CN115477763A - Method for constructing functional material of Cu and Ni bimetal position by utilizing metal organic framework MOF-303 - Google Patents
Method for constructing functional material of Cu and Ni bimetal position by utilizing metal organic framework MOF-303 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 19
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
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- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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
- 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
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J31/2226—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
-
- B01J35/39—
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
-
- 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
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Abstract
The invention discloses a method for constructing a functional material of Cu and Ni bimetal positions by using a metal organic framework MOF-303, belonging to the preparation of the functional material and the photocatalysis of CO 2 The technical field of reduction. The MOF-303 carrier is synthesized by a simple one-step method, and the coordinated unsaturated N locus in the MOF-303 carrier structure with large specific surface area is utilized to chelate Cu and Ni bimetal, so that the MOF new functional material modified by bimetal CuNi can be controllably prepared; and Cu 2+ 、Ni 2+ The synergistic effect of the bimetallic ions prolongs the charge life and promotes CO 2 The MOF-303-CuNi functional material photocatalytically reduces CO 2 Activity ofHigh; high catalytic activity can be still maintained after multiple circulation experiments, and the stability is good.
Description
Technical Field
The invention belongs to the field of functional material preparation and photocatalytic CO 2 The technical field of reduction, in particular to a functional material for forming bimetal positions by chelating Cu and Ni bimetal through the double pyrazole positions in a metal organic framework MOF-303 and a preparation method and application thereof.
Background
With the rapid development of industry and the mass combustion of fossil fuels, CO 2 The emission amount is increased year by year, global temperature rise and climate change are caused by greenhouse effect, and carbon emission reduction and temperature control are not slow at all. Introducing CO 2 Selective reduction to fuel is an effective strategy that helps mitigate environmental and energy issues with the strategic goals of "carbon peak-to-peak, carbon neutralization". Photocatalytic CO 2 The reduction process utilizes solar energy and photocatalyst to simulate natural photosynthesis to convert CO into CO 2 And H 2 And performing catalytic conversion on the O. The technology can not only reduce CO 2 Can produce fuel and high value-added chemicals, realize CO 2 And (5) resource utilization.
In recent years, bimetallic sites have been used for photocatalytic reduction of CO 2 The advantages of (a) have received attention from a number of researchers. Researches show that the synergistic effect of double metal sites can promote CO 2 Molecular adsorption, stabilization of key intermediate species, contribution to CO 2 The photocatalytic conversion efficiency and the product selectivity are obviously improved. Thus, the construction of bimetallic sites in catalytic materials for photocatalytic reduction of CO 2 Is an effective strategy. However, bimetallic materials are generally unstable and, therefore, a suitable support must be selected as the site-stable metal.
The Metal Organic Frameworks (MOFs) are ideal catalytic material carriers due to the characteristics of large specific surface area, high porosity, coordination unsaturated metal sites and the like. Wherein the MOF-303 with the xhh topological structure is formed by alternating cis-trans units AlO 6 Octahedral, connected by 1-H-3, 5-pyrazoledicarboxylic acid, with the presence of pyrazole functions adjacent and directed towards each other in the arrangement. Adjacent N atom pairs of pyrazole dicarboxylic acid in the MOF-303 structure have lone pair electrons, can effectively and accurately chelate metal ions, and is used for constructing doubleIdeal material for metal sites.
Disclosure of Invention
Aiming at the problems in the prior art, the first technical problem to be solved by the invention is to provide a method for constructing a functional material with double metal positions by utilizing double metal of double pyrazole position chelated Cu and Ni in a metal organic framework MOF-303; the second technical problem to be solved by the invention is to provide the MOF-303-CuNi functional material prepared by the method; the third technical problem to be solved by the invention is to provide the MOF-303-CuNi functional material for the photocatalytic reduction of CO 2 The use of (1).
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for constructing a functional material with Cu and Ni bimetallic sites by using a metal organic framework MOF-303 comprises the following steps:
1) Dissolving 1-H-3, 5-pyrazole dicarboxylic acid monohydrate in NaOH aqueous solution, stirring until the solution is clear, then adding aluminum chloride hexahydrate into the solution, stirring until the solution is completely dissolved, heating in an oil bath, filtering after complete reaction to obtain precipitate, washing the precipitate for multiple times by deionized water and methanol respectively, and drying in vacuum to obtain an MOF-303 carrier; the molar ratio of the 1-H-3, 5-pyrazole dicarboxylic acid monohydrate to the aluminum chloride hexahydrate is 1: 1;
2) Activating the MOF-303 carrier prepared in the step 1) for 12 hours at 150 ℃, and weighing the activated MOF-303 carrier and Cu (NO) according to the dosage ratio of 2: 1 3 ) 2 And Ni (NO) 3 ) 2 Adding acetonitrile solution, and stirring until Cu (NO) 3 ) 2 、Ni(NO 3 ) 2 And (3) completely dissolving, placing in a constant-temperature preheating oven for reaction, naturally cooling to room temperature after the reaction is finished, filtering to obtain a precipitate, washing the precipitate with acetonitrile for multiple times until the supernatant is colorless, and drying in vacuum to obtain the MOF-303-CuNi functional material.
Further, in the step 1), the temperature of the oil bath is 100 ℃, and the heating time of the oil bath is 24 hours.
Further, in the step 2), the precipitate is washed 3 to 5 times by deionized water and methanol respectively.
Further, in the step 1), the temperature of vacuum drying is 50-60 ℃, and the time of vacuum drying is 6 hours.
Further, in the step 2), the temperature of the constant-temperature preheating oven is 70 ℃, and the reaction time is 48 hours.
Further, in the step 2), the precipitate is washed for 3 to 5 times by acetonitrile until the supernatant is colorless.
Further, in the step 2), the temperature of vacuum drying is 50-60 ℃, and the time of vacuum drying is 2 hours.
The MOF-303-CuNi functional material prepared by the method.
The prepared MOF-303-CuNi functional material is used for photocatalytic reduction of CO 2 The use of (1).
Compared with the prior art, the invention has the beneficial effects that:
(1) The MOF-303 carrier is synthesized by a simple one-step method, and the coordinated unsaturated N locus in the MOF-303 carrier structure with large specific surface area is utilized to chelate Cu and Ni bimetal, so that the MOF new functional material modified by bimetal CuNi can be controllably prepared;
(2) The MOF-303-CuNi functional material prepared by the invention is Cu 2+ 、Ni 2+ Synergistic effect of bimetallic ions to prolong charge life and promote CO 2 The MOF-303-CuNi functional material carries out photocatalytic reduction on CO 2 The activity is high, and compared with the MOF-303 carrier, the performance is improved by about 3 times; high catalytic activity can be still maintained after multiple circulation experiments, and the stability is good.
Drawings
FIG. 1 is an XRD spectrum of the MOF-303-CuNi functional material prepared by the invention;
FIG. 2 is an FTIR spectrum of the MOF-303-CuNi functional material prepared by the invention;
FIG. 3 is an SEM image of an MOF-303 support and an MOF-303-CuNi functional material prepared by the invention; in the figure, a and b are SEM images of MOF-303, c and d are SEM images of MOF-303-CuNi functional materials;
FIG. 4 is a UV-vis DRS spectrum of MOF-303 support and MOF-303-CuNi functional material prepared by the present invention;
FIG. 5 shows the MOF-303-CuNi functional material prepared by the invention and the MOF-303 carrier photocatalytic reduction CO 2 An activity comparison plot;
FIG. 6 is a diagram of the cycle stability of the MOF-303-CuNi functional material prepared by the present invention.
Detailed Description
The invention is further described with reference to specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention. In the following examples, unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
EXAMPLE 1 preparation of MOF-303 catalyst
Weighing 2.60g of NaOH and dissolving in 750mL of deionized water; weighing 7.50g of 1-H-3, 5-pyrazole dicarboxylic acid monohydrate and dissolving in NaOH solution; the resulting mixture was stirred until the solution was clear. 10.4g of AlCl are then added to the solution 3 ·6H 2 And O, stirring until the materials are completely dissolved. The mixture was heated in an oil bath at 100 ℃ for 24h. The resulting precipitate was filtered and washed three times with deionized water and methanol, respectively. And (3) carrying out vacuum drying for 6h in a vacuum drying oven at 60 ℃ to obtain the MOF-303.
EXAMPLE 2 preparation of MOF-303-CuNi catalyst
And (3) putting the prepared MOF-303 into a vacuum drying oven at 150 ℃ for activation for 12h. 100mg of the activated sample was weighed and transferred to a 10mL screw-stoppered glass bottle, and 50mg of Cu (NO) was weighed 3 ) 2 And Ni (NO) 3 ) 2 Transfer to glass vial. 10mL of acetonitrile was added to the flask and stirred until the metal salt was completely dissolved. The glass bottles were placed in a pre-heat oven at 70 ℃ for 48h. And (3) collecting the precipitate, washing the precipitate for three times by using an acetonitrile solution until the supernatant is colorless, and performing vacuum drying for 2 hours at the temperature of 60 ℃ to obtain the MOF-303-CuNi catalyst.
FIG. 1 is an XRD pattern of MOF-303 and MOF-303-CuNi. As can be seen from the figure, the XRD diffraction peak of the MOF-303 is not obviously changed after the Cu and the Ni are chelated, which indicates that the crystal structure of the MOF-303 material modified by the Cu and the Ni bimetal does not change.
FIG. 2 is an FT-IR spectrum of MOF-303 and MOF-303-CuNi. As can be seen from the figure, 1002cm -1 The peak intensity is obviously reduced after the coordination unsaturated N site chelates Cu and Ni; at the same time at 435cm -1 A vibrational peak attributable to coordination of N and metal ions appears. The change of the FT-IR oscillation peak proves that Cu and Ni are chelated in the MOF-303 material through N coordination on pyrazole.
FIGS. 3a and 3b are SEM (scanning electron microscope) photographs of MOF-303, and FIGS. 3c and 3d are SEM photographs of MOF-303-CuNi, and we can see that MOF-303 and MOF-303-CuNi are both sheet-shaped structures and have no change in morphology before and after adsorption.
FIG. 4 is a UV-vis DRS map of MOF-303 and MOF-303-CuNi. As can be seen from the figure, the absorption capacity of MOF-303-CuNi is improved compared with that of MOF-303, and the absorption range is expanded to the visible light region. The change in light absorption further demonstrates the successful chelation of the Cu and Ni bimetal in the MOF-303 material. Meanwhile, the MOF-303-CuNi material can effectively improve the utilization rate of light and generate more photo-generated charges for photocatalytic reaction.
Tables 1 and 2 are the results of inductively coupled plasma-optical emission spectroscopy (ICP-OES) and BET specific surface area measurements of MOF-303 and MOF-303-CuNi, respectively. The result shows that the MOF-303-CuNi contains Cu and Ni ions, and the bimetal Cu and Ni is successfully chelated in the MOF-303 material. Meanwhile, the specific surface area of the MOF-303-CuNi is greatly reduced compared with that of the MOF-303, and the fact that the adsorption of the MOF-303-CuNi is located in an MOF-303 pore channel is proved.
TABLE 1 ICP-OES results for samples prepared
Note: the unit is mg/g.
TABLE 2 BET specific surface area test results of the prepared samples
Note: the unit is (m) 2 /g)。
EXAMPLE 3 preparation of UiO-66-NH 2 -CuNi catalyst
362mg of 2-amino terephthalic acid was dissolved in 20mL of N, N-dimethylformamide and formic acid (v) 1 ∶v 2 = 9: 1) mixed solution; 233mg of zirconium chloride was weighed and dissolved in the above mixed solution, and the above mixed solution was transferred to a 20mL screw-stoppered glass bottle. Putting the mixed solution in a 120 ℃ oven for 24h, filtering the obtained precipitate, washing the precipitate with N, N-dimethylformamide and methanol solution for three times respectively to obtain UiO-66-NH 2 And (3) a solid.
The above-mentioned UiO-66-NH is reacted with 2 The sample was placed in a vacuum oven and activated at 120 ℃ for 12h. 100mg of the activated sample is weighed and transferred to a 10mL screw-stoppered glass bottle, and 50mg of Cu (NO) is added 3 ) 2 And Ni (NO) 3 ) 2 Into a glass bottle. 10mL of acetonitrile was added and stirred until the metal salt was completely dissolved. The glass bottles were placed in a pre-heat oven at 70 ℃ for 48h. Collecting the precipitate, washing the precipitate with acetonitrile solution for three times until the supernatant is colorless, and vacuum drying at 60 deg.C for 2h to obtain UiO-66-NH 2 -a CuNi catalyst.
Example 4 MOF-303-CuNi functional Material photocatalytic CO 2 Reduction Property
Photocatalytic reduction of Co 2 The reaction tests were carried out in a closed reactor. 10mg of catalyst was weighed and uniformly dispersed in a quartz sand plate reactor having a diameter of 4.2cm, placed in a 100mL stainless steel reactor, and covered with a stainless steel lid having a quartz open window having a diameter of 4.5 cm. High purity CO of 0.4MPa 2 Introducing gas into a reactor, opening a 280W xenon lamp for 4h of photocatalytic reaction, detecting and analyzing products every 2h by using an online gas chromatography GC-7920, and calculating the yield of CO products according to the following formula:
in the formula A t Is the peak area of CO at a certain time, A CO And [ CO ]] s Peak area and concentration (ppm) of CO standard gas, respectively. P, V and T are respectively the pressure (Pa) and the volume (m) inside the reactor 3 ) Temperature (K). R represents a universal gas constant. m is the mass (g) of the photocatalyst.
FIG. 5 is a drawing of MOF-303, MOF-303-CuNi, and the conventional photocatalytic MOF-UiO-66-NH 2 Reduction of CO by CuNi under full-spectrum irradiation 2 Catalytic performance diagram of (a). Compared with MOF-303, the MOF-303-CuNi has more excellent photocatalytic CO 2 Reducing capability, with most common photocatalytic MOF-UiO-66-NH 2 UiO-66-NH loaded with Cu and Ni bimetal 2 Compared with CuNi, MOF-303-CuNi has more excellent photocatalytic CO 2 Reduction performance. FIG. 6 is a photo-reduction C0 of MOF-303-CuNi 2 Activity profile of the cycle experiment. As can be seen from the figure, MOF-303-CuNi has good reaction stability.
Claims (9)
1. A method for constructing a functional material with Cu and Ni bimetallic sites by using a metal organic framework MOF-303 is characterized by comprising the following steps:
1) Dissolving 1-H-3, 5-pyrazole dicarboxylic acid monohydrate in NaOH aqueous solution, stirring until the solution is clear, then adding aluminum chloride hexahydrate into the solution, stirring until the solution is completely dissolved, heating in an oil bath, filtering after complete reaction to obtain precipitates, respectively washing the precipitates for multiple times by deionized water and methanol, and drying in vacuum to obtain an MOF-303 carrier; the molar ratio of 1-H-3, 5-pyrazole dicarboxylic acid monohydrate to aluminum chloride hexahydrate is 1: 1;
2) Activating the MOF-303 carrier prepared in the step 1) for 12 hours at the temperature of 150 ℃, and weighing the activated MOF-303 carrier and Cu (NO) according to the dosage ratio of 2: 1 3 ) 2 And Ni (NO) 3 ) 2 Adding acetonitrile solution, and stirring until Cu (NO) 3 ) 2 、Ni(NO 3 ) 2 Completely dissolving, placing in a constant-temperature preheating oven for reaction, and standingAnd naturally cooling to room temperature after the reaction is finished, filtering to obtain a precipitate, washing the precipitate with acetonitrile for multiple times until the supernatant is colorless, and drying in vacuum to obtain the MOF-303-CuNi functional material.
2. The method for constructing the functional material with the bimetallic position of Cu and Ni by using the metal organic framework MOF-303 as claimed in claim 1, wherein in the step 1), the temperature of the oil bath is 100 ℃, and the heating time of the oil bath is 24h.
3. The method for constructing the functional material with the bimetallic position of Cu and Ni by using the metal organic framework MOF-303 as claimed in claim 1, wherein in the step 2), the precipitate is washed 3-5 times by deionized water and methanol respectively.
4. The method for constructing the functional material with the Cu and Ni bimetal sites by using the metal organic framework MOF-303 as claimed in claim 1, wherein in the step 1), the temperature for vacuum drying is 50-60 ℃ and the time for vacuum drying is 6h.
5. The method for constructing the functional material with the Cu and Ni bimetal sites by using the metal organic framework MOF-303 according to claim 1, wherein in the step 2), the temperature of the constant-temperature preheating oven is 70 ℃, and the reaction time is 48h.
6. The method for constructing the functional material with the Cu and Ni bimetal sites by using the metal organic framework MOF-303 as claimed in claim 1, wherein in the step 2), the precipitate is washed 3-5 times by acetonitrile until the supernatant is colorless.
7. The method for constructing the functional material with the Cu and Ni bimetal sites by using the metal organic framework MOF-303 as claimed in claim 1, wherein in the step 2), the temperature for vacuum drying is 50-60 ℃, and the time for vacuum drying is 2h.
8. A MOF-303-CuNi functional material prepared by the method of any one of claims 1 to 7.
9. The MOF-303-CuNi functional material of claim 8 in photocatalytic reduction of CO 2 The use of (1).
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| WO2017210874A1 (en) * | 2016-06-08 | 2017-12-14 | Xia, Ling | Imperfect mofs (imofs) material, preparation and use in catalysis, sorption and separation |
| CN111054443A (en) * | 2019-12-26 | 2020-04-24 | 华南理工大学 | Zirconium-based MOF catalyst loaded with double active sites and preparation method and application thereof |
| CN114768878A (en) * | 2022-05-07 | 2022-07-22 | 中国科学技术大学 | Preparation method of bimetallic conductive MOF catalyst |
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| WO2017210874A1 (en) * | 2016-06-08 | 2017-12-14 | Xia, Ling | Imperfect mofs (imofs) material, preparation and use in catalysis, sorption and separation |
| CN111054443A (en) * | 2019-12-26 | 2020-04-24 | 华南理工大学 | Zirconium-based MOF catalyst loaded with double active sites and preparation method and application thereof |
| CN114768878A (en) * | 2022-05-07 | 2022-07-22 | 中国科学技术大学 | Preparation method of bimetallic conductive MOF catalyst |
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| CN117143350A (en) * | 2023-08-29 | 2023-12-01 | 广东工业大学 | Dissimilar metal organic molecular cage material, preparation method and application thereof, and preparation method for oxidizing thioether into sulfone |
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