CN113731411B - Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation method and application of ternary composite catalyst - Google Patents

Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation method and application of ternary composite catalyst Download PDF

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CN113731411B
CN113731411B CN202111120789.0A CN202111120789A CN113731411B CN 113731411 B CN113731411 B CN 113731411B CN 202111120789 A CN202111120789 A CN 202111120789A CN 113731411 B CN113731411 B CN 113731411B
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CN113731411A (en
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李育珍
王晓爽
夏云生
谭思洋
李鑫
王少杰
易思远
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Taiyuan University of Technology
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Abstract

The invention discloses a Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g‑C 3 N 4 The preparation method and application of the ternary composite catalyst are characterized in that the catalyst is prepared from the following raw materials in parts by weight: cu (Cu) 2 MoS 2 O 4 : 1-10 parts of Ag 2 V 4 O 11 /g‑C 3 N 4 :10 parts. The preparation method comprises the following steps: (1) Cu (Cu) 2 MoS 2 O 4 Is prepared by the steps of (1); (2) Ag (silver) 2 V 4 O 11 /g‑C 3 N 4 Preparing a binary composite material; (3) Cu (Cu) 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g‑C 3 N 4 And (3) preparing the ternary composite catalytic material. The invention synthesizes Cu by wet impregnation method 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g‑C 3 N 4 The ternary photocatalyst has the advantages of convenient operation, low cost, good effect on organic wastewater and good prospect in practical production and commercial application.

Description

Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation method and application of ternary composite catalyst
Technical Field
The invention relates to a Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 A 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 an inevitable hazard in the development process of modern industries such as textile, paper making and the like. The printing and dyeing wastewater has strong toxicity, high chromaticity and difficult degradation under natural conditions, so the treatment process is always focused on by researchers. The photocatalysis technology is characterized by green environmental protection, low cost and no secondary pollution, and is a distinct treatment technology.
Graphite phase carbon nitride (g-C) 3 N 4 ) The semiconductor photocatalytic material has the advantages of wide application, low cost and low production cost, is easy to obtain raw materials, has visible light activity and high chemical and thermal stability, and is used in the fields of photocatalytic decomposition of water, degradation of organic pollutants and the like. However, g-C 3 N 4 The forbidden bandwidth is wide (2.7 eV), the specific surface area is small, the visible light response range is narrow, and the photocatalytic performance is greatly limited. Thus, modifying g-C 3 N 4 To overcome the defects and improve the photocatalytic activity of g-C 3 N 4 One of the focus of the study.
Disclosure of Invention
The present invention aims to provide a Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation method and application of ternary composite catalyst and Cu used in preparation method 2 MoS 2 O 4 And Ag 2 V 4 O 11 Co-modification of g-C 3 N 4 To improve its photocatalytic efficiency.
In the invention, ag 2 V 4 O 11 Belongs to transition V-group oxide, has narrow forbidden band width (only 1.45 eV), proper energy band structure and strong electron transfer rate, and is one of the emerging photocatalytic materials. Cu (Cu) 2 MoS 2 O 4 Is Bi in 2 MoS 2 O 4 Is based on CuThe sulfur oxide formed instead of Bi, sulfur, can shorten the band gap of the semiconductor. Cu (Cu) 2 MoS 2 O 4 The monomer does not have photocatalytic activity, but after heterojunction is formed with other semiconductors, the photocatalytic activity of the semiconductor can be effectively improved.
The invention provides a Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The ternary composite catalyst consists of the following raw materials in parts by weight:
Cu 2 MoS 2 O 4 :1 to 10 parts of a compound containing,
Ag 2 V 4 O 11 /g-C 3 N 4 :10 parts of Ag 2 V 4 O 11 ：g-C 3 N 4 The mass ratio of (1-100): 100.
the invention provides the Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The preparation method of the ternary composite catalyst is characterized by comprising the following steps:
（1）Cu 2 MoS 2 O 4 is prepared from the following steps:
under magnetic stirring, 0.5-0.8 g (NH) 4 ） 6 Mo 7 O 24 ·12H 2 O is dissolved in 60-150 mL of distilled water, and then 3.8-5.4 g of Na is added 2 S, stirring was continued until a clear yellow color was obtained. HCl was added dropwise to produce a brown substance and to give off a pungent odor. When the pH is adjusted to 6-8, stirring for 10-30 min, adding 3.6-5.6 g Cu (NO) 3 ） 2 ·3H 2 O, after stirring uniformly, condensing and refluxing for 9-12 hours at 60-80 ℃, collecting an obtained sample, washing the sample with water and absolute ethyl alcohol for several times, drying the sample at 50-80 ℃ for 10-24 hours, and grinding the sample;
（2）Ag 2 V 4 O 11 /g-C 3 N 4 preparation of binary composite material:
AgNO is to be carried out 3 Dissolving in 10-20 mL of distilled water to form a solution A, wherein the concentration is 1-6 mmol/L. Under the condition of heating and magnetic stirring, NH 4 VO 3 Dissolving in 30And (3) in distilled water of 60-mL, a pale yellow clear solution is formed, and is regarded as a solution B, and the concentration is 0.5-2 mmol/L. And adding the solution A into the solution B to generate yellow floccules, wherein the solution A is 0.8-1.2 parts, and the solution B is 1 part.
By HNO 3 And adjusting the pH value of the solution to be 2.2-2.6, and deepening the color of the solution to be orange. Stirring is continued for 30-60 min under heating, and the solution turns to be brownish red. At room temperature, 0.1-2 g g-C is added 3 N 4 Ultrasonic treatment is carried out for 30-60 min, stirring is carried out for 10-24 h, hydrothermal reaction is carried out, reaction products are respectively washed for a plurality of times by distilled water and absolute ethyl alcohol, and drying is carried out for 8-24 h at 50-80 ℃. Ag in the product 2 V 4 O 11 ：g-C 3 N 4 The mass ratio is 1-100: 100;
（3）Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 preparation of a ternary composite catalyst:
weighing 0.02-1.0 g of monomer Cu 2 MoS 2 O 4 And 0.4-1.0 g Ag 2 V 4 O 11 /g-C 3 N 4 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. Centrifuging the obtained product for 5-10 min at 8000-10000 r/min, taking the precipitate, drying in an oven at 50-80 ℃ for 10-24 h, and grinding to obtain the ternary composite catalyst.
The Cu mentioned above 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The 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 ℃.
The Cu mentioned above 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation method of ternary composite catalyst, cu in step (3) 2 MoS 2 O 4 And Ag 2 V 4 O 11 /g-C 3 N 4 The mass ratio of (2) is 1-10:10.
The Cu mentioned above 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The preparation method of the ternary composite catalyst comprises the step (3), wherein the solution is distilled water, methanol or distilled water/methanol mixture.
The invention provides the Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The ternary composite catalyst is applied to catalytic degradation of organic dye under the condition of visible light.
Taking organic dye active blue 19 as an example, 250 mL active blue 19 with the concentration of 20 mg/L is prepared, and then 0.05-0.12 g Cu is weighed 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Adding a three-way catalyst into the active blue 19 solution, performing ultrasonic treatment under dark condition for 10 min to uniformly disperse the catalyst, and then performing magnetic stirring in a dark box for 30 min to make the solution reach adsorption-desorption equilibrium; then adopting a 300W xenon lamp and adding a 420 nm optical filter as a visible light source to carry out photocatalytic reaction, taking one sample every 10 min for the total time of the photocatalytic reaction to be 40 min, taking supernatant after centrifugal separation to measure the absorbance, and calculating a corresponding concentration value according to the absorbance value; the removal rate of active blue 19 was obtained according to the removal rate formula (1):
（1）
wherein: c (C) 0 Is the initial concentration of active blue 19, mg.L -1 ；
C t The concentration of active blue 19 after time t is mg.L -1 。
The removal rate achieved by the method is 98-100%.
The invention has the beneficial effects that:
(1) The invention synthesizes Cu 2 MoS 2 O 4 And narrow bandgap Ag 2 V 4 O 11 And is used for modifying g-C 3 N 4 The visible light response range is widened, the light absorption intensity is enhanced, the photon-generated carrier recombination rate is inhibited, and the g-C is improved 3 N 4 Is used for the photocatalytic performance of the catalyst.
(2) The preparation method provided by the invention is simple and convenient, low in cost, easy to operate and has practical application significance.
(3) Cu in the invention 2 MoS 2 O 4 Effectively improves the binary Ag 2 V 4 O 11 /g-C 3 N 4 The crystallization condition of the catalyst further improves the photocatalysis performance.
(4) Cu synthesized by the invention 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The ternary catalyst can degrade 20 mg/L active blue 19 solution within 40 min, and the degradation rate can reach more than 99%.
Drawings
FIG. 1 is a graph of g-C prepared in example 1 3 N 4 、Cu 2 MoS 2 O 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 X-ray diffraction pattern of ternary composite catalyst;
FIG. 2 is a graph of g-C prepared in example 1 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 An ultraviolet-visible diffuse reflection spectrogram of the ternary composite catalyst;
FIG. 3 is a graph of g-C prepared in example 1 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Band gap diagram of ternary composite catalyst;
FIG. 4 is a graph of g-C prepared in example 1 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Of ternary complex catalystsA fluorescence spectrum;
FIG. 5 is a graph of g-C prepared in example 1 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The degradation effect of the ternary composite catalyst on 20 mg/L active blue 19 is shown.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Example 1:
（1）Cu 2 MoS 2 O 4 is prepared from the following steps:
under magnetic stirring, 0.6621 g (NH 4 ） 6 Mo 7 O 24 ·12H 2 O was dissolved in 80. 80 mL distilled water, followed by addition of 4.6. 4.6 g Na 2 S, stirring was continued until a clear yellow color was obtained. HCl was added dropwise to produce a brown substance and to give off a pungent odor. When the pH was adjusted to 7, cu (NO) of 4.6375 g was added after stirring for 15 min 3 ） 2 ·3H 2 O, after stirring to be uniform, condensing and refluxing 10 h at 70 ℃, collecting the obtained sample, washing the sample with water and absolute ethyl alcohol for several times, drying the sample at 60 ℃ for 12 h, and grinding the sample;
（2）Ag 2 V 4 O 11 /g-C 3 N 4 preparation of binary composite material:
AgNO is to be carried out 3 Dissolving in 10 mL distilled water to obtain solution A; concentration of 1.2 mmol/L, NH was added under magnetic stirring at 40 ℃ 4 VO 3 Dissolved in 50 mL distilled water to form a pale yellow clear solution, designated solution B, at a concentration of 2.4 mmol/L. Solution a was added to solution B to produce a yellow floc.
By HNO 3 The pH of the solution was adjusted to 2.45, and the color of the solution was then darkened to orange. Stirring continuously for 30 min under heating; the solution turned brownish red. 0.2955 g of C was added at room temperature 3 N 4 Ultrasonic treatment for 60 min, stirring for 11 h; carrying out hydrothermal reaction, and respectively using distilled water and absolute ethyl alcohol to obtain reaction productsWashed three times and dried at 60℃to 14 h.
（3）Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation of a ternary composite catalytic material:
weigh 0.24 and g Cu 2 MoS 2 O 4 Mixing with 20A/CN of 0.4. 0.4 g in 30 mL water, ultrasonic treating for 60 min, stirring for 12 h, washing with water and absolute ethanol for several times, centrifuging at 8000 r/min for 6 min, collecting precipitate, drying in oven at 60deg.C for 12 h, and grinding to obtain ternary composite catalytic material.
Preparing 250 mL active blue 19 with the concentration of 20 mg/L, and weighing 0.05-0.12 g Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Adding a three-way catalyst into the active blue 19 solution, performing ultrasonic treatment under dark condition for 10 min to uniformly disperse the catalyst, and then performing magnetic stirring in a dark box for 30 min to make the solution reach adsorption-desorption equilibrium; then adopting a 300W xenon lamp and adding a 420 nm optical filter as a visible light source to carry out photocatalysis reaction, taking one sample every 10 min for the total time of the photocatalysis reaction, taking supernatant after centrifugal separation to measure the absorbance, and calculating a corresponding concentration value according to the absorbance value, wherein the total time of the photocatalysis reaction is 40 min, and the concentration value is shown in figure 5.
FIG. 1 is a graph of g-C prepared in example 1 3 N 4 、Cu 2 MoS 2 O 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 X-ray diffraction pattern of ternary composite catalyst. As can be seen by comparison with standard cards (JCPCDS 87-1526 and JCPCDS 49-0166), the alloy is made of Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 g-C was found in the XRD pattern of (C) 3 N 4 And Ag 2 V 4 O 11 Is equivalent to Cu 2 MoS 2 O 4 Characteristic peaks corresponding to monomers can also be found therein, indicating Ag 2 V 4 O 11 And Cu 2 MoS 2 O 4 Successful complexing to g-C 3 N 4 Is a kind of medium.
FIG. 2 is a graph of g-C prepared in example 1 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Ultraviolet-visible diffuse reflection spectrogram of ternary composite catalyst. g-C 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Is 470 nm,495 nm and 520 nm, respectively. Indicating Ag 2 V 4 O 11 And Cu 2 MoS 2 O 4 Load of (C) is g-C 3 N 4 The light absorbing edge is red shifted.
FIG. 3 is a graph of g-C prepared in example 1 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Band gap diagram of ternary composite catalyst. Ag (silver) 2 V 4 O 11 Let g-C 3 N 4 The band gap is reduced from 2.74 eV to 2.64 eV, cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The formation of the three-way composite catalyst further reduces its bandgap to 2.5 eV.
FIG. 4 is a graph of g-C prepared in example 1 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 PL diagram of ternary composite catalyst. Cu (Cu) 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The ternary composite material has the lowest fluorescence intensity, which shows that the synthesis thereof effectively inhibits g-C 3 N 4 Is a photo-generated electron-hole recombination rate.
FIG. 5 is a graph of g-C prepared in example 1 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The degradation effect of the ternary composite catalyst on 20 mg/L active blue 19 is shown. g-C under 40 min photoreaction conditions 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Degradation rates for active blue 19 were 37.04%, 77.78% and 99.99%, respectively, for Ag 2 V 4 O 11 And Cu 2 MoS 2 O 4 Load of (2) increases g-C 3 N 4 Is a component of the photocatalytic activity of the catalyst.
Example 2:
（1）Cu 2 MoS 2 O 4 is prepared from the following steps:
under magnetic stirring, 0.8. 0.8 g (NH 4 ） 6 Mo 7 O 24 ·12H 2 O was dissolved in 120. 120 mL distilled water, followed by addition of 5.2. 5.2 g Na 2 S, stirring was continued until a clear yellow color was obtained. HCl was added dropwise to give a brown material. When the pH was adjusted to 8, after stirring for 30 min, cu (NO) of 5 g was added 3 ） 2 ·3H 2 O, after stirring to be uniform, condensing and refluxing 11 h at 70 ℃, collecting the obtained sample, washing the sample with water and absolute ethyl alcohol for several times, drying the sample at 80 ℃ for 18 h, and grinding the sample;
（2）Ag 2 V 4 O 11 /g-C 3 N 4 preparation of binary composite material:
AgNO is to be carried out 3 Dissolving in 20 mL distilled water to obtain solution A; concentration of 3 mmol/L, NH was added under magnetic stirring at 50deg.C 4 VO 3 Dissolved in 40 mL distilled water to form a pale yellow clear solution, which was regarded as solution B, at a concentration of 6 mmol/L. Solution a was added to solution B to produce a yellow floc.
By HNO 3 The pH of the solution was adjusted to 2.5, and the color of the solution was then darkened to orange. Under heating conditionsStirring for 50 min; the solution turned brownish red. At room temperature, 1 g of C-C was added 3 N 4 Ultrasonic for 50 min, stirring for 15 h; the hydrothermal reaction was carried out, and the reaction product was washed three times with distilled water and absolute ethanol, respectively, and dried at 75℃for 24 h.
（3）Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation of a ternary composite catalytic material:
weigh 0.7. 0.7 g Cu 2 MoS 2 O 4 Mixing with 20A/CN of 0.6 g in 70 mL water, ultrasonic treating for 100 min, stirring for 8 h, washing with water and absolute ethanol for several times, centrifuging at 10000 r/min for 10 min, collecting precipitate, drying in oven at 80deg.C for 15 h, and grinding to obtain ternary composite catalytic material.
Preparing 250 mL active blue 19 with the concentration of 20 mg/L, and weighing 0.05-0.12 g Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Adding a three-way catalyst into the active blue 19 solution, performing ultrasonic treatment under dark condition for 10 min to uniformly disperse the catalyst, and then performing magnetic stirring in a dark box for 30 min to make the solution reach adsorption-desorption equilibrium; then adopting a 300W xenon lamp and adding a 420 nm optical filter as a visible light source to carry out photocatalysis reaction, taking one sample every 10 min for 40 min, taking supernatant after centrifugal separation to measure the absorbance, calculating a corresponding concentration value according to the absorbance value, and preparing a concentration C t Curves over time t to test their photocatalytic effect. Experiments show that: under the light reaction condition of 40 min, cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The degradation rate for active blue 19 was 99%.
Example 3:
（1）Cu 2 MoS 2 O 4 is prepared from the following steps:
under magnetic stirring, 0.7. 0.7 g (NH 4 ） 6 Mo 7 O 24 ·12H 2 O was dissolved in 100 mL distilled water, followed by addition of 5 g Na 2 S, stirring was continued until a clear yellow color was obtained. Drop (D)HCl was added to give a brown material. When the pH was adjusted to 6, after stirring for 20 min, cu (NO) of 4.2. 4.2 g was added 3 ） 2 ·3H 2 O, after stirring to be uniform, condensing and refluxing 9 h at 65 ℃, collecting the obtained sample, washing the sample with water and absolute ethyl alcohol for several times, drying the sample at 70 ℃ for 14 h, and grinding the sample;
（2）Ag 2 V 4 O 11 /g-C 3 N 4 preparation of binary composite material:
AgNO is to be carried out 3 Dissolving in 15 mL distilled water to obtain solution A; concentration of 2 mmol/L, NH was added under magnetic stirring at 40 ℃ 4 VO 3 Dissolved in 60 mL distilled water to form a pale yellow clear solution, which was regarded as solution B, at a concentration of 4 mmol/L. Solution a was added to solution B to produce a yellow floc.
By HNO 3 The pH of the solution was adjusted to 2.3, and the color of the solution was then darkened to orange. Stirring continuously under heating for 40 min; the solution turned brownish red. At room temperature, 0.5 g of C-C was added 3 N 4 Ultrasonic treatment for 40 min, 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）Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 preparation of a ternary composite catalytic material:
weigh 0.5. 0.5 g Cu 2 MoS 2 O 4 Mixing with 20A/CN of 0.8. 0.8 g in 50 mL water, ultrasonic treating for 80 min, stirring for 10 h, washing with water and absolute ethanol for several times, centrifuging at 9000 r/min for 8 min, collecting precipitate, drying in oven at 70deg.C for 10 h, and grinding to obtain ternary composite catalytic material.
Preparing 250 mL active blue 19 with the concentration of 20 mg/L, and weighing 0.05-0.12 g Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Adding a three-way catalyst into the active blue 19 solution, performing ultrasonic treatment under dark condition for 10 min to uniformly disperse the catalyst, and then performing magnetic stirring in a dark box for 30 min to make the solution reach adsorption-desorption equilibrium; later is collectedPerforming photocatalytic reaction with 300W xenon lamp and 420 nm filter as visible light source for 40 min, taking one sample every 10 min, centrifuging, collecting supernatant, measuring absorbance, calculating corresponding concentration value according to absorbance value, and making concentration C t Curves over time t to test their photocatalytic effect. Experiments show that: under the light reaction condition of 40 min, cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The degradation rate for active blue 19 was 98.89%.

Claims (6)

1. Cu (copper) alloy 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The ternary composite catalyst is characterized by comprising the following raw materials in parts by weight:
Cu 2 MoS 2 O 4 :1 to 10 parts of a compound containing,
Ag 2 V 4 O 11 /g-C 3 N 4 :10 parts of Ag therein 2 V 4 O 11 ：g-C 3 N 4 The mass ratio of (1-100): 100;
the Cu is 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The preparation method of the ternary composite catalyst comprises the following steps:
（1）Cu 2 MoS 2 O 4 is prepared from the following steps:
under magnetic stirring, 0.5-0.8 g (NH) 4 ） 6 Mo 7 O 24 ·12H 2 O is dissolved in 60-150 mL of distilled water, and then 3.8-5.4 g of Na is added 2 S, continuously stirring until the mixture is clear yellow; dripping HCl to generate brown substances and giving off pungent odor; when the pH is adjusted to 6-8, stirring for 10-30 min, adding 3.6-5.6 g Cu (NO) 3 ） 2 ·3H 2 O, after stirring uniformly, condensing and refluxing for 9-12 hours at 60-80 ℃, collecting an obtained sample, washing the sample with water and absolute ethyl alcohol for several times, drying the sample at 50-80 ℃ for 10-24 hours, and grinding the sample;
（2）Ag 2 V 4 O 11 /g-C 3 N 4 preparation of binary composite material:
AgNO is to be carried out 3 Dissolving in 10-20 mL of distilled water to form a solution A, wherein the concentration is 1-6 mmol/L; NH was stirred under heated magnetic force 4 VO 3 Dissolving the solution in 30-60 mL of distilled water to form a pale yellow clear solution, wherein the pale yellow clear solution is regarded as solution B, and the concentration is 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, a step of;
by HNO 3 Adjusting the pH value of the solution to be 2.2-2.6, and deepening the color of the solution to be orange; continuously stirring for 30-60 min under heating, and changing the solution into brownish red; at room temperature, 0.1-2 g g-C is added 3 N 4 Performing ultrasonic treatment for 30-60 min, stirring for 10-24 h, performing hydrothermal reaction, washing the reaction product with distilled water and absolute ethyl alcohol for several times, and drying at 50-80 ℃ for 8-24 h;
（3）Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 preparation of a ternary composite catalyst:
weighing quantitative monomer Cu 2 MoS 2 O 4 And 0.4-1.0 g Ag 2 V 4 O 11 /g-C 3 N 4 Placing the mixture in a beaker, adding 30-100 mL of solution, performing ultrasonic dispersion for 60-120 min, and stirring for 2-14 h in a fume hood; centrifuging the obtained product for 5-10 min at 8000-10000 r/min, taking the precipitate, drying in an oven at 50-80 ℃ for 10-24 h, and grinding.
2. Cu according to claim 1 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 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 ℃.
3. Cu according to claim 1 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Ternary elementThe composite catalyst is characterized in that the solution used in the step (3) is one or a mixture of distilled water and methanol.
4. A Cu according to claim 1 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Application of ternary composite catalyst in catalyzing and degrading organic dye under visible light condition.
5. The use according to claim 4, characterized in that: the organic dye comprises one of active blue 19, rhodamine B and malachite green.
6. The use according to claim 5, characterized in that: preparing 250 mL active blue 19 with the concentration of 20 mg/L, and weighing 0.05-0.12 g Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Adding a three-way catalyst into the active blue 19 solution, performing ultrasonic treatment under dark condition for 10 min to uniformly disperse the catalyst, and then performing magnetic stirring in a dark box for 30 min to make the solution reach adsorption-desorption equilibrium; then adopting a 300W xenon lamp and adding a 420 nm optical filter as a visible light source to carry out photocatalytic reaction, taking one sample every 10 min for the total time of the photocatalytic reaction to be 40 min, taking supernatant after centrifugal separation to measure the absorbance, and calculating a corresponding concentration value according to the absorbance value; the removal rate of active blue 19 was obtained according to the removal rate formula (1):
（1）
wherein: c (C) 0 Is the initial concentration of active blue 19, mg.L -1 ；
C t The concentration of active blue 19 after time t is mg.L -1 。
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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
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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Publication number Priority date Publication date Assignee Title
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
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