CN108855216B - Cadmium sulfide-coated metal organic framework MIL-101(Cr) photocatalytic composite material and preparation method and application thereof - Google Patents
Cadmium sulfide-coated metal organic framework MIL-101(Cr) photocatalytic composite material and preparation method and application thereof Download PDFInfo
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- 239000013178 MIL-101(Cr) Substances 0.000 title claims abstract description 98
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 97
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 68
- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 62
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960003151 mercaptamine Drugs 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 5
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 5
- 239000011636 chromium(III) chloride Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01J31/22—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
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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Abstract
The invention discloses a cadmium sulfide coated metal organic framework MIL-101(Cr) photocatalytic composite material and a preparation method and application thereof, wherein the metal organic framework MIL-101(Cr) is firstly prepared, then impurity removal and activation are carried out on the metal organic framework MIL-101(Cr), and the metal organic framework MIL-101(Cr) is further mixed with mercaptoethylamine, Cd (Ac)2·2H2O and thioacetamide react to obtain the metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide, and the material has good conversion rate and selectivity in the photocatalytic selective reduction of nitro compounds. The preparation method is simple in preparation process and mild in reaction condition, and has important reference function and practical application value for optimizing the microstructure of the composite material and expanding the application of the composite material in selective organic conversion reaction.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a cadmium sulfide coated metal organic framework MIL-101(Cr) photocatalytic composite material and a preparation method and application thereof.
Background
The photocatalysis technology is a green technology, and can be used for treating environmental pollution such as water, air, soil and the like on one hand; on the other hand, the method can also be used for hydrogen production by photolysis of water, carbon dioxide reduction, organic conversion reaction and the like. With the continuous development of the technology, the research of applying the photocatalytic technology to the field of green organic synthesis is receiving much attention. In recent years, metal organic framework materials have become potential heterogeneous photocatalyst materials due to the characteristics of large specific surface area, abundant topological structures, adjustable energy band structures, tailorability, designability, easy modulation and the like. Cadmium sulfide has a suitable energy band structure and is an excellent visible light semiconductor photocatalytic material. Therefore, the metal organic framework MIL-101(Cr) is combined with cadmium sulfide, the advantages of the metal organic framework MIL-101(Cr) and the cadmium sulfide are fully exerted, and the metal organic framework MIL-101(Cr) has important scientific research significance in the fields of material synthesis and photocatalysis. However, because the synthesis conditions of the metal organic framework material and the cadmium sulfide are not matched, the traditional combination mode has the problems that the cadmium sulfide particles are loaded on the metal organic framework unevenly, the particle size and the loading quantity cannot be controlled, and the like. Based on the method, a new preparation method is developed, the metal organic framework-cadmium sulfide composite material with good interface effect is constructed, and the method has wide application prospect in fully exerting the advantages of the metal organic framework-cadmium sulfide composite material and being used for photocatalytic selective organic synthesis reaction.
Disclosure of Invention
The invention aims to provide a metal organic framework MIL-101(Cr) photocatalytic composite material coated by cadmium sulfide, a preparation method thereof and application of the photocatalytic composite material in selective organic conversion reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide comprises the following steps:
(1) preparation of metal organic framework MIL-101 (Cr): CrCl was added to 25 mL of Teflon liner3·6H2O, terephthalic acid and deionized water, and carrying out ultrasonic treatment for 15-25 min; then placing the polytetrafluoroethylene lining in an oven at the temperature of 200-220 ℃ for reaction for 24-28 h, centrifuging, taking the precipitate and drying to obtain the metal organic frameworkMIL-101(Cr)；
(2) Removing impurities and activating a metal organic framework MIL-101 (Cr): dispersing metal organic framework MIL-101(Cr) in absolute ethyl alcohol, refluxing for 20-24 h at 75-85 ℃, and then washing and drying the metal organic framework MIL-101(Cr) by using the absolute ethyl alcohol;
(3) preparing a metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide: dispersing the dried metal organic framework MIL-101(Cr) in absolute ethyl alcohol, adding mercaptoethylamine and stirring for 5-10 min, and then reacting the mixture at 80-85 ℃ for 2-2.5 h; adding Cd (Ac)2·2H2Continuously reacting for 2-2.5 h; adding thioacetamide to continue reacting for 12-14 h; and centrifuging, washing and drying the product to obtain the cadmium sulfide coated metal organic framework MIL-101(Cr) photocatalytic composite material.
In the step (1), the CrCl3·6H2The mass ratio of O to terephthalic acid was 266.6: 160-170, preferably 266.6: 166.6.
In the step (1), the centrifugal operation is specifically as follows: the product is firstly centrifuged for 3-4 min at the rotating speed of 3000-3500 r/min, the filtrate is taken and centrifuged for 2 times at the rotating speed of 3000-3500 r/min, then the filtrate is centrifuged for 5-6 min at the rotating speed of 8000-8500 r/min, and the precipitates obtained by each centrifugation are combined.
In the step (2), the drying is carried out in an oven with the temperature of 110-130 ℃ for 10-14 h.
In the step (3), the metal organic framework MIL-101(Cr), mercaptoethylamine, Cd (Ac)2·2H2The mass ratio of the O-thioacetamide is 40: 35-45: 40-50: 10-15, preferably 40: 44.2: 12.4.
In the step (3), the dosage ratio of the metal organic framework MIL-101(Cr) to the ethanol is 40 mg: 20-30 mL.
In the step (3), the washing is carried out by sequentially adopting absolute ethyl alcohol and deionized water, and the drying temperature is 60-65 ℃.
In the metal organic framework MIL-101(Cr) photocatalytic composite material coated by cadmium sulfide prepared by the invention, the cadmium sulfide can be uniformly coated on the surface of the metal organic framework MIL-101(Cr), and the material can be applied to photocatalytic selective organic conversion reaction and used for photocatalytic selective reduction of nitro compounds, and the specific steps are as follows:
(1) placing a certain amount of a metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by a paranitroaniline solution, ammonium formate and cadmium sulfide in a reaction bottle, introducing nitrogen (60 mL/min), and adsorbing for a certain time in a dark state to ensure that the paranitroaniline solution is in adsorption balance on the surface of a photocatalyst;
(2) under the protection of nitrogen, visible light (lambda is more than 420 nm) is irradiated to the system, a proper amount of reaction liquid is taken at regular intervals, after the reaction is finished, the taken reaction liquid is centrifuged (10000 rpm/min), and an ultraviolet visible spectrophotometer is adopted to analyze supernatant.
The invention has the following remarkable advantages:
(1) the metal organic framework MIL-101(Cr) photocatalytic composite material coated by the cadmium sulfide is uniform in size, and the cadmium sulfide is better coated on the surface of the metal organic framework MIL-101 (Cr).
(2) The metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide has high photocatalytic activity, low manufacturing cost and simple production process.
Drawings
FIG. 1 is an XRD pattern of a cadmium sulfide coated metal organic framework MIL-101(Cr) photocatalytic composite material.
FIG. 2 is a DRS diagram of a cadmium sulfide encapsulated metal organic framework MIL-101(Cr) photocatalytic composite material.
Fig. 3 is an SEM image of a cadmium sulfide coated metal organic framework MIL-101(Cr) photocatalytic composite material.
FIG. 4 is a graph of the catalytic activity of cadmium sulfide coated metal organic framework MIL-101(Cr) photocatalytic composite material and cadmium sulfide.
Detailed Description
A preparation method of a metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide comprises the following steps:
(1) preparation of metalsOrganic framework MIL-101 (Cr): CrCl was added to 25 mL of Teflon liner3·6H2O, terephthalic acid and deionized water, and carrying out ultrasonic treatment for 15-25 min; then placing the polytetrafluoroethylene lining in an oven at the temperature of 200-;
wherein, CrCl3·6H2The mass ratio of O to terephthalic acid was 266.6: 160-170, preferably 266.6: 166.6;
(2) removing impurities and activating a metal organic framework MIL-101 (Cr): dispersing metal organic framework MIL-101(Cr) in absolute ethyl alcohol, refluxing for 20-24 h at 75-85 ℃, and then washing and drying the metal organic framework MIL-101(Cr) by using the absolute ethyl alcohol;
(3) preparing a metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide: dispersing the dried metal organic framework MIL-101(Cr) in absolute ethyl alcohol, adding mercaptoethylamine and stirring for 5-10 min, and then reacting the mixture at 80-85 ℃ for 2-2.5 h; adding Cd (Ac)2·2H2Continuously reacting for 2-2.5 h; adding thioacetamide to continue reacting for 12-14 h; centrifuging the product, washing the precipitate with absolute ethyl alcohol and deionized water in sequence, and drying at 60-65 ℃ to obtain the metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide;
wherein the metal organic framework MIL-101(Cr), mercaptoethylamine, Cd (Ac)2·2H2The mass ratio of the O-thioacetamide is 40: 35-45: 40-50: 10-15, preferably 40: 44.2: 12.4;
the dosage ratio of the metal organic framework MIL-101(Cr) to the ethanol is 40 mg: 20-30 mL.
Example 1
Preparation of metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide
(1) Preparation of metal organic framework MIL-101 (Cr): 266.6 mgCrCl3·6H2Adding O into 25 mL of polytetrafluoroethylene lining; adding 166.6 mg of terephthalic acid, adding 7.2 mL of deionized water, and performing ultrasonic treatment for 15 min; reacting for 24 hours in an oven at 210 ℃; centrifuging at 3000 rpm/min for 3min, centrifuging the filtrate for 2 times, centrifuging at 8000 rpm/min for 5min, and oven drying the precipitate.
(2) Removing impurities and activating a metal organic framework MIL-101 (Cr): dispersing a certain amount of MIL-101(Cr) in 200 mL of absolute ethyl alcohol, and refluxing for 24 h at 80 ℃; washing the product with absolute ethyl alcohol, and vacuum-drying in a vacuum oven at 120 ℃ for 12 h;
(3) preparing a metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide: dispersing 40 mg of vacuum-dried MIL-101(Cr) in 20 mL of absolute ethanol, adding 40 mg of mercaptoethylamine, stirring for 5min, and reacting at 80 ℃ for 2 h; 44.2 mg Cd (Ac) was added2·2H2Continuously reacting for 2 hours; adding 12.4 mg thioacetamide to continue reacting for 12 h; and centrifuging the product, respectively washing the precipitate with absolute ethyl alcohol and deionized water, and drying at 60 ℃ to obtain the metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide.
Fig. 1-3 are XRD, DRS and SEM images, respectively, of a cadmium sulfide coated metal organic framework MIL-101(Cr) photocatalytic composite material.
Bis, photocatalytic selective reduction of nitro compounds
The metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide is dispersed in 20 mL of p-nitroaniline solution with the concentration of 10 ppm, dark adsorption is carried out for 0.5 h, the metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide can be placed under visible light (lambda is more than 420 nm) to be irradiated under the condition of introducing nitrogen (60 mL/min), and 98% of p-nitroaniline can be converted into p-phenylenediamine within 8 min.
Comparative example 1
Preparation of cadmium sulfide
Adding 40 mg mercaptoethylamine into 20 mL of absolute ethanol, and stirring for 5 min; 44.2 mg Cd (Ac) was added2·2H2O, reacting for 2 hours at 80 ℃; 12.4 mg of thioacetamide was added to continue the reaction12 h; centrifuging the product, and washing the precipitate with anhydrous ethanol and deionized water respectively; drying at 60 ℃ to obtain pure cadmium sulfide.
Bis, photocatalytic selective reduction of nitro compounds
The cadmium sulfide powder is dispersed in 20 mL of 10 ppm p-nitroaniline solution, dark adsorption is carried out for 0.5 h, the solution is placed under visible light (lambda is more than 420 nm) for illumination under the condition of introducing nitrogen (60 mL/min), and the cadmium sulfide powder material can only convert 46 percent of p-nitroaniline into p-phenylenediamine within 8 min.
FIG. 4 is a graph of the catalytic activity of cadmium sulfide coated metal organic framework MIL-101(Cr) photocatalytic composite material and cadmium sulfide. From example 1 and comparative example 1, it can be seen that the metal organic framework MIL-101(Cr) photocatalytic composite material coated with cadmium sulfide has higher photocatalytic performance than that of blank cadmium sulfide, which indicates that the metal organic framework MIL-101(Cr) photocatalytic composite material coated with cadmium sulfide can better exert excellent performance and further exhibit better photocatalytic activity.
Example 2
A preparation method of a metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide comprises the following steps:
(1) preparation of metal organic framework MIL-101 (Cr): 266.6 mg CrCl3·6H2Adding O into 25 mL of polytetrafluoroethylene lining; adding 160 mg of terephthalic acid, adding 7 mL of deionized water, and performing ultrasonic treatment for 15 min; then placing the polytetrafluoroethylene lining in an oven at 200 ℃ for reaction for 28 h, centrifuging the product for 4 min at the rotating speed of 3000 r/min, taking the filtrate, centrifuging the filtrate for 2 times at the rotating speed of 3000 r/min again, centrifuging the filtrate for 6 min at the rotating speed of 8000 r/min, combining precipitates obtained by each centrifugation, and drying to obtain a metal organic framework MIL-101 (Cr);
(2) removing impurities and activating a metal organic framework MIL-101 (Cr): dispersing metal organic framework MIL-101(Cr) in absolute ethyl alcohol, refluxing for 24 hours at 75 ℃, then washing and drying the metal organic framework MIL-101(Cr) by the absolute ethyl alcohol;
(3) preparing a metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide: drying 40 mg of the metal organic frameDispersing the frame MIL-101(Cr) in 20 mL of absolute ethanol, adding 35 mg of mercaptoethylamine, stirring for 5min, and reacting the mixture at 80 ℃ for 2.5 h; then 40 mg Cd (Ac)2·2H2Continuously reacting for 2.5 h; then 10 mg of thioacetamide is added to continue the reaction for 14 h; and then centrifuging the product, sequentially washing the precipitate with absolute ethyl alcohol and deionized water, and drying at 60 ℃ to obtain the metal organic framework MIL-101(Cr) photocatalytic composite material coated with cadmium sulfide.
Example 3
A preparation method of a metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide comprises the following steps:
(1) preparation of metal organic framework MIL-101 (Cr): 266.6 mg CrCl3·6H2Adding O into 25 mL of polytetrafluoroethylene lining; adding 170 mg of terephthalic acid, adding 7.5 mL of deionized water, and performing ultrasonic treatment for 25 min; then placing the polytetrafluoroethylene lining in an oven at 220 ℃ for reaction for 24 h, firstly centrifuging the product for 3min at the rotating speed of 3500 r/min, taking the filtrate, centrifuging the filtrate for 2 times at the rotating speed of 3500 r/min, then centrifuging the filtrate for 5min at the rotating speed of 8500 r/min, combining precipitates obtained by each centrifugation, and drying to obtain a metal organic framework MIL-101 (Cr);
(2) removing impurities and activating a metal organic framework MIL-101 (Cr): dispersing metal organic framework MIL-101(Cr) in absolute ethyl alcohol, refluxing for 20 hours at 85 ℃, and then washing and drying the metal organic framework MIL-101(Cr) by using the absolute ethyl alcohol;
(3) preparing a metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide: dispersing 40 mg of dried metal organic framework MIL-101(Cr) in 30mL of absolute ethyl alcohol, adding 45 mg of mercaptoethylamine, stirring for 10min, and reacting the mixture at 85 ℃ for 2 h; then 50 mg Cd (Ac)2·2H2Continuously reacting for 2 hours; adding 15 mg thioacetamide and continuing to react for 12 h; and then centrifuging the product, sequentially washing the precipitate with absolute ethyl alcohol and deionized water, and drying at 65 ℃ to obtain the metal organic framework MIL-101(Cr) photocatalytic composite material coated with cadmium sulfide.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. A preparation method of a metal organic framework MIL-101(Cr) photocatalytic composite material coated by cadmium sulfide is characterized by comprising the following steps: which comprises the following steps:
(1) preparation of metal organic framework MIL-101 (Cr): adding CrCl into the polytetrafluoroethylene lining3·6H2O, terephthalic acid and deionized water, and carrying out ultrasonic treatment for 15-25 min; then placing the polytetrafluoroethylene lining in an oven at the temperature of 200-220 ℃ for reaction for 24-28 h, centrifuging the product, taking the precipitate and drying to obtain a metal organic framework MIL-101 (Cr);
(2) removing impurities and activating a metal organic framework MIL-101 (Cr): dispersing metal organic framework MIL-101(Cr) in absolute ethyl alcohol, refluxing for 20-24 h at 75-85 ℃, and then washing and drying the metal organic framework MIL-101(Cr) by using the absolute ethyl alcohol;
(3) preparing a metal organic framework MIL-101(Cr) photocatalytic composite material wrapped by cadmium sulfide: dispersing the dried metal organic framework MIL-101(Cr) in absolute ethyl alcohol, adding mercaptoethylamine and stirring for 5-10 min, and then reacting the mixture at 80-85 ℃ for 2-2.5 h; adding Cd (Ac)2·2H2Continuously reacting for 2-2.5 h; adding thioacetamide to continue reacting for 12-14 h; and centrifuging, washing and drying the product to obtain the cadmium sulfide coated metal organic framework MIL-101(Cr) photocatalytic composite material.
2. The method for preparing the metal organic framework MIL-101(Cr) photocatalytic composite material coated by cadmium sulfide as claimed in claim 1, wherein the metal organic framework MIL-101(Cr) photocatalytic composite material comprises the following steps: in the step (1), the CrCl3·6H2The mass ratio of O to terephthalic acid was 266.6: 160-170.
3. The method for preparing the metal organic framework MIL-101(Cr) photocatalytic composite material coated by cadmium sulfide as claimed in claim 1, wherein the metal organic framework MIL-101(Cr) photocatalytic composite material comprises the following steps: in the step (1), the centrifugal operation is specifically as follows: the product is firstly centrifuged for 3-4 min at the rotating speed of 3000-3500 r/min, the filtrate is taken and centrifuged for 2 times at the rotating speed of 3000-3500 r/min, then the filtrate is centrifuged for 5-6 min at the rotating speed of 8000-8500 r/min, and the precipitates obtained by each centrifugation are combined.
4. The method for preparing the metal organic framework MIL-101(Cr) photocatalytic composite material coated by cadmium sulfide as claimed in claim 1, wherein the metal organic framework MIL-101(Cr) photocatalytic composite material comprises the following steps: in the step (2), the drying is carried out in an oven with the temperature of 110-130 ℃ for 10-14 h.
5. The method for preparing the metal organic framework MIL-101(Cr) photocatalytic composite material coated by cadmium sulfide as claimed in claim 1, wherein the metal organic framework MIL-101(Cr) photocatalytic composite material comprises the following steps: in the step (3), the metal organic framework MIL-101(Cr), mercaptoethylamine, Cd (Ac)2·2H2The mass ratio of O to thioacetamide is 40: 35-45: 40-50: 10-15.
6. The method for preparing the metal organic framework MIL-101(Cr) photocatalytic composite material coated by cadmium sulfide as claimed in claim 1, wherein the metal organic framework MIL-101(Cr) photocatalytic composite material comprises the following steps: in the step (3), the dosage ratio of the metal organic framework MIL-101(Cr) to the ethanol is 40 mg: 20-30 mL.
7. The method for preparing the metal organic framework MIL-101(Cr) photocatalytic composite material coated by cadmium sulfide as claimed in claim 1, wherein the metal organic framework MIL-101(Cr) photocatalytic composite material comprises the following steps: in the step (3), the washing is carried out by sequentially adopting absolute ethyl alcohol and deionized water, and the drying temperature is 60-65 ℃.
8. The metal organic framework MIL-101(Cr) photocatalytic composite material coated by cadmium sulfide is obtained according to any preparation method of claims 1 to 7.
9. Use of a cadmium sulphide coated metal organic framework MIL-101(Cr) photocatalytic composite material according to claim 8, characterized in that: the photocatalytic composite material is used for photocatalytic selective reduction of nitro compounds.
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