enable the solution to reach adsorption-desorption balance; then a 300W xenon lamp is adopted and a 420 nm filter is added as a visible light source for carrying out photocatalytic reaction, the total time of the photocatalytic reaction is 40 min, samples are taken every 10 min, after centrifugal separation, supernatant liquid is taken for measuring the absorbance, a corresponding concentration value is calculated according to the value of the absorbance,as shown in fig. 5.
FIG. 1 is g-C prepared in example 13N4、Cu2MoS2O4、Ag2V4O11/g-C3N4And Cu2MoS2O4/Ag2V4O11/g-C3N4X-ray diffraction pattern of the three-way composite catalyst. By comparison with standard cards (JCPDS 87-1526 and JCPDS 49-0166), it can be seen that in Cu2MoS2O4/Ag2V4O11/g-C3N4The XRD pattern of the compound shows that g-C is found3N4And Ag2V4O11Characteristic peak of (1), and Cu2MoS2O4The corresponding characteristic peak of the monomer can be found in the monomer, which indicates that Ag2V4O11And Cu2MoS2O4Successfully compounding to g-C3N4In (1).
FIG. 2 is g-C prepared in example 13N4、Ag2V4O11/g-C3N4And Cu2MoS2O4/Ag2V4O11/g-C3N4Ultraviolet-visible diffuse reflection spectrogram of the three-way composite catalyst. g-C3N4、Ag2V4O11/g-C3N4And Cu2MoS2O4/Ag2V4O11/g-C3N4The absorption edges of (a) are 470 nm, 495 nm and 520 nm, respectively. Indicates Ag2V4O11And Cu2MoS2O4Loading of (g) to (C)3N4The light absorbing edge is red-shifted.
FIG. 3 is g-C prepared in example 13N4、Ag2V4O11/g-C3N4And Cu2MoS2O4/Ag2V4O11/g-C3N4Band gap diagram of the three-way composite catalyst. Ag2V4O11Let g-C3N4The band gap is reduced from 2.74 eV to 2.64 eV, and Cu2MoS2O4/Ag2V4O11/g-C3N4The formation of the three-way composite catalyst further narrows its band gap to 2.5 eV.
FIG. 4 is g-C prepared in example 13N4、Ag2V4O11/g-C3N4And Cu2MoS2O4/Ag2V4O11/g-C3N4PL diagram of three-way composite catalyst. Cu2MoS2O4/Ag2V4O11/g-C3N4The ternary composite material has the lowest fluorescence intensity, and the synthesis of the ternary composite material effectively inhibits g-C3N4The rate of photogenerated electron-hole recombination.
FIG. 5 is g-C prepared in example 13N4、Ag2V4O11/g-C3N4And Cu2MoS2O4/Ag2V4O11/g-C3N4The degradation effect of the three-way composite catalyst on 20 mg/L active blue 19 is shown. g-C under 40 min photoreaction3N4、Ag2V4O11/g-C3N4And Cu2MoS2O4/Ag2V4O11/g-C3N4The degradation rates of the active blue 19 are respectively 37.04%, 77.78% and 99.99%, and the degradation rate of Ag is2V4O11And Cu2MoS2O4Is increased in g-C3N4Photocatalytic activity of (1).
Example 2:
（1）Cu2MoS2O4the preparation of (1):
0.8 g of (NH) was added under magnetic stirring4）6Mo7O24·12H2O was dissolved in 120 mL of distilled water, followed by addition of 5.2 g of Na2And S, continuously stirring until the color becomes clear yellow. HCl was added dropwise to yield a brown material. When the pH value is adjusted to 8,after stirring for 30 min, 5 g of Cu (NO) was added3）2·3H2O, after being stirred to be uniform, the mixture is condensed and refluxed for 11 hours at the temperature of 70 ℃, the obtained sample is collected and washed by water and absolute ethyl alcohol for a plurality of times, and is dried for 18 hours at the temperature of 80 ℃ and ground;
（2）Ag2V4O11/g-C3N4preparing a binary composite material:
mixing AgNO3Dissolving in 20 mL of distilled water to obtain a solution A; NH with a concentration of 3 mmol/L was added under magnetic stirring at 50 ℃4VO3Dissolved in 40 mL of distilled water to form a pale yellow clear solution, identified as solution B, at a concentration of 6 mmol/L. Solution a was added to solution B to produce yellow flocs.
With HNO3The pH of the solution is adjusted to 2.5, and the solution color is deepened and becomes orange yellow. Continuously stirring for 50 min under heating condition; the solution turned a brownish red color. Adding 1 g g-C at room temperature3N4Performing ultrasonic treatment for 50 min, and stirring for 15 h; carrying out hydrothermal reaction, washing the reaction product with distilled water and absolute ethyl alcohol for three times respectively, and drying at 75 ℃ for 24 h.
（3）Cu2MoS2O4/Ag2V4O11/g-C3N4Preparing a ternary composite catalytic material:
0.7 g of Cu was weighed2MoS2O4And 0.6 g of 20A/CN are mixed in 70 mL of water, the mixture is subjected to ultrasonic treatment for 100 min, the mixture is stirred for 8 h, the mixture is washed with water and absolute ethyl alcohol for a plurality of times, the obtained product is centrifugally separated for 10 min at 10000 r/min, the precipitate is taken out, the dried product is dried for 15 h in an oven at 80 ℃, and the ground product is obtained, thus obtaining the ternary composite catalytic material.
Preparing 250 mL of active blue 19 with the concentration of 20 mg/L, and then weighing 0.05-0.12 g of Cu2MoS2O4/Ag2V4O11/g-C3N4Adding the three-way catalyst into the active blue 19 solution, performing ultrasonic treatment for 10 min under a dark condition to uniformly disperse the catalyst, and then performing magnetic stirring in a dark box for 30 min to enable the solution to reach adsorption-desorption balance; then, a 300W xenon lamp is adopted and a 420 nm optical filter is added as a visible light source for carrying outPerforming photocatalytic reaction, wherein the total time of the photocatalytic reaction is 40 min, sampling every 10 min, centrifuging, collecting supernatant, measuring absorbance, calculating corresponding concentration value according to the absorbance value, and making concentration CtThe photocatalytic effect was tested on the curve over time t. Experiments show that: under the condition of 40 min photoreaction, Cu2MoS2O4/Ag2V4O11/g-C3N4The degradation rate of the active blue 19 is 99%.
Example 3:
（1）Cu2MoS2O4the preparation of (1):
0.7 g of (NH) was added under magnetic stirring4）6Mo7O24·12H2O in 100 mL of distilled water, followed by addition of 5 g of Na2And S, continuously stirring until the color becomes clear yellow. HCl was added dropwise to yield a brown material. When the pH was adjusted to 6, after stirring for 20 min, 4.2 g of Cu (NO) was added3）2·3H2O, after being stirred to be uniform, the mixture is condensed and refluxed for 9 hours at the temperature of 65 ℃, the obtained sample is collected and washed for a plurality of times by water and absolute ethyl alcohol, and is dried for 14 hours at the temperature of 70 ℃ and ground;
（2）Ag2V4O11/g-C3N4preparing a binary composite material:
mixing AgNO3Dissolving in 15 mL of distilled water to obtain a solution A; the NH concentration is 2 mmol/L, and the mixture is magnetically stirred at the temperature of 40 DEG C4VO3Dissolved in 60 mL of distilled water to form a pale yellow clear solution, identified as solution B, at a concentration of 4 mmol/L. Solution a was added to solution B to produce yellow flocs.
With HNO3The pH value of the solution is adjusted to 2.3, and the color of the solution is deepened and becomes orange yellow. Continuously stirring under heating condition for 40 min; the solution turned a brownish red color. Adding 0.5 g g-C at room temperature3N4Performing ultrasonic treatment for 40 min, and stirring for 18 h; carrying out hydrothermal reaction, washing the reaction product with distilled water and absolute ethyl alcohol for three times respectively, and drying at 70 ℃ for 18 h;
（3）Cu2MoS2O4/Ag2V4O11/g-C3N4preparing a ternary composite catalytic material:
0.5 g of Cu was weighed2MoS2O4And 0.8 g of 20A/CN are mixed in 50 mL of water, ultrasonic treatment is carried out for 80 min, stirring is carried out for 10 h, the mixture is washed for a plurality of times by water and absolute ethyl alcohol, the obtained product is centrifugally separated for 8 min at 9000 r/min, sediment is taken, the obtained product is dried for 10 h in an oven at 70 ℃, and grinding is carried out, thus obtaining the ternary composite catalytic material.
Preparing 250 mL of active blue 19 with the concentration of 20 mg/L, and then weighing 0.05-0.12 g of Cu2MoS2O4/Ag2V4O11/g-C3N4Adding the three-way catalyst into the active blue 19 solution, performing ultrasonic treatment for 10 min under a dark condition to uniformly disperse the catalyst, and then performing magnetic stirring in a dark box for 30 min to enable the solution to reach adsorption-desorption balance; then, a 300W xenon lamp and a 420 nm optical filter are adopted as visible light sources to carry out photocatalytic reaction, the total time of the photocatalytic reaction is 40 min, samples are taken every 10 min, after centrifugal separation, supernatant liquid is taken to measure the absorbance of the samples, corresponding concentration values are calculated according to the absorbance values, and the concentration C is obtainedtThe photocatalytic effect was tested on the curve over time t. Experiments show that: under the condition of 40 min photoreaction, Cu2MoS2O4/Ag2V4O11/g-C3N4The degradation rate of the active blue 19 is 98.89%.
Claims (7)
1. Cu2MoS2O4/Ag2V4O11/g-C3N4The ternary composite catalyst is characterized by comprising the following raw materials in parts by weight:
Cu2MoS2O4:1 to 10 parts by weight of a surfactant,
Ag2V4O11/g-C3N4:10 parts of, wherein Ag2V4O11：g-C3N4The mass ratio of (A) to (B) is 1-100: 100.
2. cu according to claim 12MoS2O4/Ag2V4O11/g-C3N4The preparation method of the three-way composite catalyst is characterized by comprising the following steps:
（1）Cu2MoS2O4the preparation of (1):
under magnetic stirring, 0.5-0.8 g of (NH)4）6Mo7O24·12H2Dissolving O in 60-150 mL of distilled water, and adding 3.8-5.4 g of Na2S, continuously stirring until the color is clear yellow;
dropwise adding HCl to generate a brown substance and emitting pungent smell; when the pH value is adjusted to 6-8, stirring for 10-30 min, and adding 3.6-5.6 g of Cu (NO)3）2·3H2O, after being stirred uniformly, the mixture is condensed and refluxed for 9-12 h at the temperature of 60-80 ℃, the obtained sample is collected and washed for a plurality of times by water and absolute ethyl alcohol, and is dried for 10-24 h at the temperature of 50-80 ℃ and ground;
（2）Ag2V4O11/g-C3N4preparing a binary composite material:
mixing AgNO3Dissolving the mixture in 10-20 mL of distilled water to form a solution A with the concentration of 1-6 mmol/L; under magnetic stirring with heating, NH is added4VO3Dissolving the mixture in 30-60 mL of distilled water to form a light yellow clear solution, namely a solution B with the concentration of 0.5-2 mmol/L; adding the solution A into the solution B to generate yellow floccules, wherein the mass ratio of the solution A to the solution B is 0.8-1.2: 1;
with HNO3Adjusting the pH of the solution to be 2.2-2.6, and then deepening the color of the solution to be orange yellow; continuously stirring for 30-60 min under heating, and enabling the solution to become brownish red; adding 0.1-2 g g-C at room temperature3N4Carrying out ultrasonic treatment for 30-60 min, stirring for 10-24 h, carrying out hydrothermal reaction, washing reaction products for several times by using distilled water and absolute ethyl alcohol respectively, and drying at 50-80 ℃ for 8-24 h;
（3）Cu2MoS2O4/Ag2V4O11/g-C3N4preparing a three-way composite catalyst:
weighing quantitative monomer Cu2MoS2O4And 0.4-1.0 g Ag2V4O11/g-C3N4Placing the mixture in a beaker, adding 30-100 mL of solution, performing ultrasonic dispersion for 60-120 min, and stirring the mixture in a fume hood for 2-14 h; and centrifuging the obtained product at 8000-10000 r/min for 5-10 min, taking the precipitate, drying in an oven at 50-80 ℃ for 10-24 h, and grinding.
3. Cu according to claim 22MoS2O4/Ag2V4O11/g-C3N4The preparation method of the ternary composite catalyst is characterized in that the heating temperature of the solution in the step (2) is 20-60 ℃, and the heating temperature of the hydrothermal reaction is 160-190 ℃.
4. Cu according to claim 22MoS2O4/Ag2V4O11/g-C3N4The preparation method of the three-way composite catalyst is characterized in that the solution used in the step (3) is one or a mixture of two of distilled water and methanol.
5. Cu according to claim 12MoS2O4/Ag2V4O11/g-C3N4The application of the ternary composite catalyst in catalyzing and degrading organic dye under the condition of visible light.
6. Use according to claim 5, characterized in that: the organic dye comprises one of reactive blue 19, rhodamine B and malachite green.
7. Use according to claim 6, characterized in that: preparing 250 mL of active blue 19 with the concentration of 20 mg/L, and then weighing 0.05-0.12 g of Cu2MoS2O4/Ag2V4O11/g-C3N4Adding the three-way catalyst into active blue 19 solution, performing ultrasonic treatment for 10 min under dark condition to uniformly disperse the catalyst, and placing the catalyst in a dark boxMagnetically stirring for 30 min to make the solution reach adsorption-desorption balance; then, a 300W xenon lamp is adopted, a 420 nm optical filter is added as a visible light source to carry out photocatalytic reaction, the total time of the photocatalytic reaction is 40 min, samples are taken every 10 min, after centrifugal separation, supernatant liquid is taken to measure the absorbance of the samples, and a corresponding concentration value is calculated according to the value of the absorbance; the removal rate of the reactive blue 19 is obtained according to the removal rate formula (1):
wherein: c0Is the initial concentration of reactive blue 19, mg.L-1；
CtIs the concentration of active blue 19 after time t, mg.L-1。
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| CN106076384A (en) * | 2016-06-12 | 2016-11-09 | 江苏大学 | A kind of tri compound catalysis material and its production and use |
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| CN113058601A (en) * | 2021-03-26 | 2021-07-02 | 华东理工大学 | Preparation method and application of ternary composite catalyst for photocatalytic hydrogen production by water splitting |
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| CN106076384A (en) * | 2016-06-12 | 2016-11-09 | 江苏大学 | A kind of tri compound catalysis material and its production and use |
| CN108262054A (en) * | 2018-03-06 | 2018-07-10 | 内蒙古大学 | A kind of preparation method of silver vanadate/nitride porous carbon heterojunction composite photocatalyst |
| CN109225304A (en) * | 2018-10-25 | 2019-01-18 | 聊城大学 | A kind of visible light-responded Ag4V2O7/g-C3N4The preparation method of catalysis material |
| CN109806900A (en) * | 2019-02-20 | 2019-05-28 | 江苏大学 | A kind of molecular imprinting Ag/Ag3VO4The preparation method and application of/CN nanometer sheet composite photo-catalyst |
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