CN114682304B - CuCd-MOF/GO-x composite material with visible light catalytic degradation performance and preparation and application thereof - Google Patents
CuCd-MOF/GO-x composite material with visible light catalytic degradation performance and preparation and application thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 19
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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Abstract
The invention discloses a CuCd-MOF/GO-x composite material with visible light catalytic degradation performance, and preparation and application thereof, wherein the CuCd-MOF/GO-x composite material is formed by combining CuCd-MOF and GO through hydrogen bonds, and 0<x<10; the chemical expression of CuCd-MOF is { [ Cu ] 2 Cd 2 (pmida) 2 (H 2 O) 7 ]·3H 2 O} n It is prepared by H 4 pmida is a ligand and contains a metal organic framework material of Cu and Cd ions; each asymmetric unit of the CuCd-MOF contains 2 deprotonated organic ligands pmida 4— 2 copper ions, 2 cadmium ions, 7 coordinated water molecules and 3 lattice water molecules. The preparation method of the composite material is simple, the structure is stable, and the composite material can degrade MB, CR, MO, rhB, LEV and other dyes in a photocatalytic manner under the irradiation of visible light, can be recycled, and has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a CuCd-MOF/GO-x composite material for degrading organic dye by visible light catalysis, and a preparation method and application thereof.
Background
The problem of water pollution has become a significant social problem that has to be faced worldwide, severely affecting the sustainable development of humans. The traditional methods for treating water pollution comprise a chemical oxidation method, a coagulation sedimentation method, a physical adsorption method, a microbial decomposition method, an electrocatalytic method and the like, and the methods have certain treatment effects, but most of the methods have the defects of large investment, time consumption, energy consumption, complex treatment process and incomplete degradation, easily cause secondary pollution and cannot completely meet the environmental protection requirements of the modern society.
The photocatalysis is a degradation method based on in-situ generation of transition substances with strong reactivity, and has the advantages of high treatment efficiency, no secondary pollution and the like compared with other traditional physicochemical methods, and is favored in the field of water pollution treatment.
In recent years, researchers have explored a large number of inorganic semiconductor photocatalytic materials (e.g., tiO 2 CdS, znO, etc.) in the degradation of organic contaminants, most of these catalytic materials can only degrade organic contaminants under uv light, which is about 4% of sunlight. The unavoidable photo-erosion, severe agglomeration and transient recombination problems of electron-hole pairs significantly limit the use of conventional semiconductors as photocatalysts. Therefore, it is obviously significant to explore new, efficient catalysts with visible light catalytic properties to further solve the problem of organic pollution.
The Metal Organic Framework (MOFs) has the characteristics of extraordinary specific surface area, rich porosity, high crystallinity and ordered structure, and the properties of the MOF material can be controllably regulated by regulating ligand structures and metal ions, so that the MOFs are also attracting more and more attention in the field of photocatalysis. Coordination polymer as one new kind of multifunctional material has the advantages of adjustability and designability, and its structure may be controlled through the selection of different organic connecting agent, metal center/metal cluster and reaction condition. Therefore, the catalyst has attracted extensive attention in the fields of adsorption, catalysis, photoelectric devices, gas storage separation and the like. Because of the abundant metal nodes and organic bridging agents and the controllability of synthesis, coordination polymers with adjustable light absorption property can be easily constructed, so that ideal photocatalytic materials are provided for degradation of organic pollutants.
Wang Ya et al (printing and dyeing, 2019, 11, 17-42) reported a paper for physical adsorption and photochemical degradation of dyes by bifunctional Cu-MOFs using bis (3, 5-dicarboxyphenyl) terephthalamide (H) 4 BDPT) and Cu (NO 3 ) 2 ·H 2 O reacts under the solvothermal condition to synthesize the Cu-H material of the metal-organic frameworks (MOFs) based on Cu-O nodes 4 L and is used for physical adsorption and visible light catalytic degradation of Methylene Blue (MB) and rhodamine B (RhB) in water. However, cu-H 4 L has visible light catalytic degradation performance, but has lower degradation efficiency, the adsorption efficiency to MB in 300min is only 85.9%, the efficient degradation of RhB dye can be realized within 5H, and only Cu-H is described in the document 4 L can be used for degradation of MB and RhB, and whether the catalyst has a broad-spectrum degradation effect is not clear.
MOFs based on organophosphonic ligands exhibit very high thermal stability and acid and base resistance compared to MOFs of other ligands. N- (phosphonomethyl) iminodiacetic acid (H) 4 pmida) is used as an organic ligand, and the pmida) contains hetero atoms such as nitrogen, phosphorus and the like, so that a plurality of coordination points with flexible coordination characteristics can be provided, a two-dimensional layered structure can be formed, thereby realizing catalytic center and rapid electronic movement, and meanwhile, the hetero atoms of nitrogen and phosphorus can adjust the energy band of a photocatalyst, so that the photocatalytic performance is enhanced. Thus, the preparation of a catalyst such as one that can utilize an organophosphonic acid ligand for photocatalytic degradation of an organic dye would be expected to significantly increase catalytic degradation efficiency.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a CuCd-MOF/GO-x composite material with visible light catalytic degradation performance, and preparation and application thereof.
In order to achieve the technical purpose, the invention is realized by the following technical scheme: the invention provides a CuCd-MOF/GO-x composite material with visible light catalytic degradation performance, wherein the CuCd-MOF and GO are combined with each other through hydrogen bonds, and the chemical expression of the CuCd-MOF is { [ Cu ] 2 Cd 2 (pmida) 2 (H 2 O) 7 ]·3H 2 O} n Or { Cu ] 2 Cd 2 P 2 O 24 C 10 H 32 N 2 } n Which is a method for preparing N- (phosphonomethyl) iminodiacetic acid (H) 4 pmida) is a ligand and contains metal organic framework materials of Cu and Cd metal ions; x represents the percentage content of graphene oxide in the composite material, 0<x<10; each asymmetric unit of the CuCd-MOF contains 2 deprotonated N- (phosphonomethyl) iminodiacetic acid groups (pmida) 4— ) The asymmetric units of 2 copper ions, 2 cadmium ions, 7 coordination water molecules and 3 lattice water molecules are connected with each other to form a two-dimensional layered structure, and the molecular structure is as follows:
as can be seen from the molecular structural formula, two Cd (II) ions have a coordination environment of a twisted octahedron with six coordination, and two Cu (II) ions have a coordination environment of a tetragonal cone with five coordination.
Preferably, the graphene oxide accounts for 5% of the composite material, and the prepared composite material is CuCd-MOF/GO-5.
Further, cuCd-MOF belongs to monoclinic system, P21/n space group, and unit cell parameters are:
β＝95.647°、/>
the preparation method of the CuCd-MOF/GO-x composite material with the visible light catalytic degradation performance comprises the following steps:
(1) Dissolving copper acetate, cadmium acetate and N- (phosphonomethyl) iminodiacetic acid in ultrapure water, uniformly mixing the solution by ultrasonic treatment, slowly adding graphene oxide into the solution system, and carrying out ultrasonic treatment for 20-30 minutes;
(2) Transferring the mixed solution obtained in the step (1) into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting in an oven, naturally cooling, filtering, washing and drying to obtain the CuCd-MOF/GO-x composite material.
Further, in the step (1), the molar ratio of the copper acetate to the cadmium acetate to the N- (phosphonomethyl) iminodiacetic acid is 1-1.2:1.
Further, in the step (2), the reaction temperature in the oven is 100-120 ℃ and the reaction time is 45-50 h.
The CuCd-MOF/GO-x composite material with photocatalytic degradation performance can efficiently and photocatalytic degrade organic pollutants such as Methylene Blue (MB), congo Red (CR), methyl Orange (MO), rhodamine B (RhB), levofloxacin (LEV) and the like, has high cycling stability, and can be recycled.
The beneficial effects of the invention are as follows:
1. the CuCd-MOF/GO-x composite material with photocatalytic degradation performance disclosed by the application is excellent in performance, can efficiently perform photocatalytic degradation on organic pollutants such as Methylene Blue (MB), congo Red (CR), methyl Orange (MO), rhodamine B (RhB), levofloxacin (LEV) and the like under visible light irradiation, has a spectral degradation effect, has more excellent photocatalytic degradation rate after limiting the content of graphene oxide, can degrade 92.0% of methylene blue within 40min, and has a wide application prospect;
2. the CuCd-MOF/GO-x composite material with photocatalytic degradation performance has higher photochemical activity and higher stability, and can be recycled;
3. the CuCd-MOF/GO-x composite material with photocatalytic degradation performance disclosed by the application is simple in synthesis method, convenient to operate and high in preparation efficiency;
4. the CuCd-MOF/GO-x composite material with photocatalytic degradation performance disclosed by the application is stable in structure, insoluble in water and common organic solvents, and can avoid secondary pollution;
5. the application provides a novel high-efficiency visible light response type CuCd-MOF/GO photocatalytic composite material, which can improve the solar energy utilization rate, provides a novel approach and method for water pollution treatment, and also provides a novel thought for the design of a novel visible light response type photocatalyst.
Drawings
FIG. 1 is a diagram of the asymmetric unit structure of the CuCd-MOF material prepared in example 1;
FIG. 2 is an X-ray diffraction pattern and a simulated X-ray diffraction pattern of CuCd-MOF, cuCd-MOF/GO-1.5, cuCd-MOF/GO-3, cuCd-MOF/GO-5, and CuCd-MOF/GO-7.5 and GO prepared in examples 1-5;
FIG. 3 is an infrared spectrum of CuCd-MOF prepared in example 1 and CuCd-MOF/GO-5 prepared in example 4;
FIG. 4 is a Raman spectrum of CuCd-MOF/GO-5 and GO prepared in example 4;
FIG. 5 is a scanning electron micrograph of a different material, wherein panel a is a scanning electron micrograph of graphene oxide, panel b is a scanning electron micrograph of the CuCd-MOF prepared in example 1, and panels c, d are scanning electron micrographs of the CuCd-MOF/GO-5 prepared in example 4;
FIG. 6 is a graph of photocatalytic degradation methylene blue performance and a table of reaction rate constants for CuCd-MOF, cuCd-MOF/GO-1.5, cuCd-MOF/GO-3, cuCd-MOF/GO-5, and CuCd-MOF/GO-7.5 prepared in examples 1-5;
FIG. 7 is a graph of the efficiency of the CuCd-MOF/GO-5 prepared in example 4 to degrade various organic contaminants;
FIG. 8 is a PXRD spectrum of CuCd-MOF/GO-5 prepared in example 4 after simulation, measurement and recycling.
Detailed Description
The following examples further illustrate the invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit of the invention are intended to be within the scope of the present invention.
Example 1: preparation of CuCd-MOF material
0.0998g of copper acetate, 0.1333g of cadmium acetate and 0.1136g N- (phosphonomethyl) iminodiacetic acid are weighed and dissolved in 6mL of water, the mixture is evenly mixed by ultrasonic waves and then transferred into a 50mL high-pressure reaction kettle, the mixture is reacted for 48 hours in a 100 ℃ oven, cooled to room temperature, washed by ultrapure water and absolute ethyl alcohol, and dried to obtain blue crystals. The blue crystal is a pure CuCd-MOF material without doping GO, namely, the value of x in CuCd/GO-x is 0, namely, the pure CuCd-MOF material.
The obtained CuCd-MOF was characterized by infrared spectrum, the specific result is IR (KBr, cm-1): 3408 (s), 1620(s), 1593(s), 1442 (w), 1402 (m), 1326 (w), 1299 (w), 1240 (w), 1149 (m), 1130 (m), 1091(s), 1070(s), 997 (m), 923 (w), 850 (w), 788 (m), 750 (m), 632 (m), 578 (m), 555 (m), 514 (w) (fig. 3).
Example 2: preparation of CuCd-MOF/GO-1.5 composite material visible light catalyst
0.0998g of copper acetate, 0.1333g of cadmium acetate and 0.1136g N- (phosphonomethyl) iminodiacetic acid are weighed and dissolved in 6mL of water, 0.0052g of graphene oxide is added into a solution system, the solution system is uniformly mixed by ultrasound, the solution is transferred into a 50mL high-pressure reaction kettle, the solution is reacted for 48 hours in a 100 ℃ oven, and after the solution is cooled to room temperature, the solution is washed by ultrapure water and absolute ethyl alcohol and dried, and blue-black crystals are obtained. The blue-black crystal is a CuCd-MOF/GO composite material with the GO doping ratio of 1.5%, and is marked as CuCd-MOF/GO-1.5.
Example 3: cuCd-MOF/GO-3 composite material visible light catalyst and preparation thereof
0.0998g of copper acetate, 0.1333g of cadmium acetate and 0.1136g N- (phosphonomethyl) iminodiacetic acid are weighed and dissolved in 6mL of water, 0.0104g of graphene oxide is added into the solution system, the mixture is uniformly mixed by ultrasound, the mixture is transferred into a 50mL high-pressure reaction kettle, the mixture is reacted for 48 hours in a 100 ℃ oven, and after cooling to room temperature, the mixture is washed by ultrapure water and absolute ethyl alcohol, and blue-black crystals are obtained after drying. The blue-black crystal is a CuCd-MOF/GO composite material with the GO doping ratio of 3 percent and is marked as CuCd-MOF/GO-3.
Example 4: preparation of CuCd-MOF/GO-5 composite material visible light catalyst
0.0998g of copper acetate, 0.1333g of cadmium acetate and 0.1136g N- (phosphonomethyl) iminodiacetic acid are weighed and dissolved in 6mL of water, 0.0173g of graphene oxide is added into a solution system, the mixture is uniformly mixed by ultrasound, then the mixture is transferred into a 50mL high-pressure reaction kettle, the mixture is reacted for 48 hours in a 100 ℃ oven, and after the mixture is cooled to room temperature, the mixture is washed by ultrapure water and absolute ethyl alcohol, and blue-black crystals are obtained after drying. The blue-black crystal is a CuCd-MOF/GO composite material with the GO doping proportion of 5%, and is marked as CuCd-MOF/GO-5.
The obtained CuCd-MOF/GO-5 was characterized by infrared spectrum, with specific results of IR (KBr, cm-1): 3406 (s), 1618(s), 1595(s), 1442 (w), 1402 (m), 1326 (w), 1300 (w), 1240 (w), 1150 (m), 1130 (m), 1091(s), 1070(s), 997 (m), 924 (w), 851 (w), 789 (m), 748 (m), 633 (m), 579 (m), 555 (m), 515 (w). (FIG. 3)
The raman spectra of CuCd/GO-5 composite and GO are shown in fig. 4. 1355cm -1 And 1591cm -1 The peak values are respectively attributed to the typical D and G peaks of graphene oxide. Typically, the G peak is hybridized to an sp2 hybridized C-C bond by in-plane vibration (E 2g Symmetry) and the D peak is the sp3 hybridized out-of-plane vibration of the carbon atom (a) associated with defects in the internal structure of the graphite layer 1g Symmetry). In the Raman spectrum of the CuCd-MOF/GO-5 composite material, 1359cm were measured -1 And 1600cm -1 The red shift of the D and G peaks was observed. This phenomenon suggests a considerable charge transfer between GO and CuCd-MOF by electrostatic forces, which is a strong demonstration of strong interactions between GO and CuCd-MOF. The comprehensive electron microscope photograph and the Raman spectrum both show that the CuCd-MOF and the graphene oxide are successfully compounded.
Example 5: preparation of CuCd-MOF/GO-7.5 composite material visible light catalyst
0.0998g of copper acetate, 0.1333g of cadmium acetate and 0.1136g N- (phosphonomethyl) iminodiacetic acid are weighed and dissolved in 6mL of water, 0.0260g of graphene oxide is added into a solution system, the solution system is uniformly mixed by ultrasound, then the solution is transferred into a 50mL high-pressure reaction kettle, reacted for 48 hours in a 100 ℃ oven, cooled to room temperature, washed by ultrapure water and absolute ethyl alcohol, and dried to obtain blue-black crystals. The blue-black crystal is a CuCd-MOF/GO composite material with the GO doping proportion of 7.5%, and is marked as CuCd-MOF/GO-7.5.
Correlation performance detection
1. XRD spectra of the CuCd-MOF, cuCd-MOF/GO-1.5, cuCd-MOF/GO-3, cuCd-MOF/GO-5 and CuCd-MOF/GO-7.5 prepared in examples 1 to 5 are shown in FIG. 2.
2. The materials prepared in examples 1 to 5 were used as a photocatalyst, and an experiment for degrading Methylene Blue (MB) organic dye by visible light catalysis was performed by using a xenon lamp to simulate a visible light source.
50mL of methylene blue aqueous solution with the concentration of 10mg/L is placed in a jacketed beaker, 30mg of the materials prepared in examples 1-5 are respectively added, the suspension is stirred for 60 minutes in a dark environment, after the adsorption-desorption equilibrium is reached, sampling is carried out once in the dark environment for 30 minutes, and the dark reaction is carried out for 3 times from the beginning to the end. And (3) turning on a xenon lamp, simulating a visible light source to perform photocatalytic degradation reaction, sampling once every 10 minutes, sampling 4 times in total, centrifuging the taken suspension at a rotation speed of 6000 rpm for 5 minutes, and analyzing the concentration of the supernatant by an ultraviolet-visible spectrophotometry.
The degradation efficiency of the materials on methylene blue is shown in figure 6, and from the figure, it can be seen that the CuCd-MOF/GO-5 composite material photocatalyst prepared in example 4 has the highest catalytic photodegradation efficiency on methylene blue, 92.0% of methylene blue can be degraded within 40min, and the rate constant reaches 0.0533min -1 。
3. A scanning electron micrograph of graphene oxide, cuCd-MOF and CuCd-MOF/GO-5 composites is shown in FIG. 5. Graphene oxide (a panels) is curled, wavy, appearing as thin and thick; cuCd-MOF (b panel) shows that the ultra-thin crystal grains have good crystallization, the average length is 2-5 μm, and the thickness is 1-2 μm; the electron microscope picture of the CuCd-MOF/GO-5 composite material (c, d small picture) shows that the surface of the flaky crystal grains uniformly disperses and clamps the morphology of the graphene oxide.
4. The CuCd-MOF/GO-5 composite material prepared in example 4 was selected as a photocatalyst, and a xenon lamp was used to simulate a visible light source for experiments of degrading different organic dyes by visible light catalysis.
(1) 50mL of Congo red solution with the concentration of 10mg/L is taken, placed in a jacketed beaker, 30mg of CuCd/GO-5 composite material prepared in example 4 is added, the suspension is stirred for 60 minutes in a dark environment, and after the adsorption-desorption equilibrium is reached, the dark reaction is sampled every 30 minutes for 3 times. And (3) turning on a xenon lamp, simulating a visible light source to perform photocatalytic degradation reaction, sampling once every 10 minutes, sampling 4 times in total, centrifuging the taken suspension at a rotation speed of 6000 rpm for 5 minutes, and analyzing the concentration of the supernatant by an ultraviolet-visible spectrophotometry. The degradation efficiency of the CuCd/GO-5 composite material on Congo red is shown in figure 7, and the degradation rate is 90.1% in 40 min.
(2) 50mL of methyl orange solution with the concentration of 10mg/L is taken, placed in a jacketed beaker, 30mg of CuCd/GO-5 composite material prepared in example 4 is added, the suspension is stirred for 60 minutes in a dark environment, and after the adsorption-desorption equilibrium is reached, the dark reaction is sampled every 30 minutes for 3 times. And (3) turning on a xenon lamp, simulating a visible light source to perform photocatalytic degradation reaction, sampling once every 10 minutes, sampling 4 times in total, centrifuging the taken suspension at a rotation speed of 6000 rpm for 5 minutes, and analyzing the concentration of the supernatant by an ultraviolet-visible spectrophotometry. The degradation efficiency of the CuCd/GO-5 composite material on methyl orange is shown in figure 7, and the degradation rate is 85.4% in 40 min.
(3) 50mL of rhodamine B solution with the concentration of 10mg/L is taken, placed in a jacketed beaker, 30mg of the CuCd/GO-5 composite material prepared in example 4 is added, the suspension is stirred for 60 minutes in a dark environment, and after the adsorption-desorption equilibrium is reached, the dark reaction is sampled every 30 minutes, and the total sampling is 3 times. And (3) turning on a xenon lamp, simulating a visible light source to perform photocatalytic degradation reaction, sampling once every 10 minutes, sampling 4 times in total, centrifuging the taken suspension at a rotation speed of 6000 rpm for 5 minutes, and analyzing the concentration of the supernatant by an ultraviolet-visible spectrophotometry. The degradation efficiency of the CuCd/GO-5 composite material on rhodamine B is shown as a figure 7, and the degradation rate is 79.6% in 40 min.
(4) 50mL of a 10mg/L levofloxacin solution was placed in a jacketed beaker, 30mg of the CuCd-MOF/GO-5 composite material prepared in example 4 was added, the suspension was stirred in a dark environment for 60 minutes, and after reaching adsorption-desorption equilibrium, the dark reaction was sampled every 30 minutes for a total of 3 times. And (3) turning on a xenon lamp, simulating a visible light source to perform photocatalytic degradation reaction, sampling once every 20 minutes, sampling four times altogether, centrifuging the taken suspension at a rotation speed of 6000 rpm for 5 minutes, and analyzing the concentration of the supernatant by an ultraviolet-visible spectrophotometry. The degradation efficiency of the CuCd/GO-5 composite material on the levofloxacin is shown in figure 7, and the degradation rate is 87.6% in 80 min.
5. The 4-cycle photocatalytic degradation experiment is carried out on the methylene blue solution by using the CuCd-MOF/GO-5 composite material photocatalyst prepared in the embodiment 4, and the PXRD diagram of the CuCd-MOF/GO-5 composite material after 4 cycles is shown in figure 8, so that the catalytic effect of the CuCd-MOF/GO-5 composite material is basically unchanged after the methylene blue solution is subjected to 4-cycle photocatalytic degradation, and the CuCd-MOF/GO-5 composite material has higher photochemical activity and higher stability and can be recycled.
The foregoing has outlined and described the basic principles, features, and advantages of the present invention. However, the foregoing is merely specific examples of the present invention, and the technical features of the present invention are not limited thereto, and any other embodiments that are derived by those skilled in the art without departing from the technical solution of the present invention are included in the scope of the present invention.
Claims (6)
1. The application of the CuCd-MOF/GO-x composite material with visible light catalytic degradation performance in the visible light catalytic degradation of organic dye is characterized in that the material can be used for the photocatalytic degradation of methylene blue, congo red, methyl orange, rhodamine B or levofloxacin under the visible light condition, has the cyclical stability and can be recycled;
the CuCd-MOF and GO are combined with each other through hydrogen bonds;
CuCthe chemical expression of d-MOF is { [ Cu ] 2 Cd 2 (pmida) 2 (H 2 O) 7 ]·3H 2 O} n Which is a kind of H 4 pmida is a ligand and contains metal organic framework materials of Cu and Cd metal ions;
x represents the percentage content of graphene oxide in the composite material, x=5;
each asymmetric unit of the CuCd-MOF contains 2 deprotonated organic ligands pmida 4- 2 copper ions, 2 cadmium ions, 7 coordinated water molecules and 3 lattice water molecules, the molecular structures of which are shown as follows:
2. the use of a CuCd-MOF/GO-x composite material with visible light catalytic degradation properties according to claim 1 for the catalytic degradation of organic dyes in visible light, characterized in that the asymmetric units of the CuCd-MOF are connected to each other forming a two-dimensional layered structure.
3. The application of the CuCd-MOF/GO-x composite material with visible light catalytic degradation performance in the visible light catalytic degradation of organic dye according to claim 1, wherein the CuCd-MOF belongs to monoclinic system, and the P21/n space group has the following unit cell parameters:
β＝95.647°、/>
4. the application of the CuCd-MOF/GO-x composite material with visible light catalytic degradation performance in the visible light catalytic degradation of organic dye as claimed in claim 1, wherein the specific preparation steps of the CuCd-MOF/GO-x composite material are as follows:
(1) Dissolving copper acetate, cadmium acetate and N- (phosphonomethyl) iminodiacetic acid in ultrapure water, uniformly mixing the solution by ultrasonic waves to obtain a solution, slowly adding graphene oxide into the solution system, and carrying out ultrasonic waves for 20-30 min;
(2) Transferring the mixed solution obtained in the step (1) into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting in an oven, naturally cooling, filtering, washing and drying to obtain the CuCd-MOF/GO-x composite material.
5. The use of the CuCd-MOF/GO-x composite material with visible light catalytic degradation property according to claim 4, wherein in the step (1), the molar ratio of copper acetate, cadmium acetate and N- (phosphonomethyl) iminodiacetic acid is 1-1.2:1.
6. The use of the CuCd-MOF/GO-x composite material with visible light catalytic degradation property according to claim 4, wherein in step (2), the reaction temperature in the oven is 100-120 ℃ and the reaction time is 45-50 h.
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