CN113398996A - CdS @ UIO-66-NH2Preparation method of core-shell composite material - Google Patents
CdS @ UIO-66-NH2Preparation method of core-shell composite material Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B01J35/23—
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- B01J35/39—
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
CdS @ UIO-66-NH2The preparation method of the core-shell composite material comprises the following steps: (1) taking a certain amount of CdS nano-particles prepared by cadmium nitrate and thiourea under a hydrothermal method, and performing ultrasonic dispersion to form uniform dispersion liquid; (2) adding a certain amount of methacrylic acid into a certain amount of zirconium n-propoxide solution, reacting for a certain time, and treating to obtain Zr6Cluster precursors; (3) adding a certain amount of CdS nano dispersion liquid into Zr6Dispersing the cluster precursor in ultrasonic wave, adding a certain amount of 2-amino terephthalic acid, and reacting for a period of time at a certain temperatureAfter the above steps, CdS @ UIO-66-NH with a certain shell thickness is obtained by treatment2A composite material with a core-shell structure. The invention solves the problem of preparing UIO-66-NH by the traditional one-pot method2HCl is easily generated in the process; the core-shell structure is constructed, so that the problem that the photocatalytic activity of CdS nanoparticles is reduced due to agglomeration is solved, and the photocatalytic efficiency is improved.
Description
Technical Field
The invention relates to CdS @ UIO-66-NH2A preparation method of a core-shell composite material, belonging to the technical field of nano composite materials.
Background
Cadmium sulfide is an inorganic substance, the chemical formula is CdS, the number of crystals is two, the alpha-type is lemon yellow powder, and the beta-type is orange red powder. Slightly soluble in water, readily soluble in acid, slightly soluble in ammonia. Can be used for preparing fireworks, glass glaze, porcelain glaze, luminescent materials and pigments. The high-purity cadmium sulfide is a good semiconductor, has strong photoelectric effect on visible light, and can be used for manufacturing photoelectric tubes, solar cells, photocatalysts and the like.
UIO-66-NH2The porous material is a metal organic framework, and has the advantages of high specific surface area, high porosity and various structures. It is made up by using Zr metal cluster as centre and 12 terephthalic acids (H)2BDC) is a metal organic framework material formed by self-assembly of organic ligands. UIO-66-NH2The crystal structure of (2) is a regular octahedron, and the pore structure of the crystal is formed by connecting regular tetrahedron cages (0.8 nm) and regular octahedron cages (1.1 nm) through triangular windows (0.6 nm). UIO-66-NH2Has good thermal stability, can still keep complete crystal structure at high temperature (500 ℃), and can keep chemical stability under the conditions of water, DMF, acetone and other solvents and certain acid and alkali. UIO-66-NH2The material has good stability, large specific surface area and adjustable active sites, and is widely applied to the research in the fields of adsorption, energy storage, catalysis and the like.
The core-shell structure is a novel two-phase heterostructure and is widely applied to the nano composite catalyst in recent years. It has the following advantages: (1) the contact area of two phases is increased, the chemical activity and stability of the core nano-particles are ensured, and secondary pollution is avoided; (2)the catalytic process is limited in a certain spatial region, so that the catalytic selectivity is improved; (3) can transfer catalytic intermediate product quickly and avoid catalyst deactivation. Generally, the core-shell structure is prepared by growing a layer of nano shell on the surface of core nano particles by a one-pot method. Unfortunately, the conventional one-pot method for preparing CdS nanoparticles and UIO-66-NH2The core-shell structure of (1) is very difficult because of UIO-66-NH2Hydrochloric acid with strong acidity is easily generated in the formation process of the crystal, so that CdS nano-particles are dissolved, and the composite material with the core-shell structure is difficult to obtain.
In conclusion, the preparation method of the CdS @ UIO-66-NH2 core-shell composite material with the adjustable shell layer thickness can be developed and developed, and the economic and effective CdS @ UIO-66-NH preparation with general applicability is found2The method of core-shell composites is very important.
Disclosure of Invention
The invention aims to provide CdS @ UIO-66-NH aiming at the problems in the preparation of the composite material with the existing core-shell structure2A preparation method of a core-shell composite material.
The technical scheme for realizing the method is as follows, in order to avoid the formation of HCl in the reaction process, Zr is synthesized in advance6O4(OH)4 12+Cluster precursors, CdS and terephthalic acid organic ligands are introduced to prepare the core-shell structure composite material, and different shell thicknesses are obtained in a layer-by-layer assembly mode.
CdS @ UIO-66-NH2The preparation method of the core-shell composite material comprises the following specific steps:
(1) taking a certain amount of CdS nano-particles prepared by cadmium nitrate and thiourea under a hydrothermal method, and performing ultrasonic dispersion to form uniform dispersion liquid;
(2) adding a certain amount of methacrylic acid into a certain amount of zirconium n-propoxide solution, reacting for a certain time, and treating to obtain Zr6Cluster precursors;
(3) adding a certain amount of CdS nano dispersion liquid into Zr6Dispersing the cluster precursor in ultrasonic wave, adding a certain amount of 2-amino terephthalic acid, and heating at a certain temperatureReacting for a period of time, and processing to obtain CdS @ UIO-66-NH with a certain shell thickness2A composite material with a core-shell structure.
The morphology and the structure of the core-shell photocatalyst are characterized by a transmission electron microscope, an XRD diffraction spectrum, a Raman spectrum and a Mapping spectrum, and the result shows that the core-shell photocatalyst is successfully prepared.
In the invention, in order to avoid HCl and Zr easily generated in the traditional method for preparing UIO-666The concentration of the cluster precursor is very important for forming the core-shell composite material, and in the invention, the concentration of the Zr6 cluster precursor is 0-1 mol/L.
In the present invention, Zr6The reaction of the cluster precursor and the ligand can be completed within a certain time, so that the reaction time required by the method is 2-12 h.
In the invention, CdS is used as a core, and the concentration of the nano-particle dispersion liquid has important influence on the formation of a core-shell structure, so that the concentration of the CdS nano-dispersion liquid is 0.1-0.5 mg/L.
Compared with the prior art, the invention has the beneficial results that: the method has simple operation and mild condition, and can successfully prepare CdS @ UIO-66-NH at room temperature2A core-shell composite material. The invention solves the problem of preparing UIO-66-NH by the traditional one-pot method2HCl is easily generated in the process, so that a core-shell structure of CdS @ UIO-66 cannot be formed, and the reaction temperature does not need high temperature. Therefore, the core-shell structure is constructed, so that the problem that the photocatalytic activity of CdS nanoparticles is reduced due to agglomeration is solved, and the photocatalytic efficiency is improved.
The CdS @ UIO-66-NH2 core-shell composite material prepared by the method can be used for photocatalytic degradation of organic pollutants, such as indoor pollution, water body pollution and the like.
Drawings
FIG. 1 is a CdS @ UIO-66-NH representation of the present invention2A flow chart for preparing the core-shell composite material;
FIG. 2 is CdS @ UIO-66-NH2A transmission electron microscope image of the core-shell composite material;
FIG. 3 is CdS @ UIO-66-NH, respectively2Core-shell composite material, CdS and UIO-66-NH2XRD pattern of (a);
FIG. 4 is CdS @ UIO-66-NH2EDS spectra of core-shell composites;
FIG. 5 is CdS @ UIO-66-NH2Core-shell composite material and Raman spectrogram of CdS.
Detailed Description
A specific embodiment of the present invention is shown in fig. 1.
Example 1: this example is a single layer thickness CdS @ UIO-66-NH2Core-shell composite material
Weighing 2.16g of cadmium nitrate, dissolving in 70mL of ethylene glycol, and uniformly stirring; then 0.78g of polyvinylpyrrolidone (PVP) was added to the solution and stirring was continued until clear, followed by adding 0.53g of thiourea to the solution and mixing well. And (3) putting the mixed solution into a 100mL reaction kettle, putting the reaction kettle into an oven, setting the temperature at 120 ℃, and reacting for 4 h. And after the reaction is finished, naturally cooling the reaction kettle at the temperature, and centrifuging the obtained yellow solution to obtain a crude product. Then, the product was washed with deionized water and anhydrous methanol, respectively, and centrifuged, repeatedly three times, and then dried in a vacuum oven at 100 ℃. And dispersing the formed CdS nano-particles in deionized water to prepare 0.25 mg/L. Adding 14mL of methacrylic acid and 0.5mL of deionized water into 20mL of zirconium n-propoxide solution, stirring for 10min, standing for 12h, performing vacuum filtration on the solution when the volume of the solution is reduced to 1/4 when the volume of the solution is reduced to the initial volume, washing the solution once with isopropanol, and performing vacuum drying to obtain Zr6And (3) precursor samples. 2mL of CdS nano-dispersion is added into 10mL of Zr6Performing ultrasonic treatment for 15min at room temperature in the precursor; then the mixture is centrifuged for 1min at 8000r/min and washed twice by ethanol. 10mL of 2-aminoterephthalic acid (BDC-NH) was then added to the above solution 21 mM) solution, and reacting for 2 hours at room temperature after 10min of ultrasonic treatment; centrifuging at 8000r/min for 1min, washing with ethanol twice, and vacuum drying to obtain single-layer CdS @ UIO-66-NH2。
The morphology and the structure of the core-shell photocatalyst are characterized by a transmission electron microscope, an XRD diffraction spectrum, a Raman spectrum and an EDS spectrum, and the result shows that the core-shell photocatalyst is successfully prepared.
FIG. 2 is a graph of CdS @ UIO-66-NH with different shell thicknesses2A transmission electron microscope image of the core-shell composite material;
the analysis shows that: CdS @ UIO-66-NH with different shell thicknesses2The core-shell photocatalyst is successfully prepared, the existence of a core-shell two phase of the composite can be obviously seen, and the appearance and the size of the central core are not changed along with the change of the cycle number. However, it is worth noting that the thickness of the outer shell of the composite is obviously increased with the increase of the cycle number, and the maximum thickness reaches about 20 nm. The above results show that the shell thickness outside the composite can be effectively controlled by varying the number of cycles of the reaction during the synthesis.
FIG. 3 is CdS @ UIO-66-NH, respectively2Core-shell composite material, CdS and UIO-66-NH2XRD pattern of (a);
it can be clearly seen from the figure that diffraction peaks exist at positions of 2 θ = 24.9 °, 26.5 °, 28.2 °, 43.8 °, 47.8 °, and 51.9 °, corresponding to (100), (002), (101), (110), (103), and (112) crystal planes of the hexagonal CdS crystal. Secondly, for pure UIO-66-NH2In other words, the positions of all diffraction peaks are consistent with those reported previously, wherein two main characteristic diffraction peaks with sharp peak shapes and stronger intensities are present at the 2 theta = 7.3 ° and 8.4 ° positions, which indicates that the prepared UIO-66-NH is2The crystal purity and crystallinity are high. And for the complex CdS @ UIO-66-NH2Not only characteristic peaks corresponding to CdS crystals can be observed, but also strong UIO-66-NH appears at 2 θ = 7.3 ° and 8.4 °2Further illustrating that the CdS outer surface of the complex is covered by UIO-66-NH2And the crystal is relatively complete and has strong crystallinity.
FIG. 4 is CdS @ UIO-66-NH2EDS spectra of core-shell composites;
as can be seen from the scanning electron micrograph of the figure a, the composite material is spherical particles. Analyzing the element distribution of the composite material according to Mapping electronic energy spectrum, wherein Zr element is a central metal atom for constructing UIO-66-NH2 crystal and is mainly distributed on the outer surface of the composite; and the distribution positions of the S element and the Cd element are positioned in the middle of the compound, and the distribution range is slightly smaller than that of the Zr element. The prepared composite is of a core-shell structure with CdS nanoparticles at the center and UIO-66-NH2 crystals at the outer layer, and the shell layer has a certain thickness. And the figure b is an element analysis (EDS) map of the composite, and characteristic peaks of elements such as Zr, O, N, S, Cd and the like can be obviously observed from the EDS map, so that the core-shell nano composite of the CdSnPs @ UIO-66-NH2 can be successfully prepared in a layer-by-layer self-assembly mode.
FIG. 5 is CdS @ UIO-66-NH2A Raman spectrum of the core-shell composite material and CdS;
it is clear from the figure that the CdSNPs are at 297cm-1And 595cm-1There are distinct characteristic peaks, respectively, which were previously reported to be consistent. Wherein 297cm-1The characteristic peak at (1 LO) is due to the vibration of the Cd-S bond in the A1 mode, and 597 cm-1The characteristic peak at (a) is the overtone of the two LO phonons. Due to UIO-66-NH2Middle apolar sp2The bond carbons have a lower density and no distinct characteristic peak, so CdS @ UIO-66-NH2-5 at 297cm-1 and 595cm-1The Raman shift peak of the CdS nano-particle is basically coincident with that of the CdS nano-particle. But due to UIO-66-NH2The electron cloud interaction between the Zr atom and the Cd atom in the CdS can cause the Raman peak to have a slight blue shift. The above results indicate that CdSNPs @ UIO-66-NH2-5 composite material, CdS nano-particles and UIO-66-NH2There are strong interaction forces in the crystal.
Example 2: 3 layer thickness CdS @ UIO-66-NH2Core-shell composite material
The procedure of example 1 was followed on the basis of the product obtained in example 1.
Example 3: 5 layer thickness CdS @ UIO-66-NH2Core-shell composite material
The procedure of example 1 was followed on the basis of the product obtained in example 2.
Example 4: 7 layer thickness CdS @ UIO-66-NH2Core-shell composite material
The procedure of example 1 was followed on the basis of the product obtained in example 3.
Claims (6)
1. CdS @ UIO-66-NH2The preparation method of the core-shell composite material is characterized in that the method utilizes the presynthesis for controlling the formation of HCl in the reaction processZr (b) of6O4(OH)4 12+Cluster precursors, and CdS nano-particles and organic ligand terephthalic acid are introduced to prepare the composite material with the CdS particles as the core and the UIO-66 as the shell, and the specific steps are as follows:
(1) taking a certain amount of CdS nano-particles prepared by cadmium nitrate and thiourea under a hydrothermal method, and performing ultrasonic dispersion to form uniform dispersion liquid;
(2) adding a certain amount of methacrylic acid into a certain amount of zirconium n-propoxide solution, reacting for a certain time, and treating to obtain Zr6Cluster precursors;
(3) adding a certain amount of CdS nano dispersion liquid into Zr6Performing ultrasonic dispersion on the cluster precursor, adding a certain amount of 2-amino terephthalic acid, reacting for a period of time at a certain temperature, and processing to obtain CdS @ UIO-66-NH with a certain shell thickness2A composite material with a core-shell structure.
2. CdS @ UIO-66-NH according to claim 12The preparation method of the core-shell composite material is characterized in that Zr6The cluster precursor can be used for preparing a core-shell structure composite material taking CdS as a core UIO-66 as a shell.
3. CdS @ UIO-66-NH according to claim 12The preparation method of the core-shell composite material is characterized in that the reaction time is 2-12 hours, and the reaction temperature is 0-120 ℃.
4. CdS @ UIO-66-NH according to claim 12The preparation method of the core-shell composite material is characterized in that Zr is adopted6The concentration of the cluster precursor is 0-1 mol/L.
5. The method for preparing CdS @ UIO-66-NH2 core-shell composite material according to claim 1, wherein the concentration of CdS nano-dispersion is 0.1-0.5 mg/L.
6. According to claim 1CdS @ UIO-66-NH2The preparation method of the core-shell composite material is characterized by comprising the following specific implementation steps:
weighing 2.16g of cadmium nitrate, dissolving in 70mL of ethylene glycol, and uniformly stirring; then adding 0.78g of polyvinylpyrrolidone into the solution, continuously stirring until the solution is transparent, then continuously adding 0.53g of thiourea into the solution, and uniformly mixing; putting the mixed solution into a 100mL reaction kettle, putting the reaction kettle into an oven, setting the temperature to be 120 ℃, and reacting for 4 hours; after the reaction is finished, naturally cooling the reaction kettle at the temperature, and centrifuging the obtained yellow solution to obtain a crude product;
washing with deionized water and anhydrous methanol respectively, centrifuging, repeating for three times, and drying at 100 deg.C in a vacuum drying oven; dispersing the formed CdS nano-particles in deionized water to prepare 0.25 mg/L; adding 14mL of methacrylic acid and 0.5mL of deionized water into 20mL of zirconium n-propoxide solution, stirring for 10min, standing for 12h, performing vacuum filtration on the solution when the volume of the solution is reduced to 1/4 when the volume of the solution is reduced to the initial volume, washing the solution once with isopropanol, and performing vacuum drying to obtain Zr6A precursor sample;
2mL of CdS nano-dispersion is added into 10mL of Zr6Performing ultrasonic treatment for 15min at room temperature in the precursor; centrifuging at 8000r/min for 1min, and washing with ethanol twice; 10mL of 2-aminoterephthalic acid (BDC-NH) was then added to the above solution21 mM) solution, and reacting for 2 hours at room temperature after 10min of ultrasonic treatment; centrifuging at 8000r/min for 1min, washing with ethanol twice, and vacuum drying to obtain single-layer CdS @ UIO-66-NH2。
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