CN109569726B - MOFs/CNT photocatalyst and preparation method thereof - Google Patents
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- 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]
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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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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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
- C02F2101/00—Nature of the contaminant
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- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses an MOFs/CNT photocatalyst and a preparation method thereof, wherein MOFs are MIL-53(Al) and UIO-66(Zr) respectively, the preparation method comprises the steps of adding a multi-wall carbon nano tube into a metal salt solution of the MOFs, reacting at 180-190 ℃ by adopting a hydrothermal method, and purifying and activating the synthesized MOFs/CNT by adopting a heat treatment method. The obtained MOFs/CNT has the characteristics of stability and high reutilization, and has a good degradation effect on phenolic pollutants.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to an MOFs/CNT photocatalyst and a preparation method thereof.
Background
Metal-organic frameworks (MOFs), also known as porous coordination polymers, are porous crystalline materials with periodic multi-dimensional network structures formed by self-assembly of metal ions or metal cluster units and organic ligands through coordination. MOFs have potential application prospects in many fields, mainly including gas storage and separation, catalysis, sensors, drug transport, proton conductors, and the like. The metal clusters in the MOFs structure are thought to play the role of semiconductor quantum dots, and the organic ligands thereof are used to activate the metal clusters under the photoexcitation condition based on the "antenna effect", thereby making the MOFs possible as a photocatalyst and being used for photocatalytic reactions. There are studies that MIL-53(Fe) can degrade Methylene Blue (MB) under uv-visible or visible light conditions, but the photodegradation rate is not too high.
The Carbon Nano Tube (CNT) has large specific surface area, high chemical stability, better adsorption capacity and unique characteristicsIntrinsic structure (one dimensional cavity, aspect ratio) exhibits unique metal or semiconductor conductivity. Research shows that the carbon nano tube and TiO2The ZnO composite can improve TiO2ZnO photocatalytic activity. The composite carbon nano tube can promote the separation of photo-generated electrons and holes, improve the content of hydroxyl radicals and enhance the photosensitive effect. How to load MOFs on a carbon nano tube to synthesize a composite photocatalyst which is stable and has high repeated utilization rate is the technical problem to be solved by the invention.
Disclosure of Invention
The invention provides an MOFs/CNT photocatalyst and a preparation method thereof, wherein MOFs are MIL-53(Al) and UIO-66(Zr) respectively, the preparation method comprises the steps of adding a multi-wall carbon nano tube into a metal salt solution of the MOFs, reacting at 180-190 ℃ by adopting a hydrothermal method, and purifying and activating the synthesized MOFs/CNT by adopting a heat treatment method. The obtained MOFs/CNT has the characteristics of stability and high reutilization, and has a good degradation effect on phenolic pollutants.
The technical scheme of the MOFs/CNT photocatalyst and the preparation method thereof is that the MOFs/CNT photocatalyst is a photocatalyst synthesized by loading MOFs on carbon nano tubes.
MOFs are MIL-53(Al) and UIO-66(Zr) respectively.
The preparation method of the MOFs/CNT photocatalyst comprises the steps of adding the multi-wall carbon nano-tube into a metal salt solution of the MOFs, reacting at 190 ℃ at 180 ℃ by adopting a hydrothermal method, and purifying and activating the synthesized MOFs/CNT by adopting a heat treatment method.
Preparation steps of the MIL-53(Al)/CNT composite material:
(1) dissolving aluminum nitrate and terephthalic acid in N, N-dimethylformamide respectively, performing ultrasonic dissolution, and adding a certain amount of multi-walled carbon nanotubes to obtain a mixture;
(2) the mixture reacts for 48 to 72 hours at 180 ℃ and 190 ℃;
(3) naturally cooling at room temperature after the reaction is finished to obtain a light brown solid-liquid mixture, filtering, washing for 1-3 times by using N, N-dimethylformamide, adding ethanol, ultrasonically washing, and moving to a 120 ℃ oven for drying;
(4) and (3) placing the dried product at the temperature of 350-650 ℃ for drying for 5-8h to obtain the activated MIL (Al) -53/CNT composite material.
In the step (1), the solid-to-liquid ratio of the multi-walled carbon nano-tube to the MIL-53(Al) is 1-50g/L, the concentration of aluminum nitrate in the MIL-53(Al) is 0.024-0.115mol/L, and the concentration of terephthalic acid is 0.016-0.069 mol/L.
In the step (2), the mixture is transferred to a polytetrafluoroethylene lining tank and then placed in a stainless steel hydrothermal reaction kettle, and the reaction kettle is sealed and then placed in an oven with the temperature of 180 ℃ and 190 ℃ for reaction for 48 to 72 hours.
UIO-66(Zr)/CNT composite material preparation steps:
weighing zirconium tetrachloride, respectively ultrasonically dissolving terephthalic acid in N, N-dimethylformamide, adding a multi-walled carbon nanotube, and ultrasonically mixing uniformly to obtain a mixture;
secondly, reacting the mixture at the temperature of 180 ℃ and 200 ℃ for 48-72 h;
taking out the reaction kettle after the reaction is finished, naturally cooling the reaction kettle at room temperature to obtain a blue-black solid-liquid mixture, filtering the mixture, washing the mixture for 1 to 3 times by using N, N-dimethylformamide, and then placing the mixture at 120 ℃ for drying;
fourthly, the dried product is placed into the temperature of 350-650 ℃ for drying for 5-8h, and the activated UI0-66 (Zr)/CNT composite material is obtained.
In the step I, the solid-to-liquid ratio of the multi-wall carbon nano tube to UIO-66(Zr) is 1-50 g/L; the concentration of zirconium tetrachloride in UIO-66(Zr) was 9.56X 10-3-0.207 mol/L, concentration of terephthalic acid, 0.0123-0.187 mol/L.
And step two, transferring the mixture into a polytetrafluoroethylene lining tank, placing the polytetrafluoroethylene lining tank into a stainless steel hydrothermal reaction kettle, sealing the reaction kettle, and placing the reaction kettle in an oven with the temperature of 180 ℃ and 200 ℃ for reaction for 48-72 hours.
The multi-walled carbon nanotube is a commercial carbon nanotube.
Evaluation method of photocatalytic performance:
the whole photocatalytic reaction is carried out in a photocatalytic reactor, 50mL of 20mg/L p-nitrophenol is respectively added into a photocatalytic test tube by taking a mercury lamp as a light source, 0.01g of MOFs/CNT photocatalyst is added, adsorption is carried out in the dark for 30min before, and then the photocatalytic degradation is carried out after opening. Samples were taken every 5 minutes and absorbance was measured using an ultraviolet-visible spectrophotometer. The concentration was recorded as a function of time.
The invention has the beneficial effects that: the invention has the advantages that MOFs and the multi-walled carbon nano-tube are compounded to prepare the novel photocatalyst, thereby enhancing the adsorption of pollutants, accelerating the migration and separation efficiency of photon-generated carriers, overcoming the defects of the MOFs, increasing the specific surface area of the MOFs and increasing the adsorption effect on the pollutants. The MOFs/CNT obtained by the invention has the characteristics of stability and high reutilization, and has a good degradation effect on phenolic pollutants.
FIG. 1 is SEM photograph showing the MIL-53(Al)/CNT, which shows that the MIL-53(Al) surface is doped with fine CNT; FIG. 2 is an SEM micrograph of UIO-66(Zr)/CNT, finely divided UIO-66(Zr) surface doped with fine CNT; FIG. 3 is an XRD picture of MIL-53(Al)/CNT with peaks consistent with MIL-53 (Al); FIG. 4 is an XRD picture of UIO-66(Zr)/CNT, with a peak shape consistent with UIO-66 (Zr).
Description of the drawings:
FIG. 1 shows an SEM micrograph of MIL-53 (Al)/CNT;
FIG. 2 shows an SEM micrograph of UIO-66 (Zr)/CNT;
FIG. 3 shows an XRD pattern of MIL-53 (Al)/CNT;
FIG. 4 shows an XRD pattern of UIO-66 (Zr)/CNT;
FIG. 5 shows the cyclic photodegradation curve of MIL-53(Al)/CNT for p-nitrophenol;
FIG. 6 shows the cyclic photodegradation curve of UIO-66(Zr)/CNT for p-nitrophenol.
The specific implementation mode is as follows:
for better understanding of the present invention, the technical solution of the present invention will be described in detail with specific examples, but the present invention is not limited thereto.
Example 1
Weighing 1.3g of aluminum nitrate and 0.288g of terephthalic acid, respectively ultrasonically dissolving the aluminum nitrate and the terephthalic acid in 25mL of N, N-dimethylformamide, adding 1g of carbon nano tube, pouring the mixture into a polytetrafluoroethylene lining tank, placing the polytetrafluoroethylene lining tank into a stainless steel reaction kettle, sealing the reaction kettle, and placing the reaction kettle in an oven at 180 ℃ for reaction for 72 hours. And after the reaction is finished, taking out the reaction kettle, naturally cooling at room temperature to obtain a light brown solid-liquid mixture, filtering, washing with N, N-dimethylformamide for three times, adding ethanol for ultrasonic washing, transferring to a 120 ℃ oven for drying, and transferring to a 350 ℃ muffle furnace for drying for 5 hours to obtain the activated MIL-53(Al)/CNT composite material.
50mL of 20mg/L p-nitrophenol solution is added into a photocatalytic test tube, 0.01g of MIL-53(Al)/CNT composite material is added, adsorption is carried out in the dark for 30min, and then a light source is turned on for photocatalytic degradation. Samples were taken every 5 minutes and absorbance was measured using an ultraviolet-visible spectrophotometer. The absorbance was recorded as a function of time. 0.01g of used MIL-53(Al)/CNT composite material is dried at low temperature and then put into 50mL of 20mg/L new p-nitrophenol for repeating the photodegradation process. The operation was repeated 5 times, and the time-dependent change in absorbance was recorded and a photodegradation graph was plotted, as shown in FIG. 5. It can be seen that the MIL-53(Al)/CNT sample has very stable performance, and the activity of the sample is not changed obviously after 5 times of cyclic operation.
Example 2
Weighing 1.449g of zirconium tetrachloride and 0.932g of terephthalic acid, respectively ultrasonically dissolving in 30mLN, N-dimethylformamide, adding 0.5g of carbon nanotubes, ultrasonically mixing uniformly, transferring the mixture into a polytetrafluoroethylene lining tank, placing the polytetrafluoroethylene lining tank into a stainless steel reaction kettle, sealing the reaction kettle, and placing the reaction kettle in an oven at 180 ℃ for reaction for 72 hours. And after the reaction is finished, taking the reaction kettle out, naturally cooling at room temperature to obtain a bluish black solid-liquid mixture, filtering, washing with N, N-dimethylformamide for three times, then placing in a 120 ℃ oven for drying, and then placing the sample in a 350 ℃ muffle furnace for drying for 5 hours to obtain the activated UI0-66 (Zr)/CNT composite material.
50mL of 20mg/L p-nitrophenol solution is added into a photocatalytic test tube, 0.01g of UIO-66(Zr)/CNT composite material is added, adsorption is carried out in the dark for 30min, and then a light source is turned on for photocatalytic degradation. Samples were taken every 5 minutes and absorbance was measured using an ultraviolet-visible spectrophotometer. The absorbance was recorded as a function of time. After 0.01g of the used UIO-66(Zr)/CNT composite material is dried at low temperature, the dried material is put into 50mL of 20mg/L p-nitrophenol again for repeating the photodegradation process. The operation was repeated 5 times, and the time-dependent change in absorbance was recorded and a photodegradation graph was plotted, as shown in FIG. 6. It can be seen that the properties of the UIO-66(Zr)/CNT sample are very stable and the activity does not change significantly after 5 cycles.
Claims (5)
1. A preparation method of MOFs/CNT photocatalyst is characterized in that the photocatalyst is synthesized by loading MOFs on carbon nanotubes; the MOFs is MIL-53(Al) or UIO-66 (Zr);
the MIL-53(Al)/CNT composite material is prepared by the following steps:
(1) dissolving aluminum nitrate and terephthalic acid in N, N-dimethylformamide respectively, performing ultrasonic dissolution, and adding a certain amount of multi-walled carbon nanotubes to obtain a mixture;
(2) reacting the mixture for 48-72h at 180-190 ℃;
(3) naturally cooling at room temperature after the reaction is finished to obtain a light brown solid-liquid mixture, filtering, washing for 1-3 times by using N, N-dimethylformamide, adding ethanol, ultrasonically washing, and moving to a 120 ℃ oven for drying;
(4) placing the dried product at 350-650 ℃ and drying for 5-8h to obtain an activated MIL (Al) -53/CNT composite material;
the UIO-66(Zr)/CNT composite material is prepared by the following steps:
weighing zirconium tetrachloride, respectively ultrasonically dissolving terephthalic acid in N, N-dimethylformamide, adding a multi-walled carbon nanotube, and ultrasonically mixing uniformly to obtain a mixture;
secondly, reacting the mixture at 180-190 ℃ for 48-72 h;
taking out the reaction kettle after the reaction is finished, naturally cooling the reaction kettle at room temperature to obtain a blue-black solid-liquid mixture, filtering the mixture, washing the mixture for 1 to 3 times by using N, N-dimethylformamide, and then placing the mixture at 120 ℃ for drying;
and fourthly, placing the dried product into a temperature of 350-650 ℃ for drying for 5-8 hours to obtain the activated UI0-66 (Zr)/CNT composite material.
2. The method of claim 1, wherein in step (1), the solid-to-liquid ratio of the multi-walled carbon nanotubes to the ultrasonically dissolved solution of aluminum nitrate and terephthalic acid in N, N-dimethylformamide is 1-50g/L, the concentration of aluminum nitrate in the ultrasonically dissolved solution of aluminum nitrate and terephthalic acid in N, N-dimethylformamide is 0.024-0.115mol/L, and the concentration of terephthalic acid in the ultrasonically dissolved solution of aluminum nitrate and terephthalic acid in N, N-dimethylformamide is 0.016-0.069 mol/L.
3. The method of claim 1, wherein in the step (2), the mixture is transferred to a polytetrafluoroethylene inner tank, and then placed in a stainless steel hydrothermal reaction kettle, and the reaction kettle is sealed and then placed in an oven at 180-190 ℃ for reaction for 48-72 h.
4. The method for preparing the MOFs/CNT photocatalyst according to claim 1, wherein in the step (r), the solid-to-liquid ratio of the multi-walled carbon nanotube to the ultrasonically dissolved N, N-dimethylformamide solution of zirconium tetrachloride and terephthalic acid is 1-50 g/L; the concentration of zirconium tetrachloride in the ultrasonically dissolved zirconium tetrachloride and terephthalic acid N, N-dimethylformamide solution is 9.56X 10-30.207 mol/L, and the concentration of terephthalic acid is 0.0123-0.187 mol/L.
5. The method of claim 1, wherein the mixture is transferred into a Teflon liner tank, and then placed in a stainless steel hydrothermal reaction kettle, and the reaction kettle is sealed and placed in an oven at 180-190 ℃ for reaction for 48-72 h.
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