CN115477763B - Method for constructing Cu and Ni bimetallic site functional material by utilizing metal organic framework MOF-303 - Google Patents
Method for constructing Cu and Ni bimetallic site functional material by utilizing metal organic framework MOF-303 Download PDFInfo
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- 229910052802 copper Inorganic materials 0.000 title claims description 20
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- 229910003336 CuNi Inorganic materials 0.000 claims abstract description 42
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- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims description 4
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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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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—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
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- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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Abstract
The invention discloses a method for constructing a Cu-Ni bimetallic site functional material by utilizing a metal-organic framework MOF-303, belonging to the preparation of functional materials and photocatalysis of CO 2 Technical field of reduction. According to the preparation method, raw materials are low, sources are wide, environment is friendly, the preparation process is simple, and the MOF-303-CuNi functional material can be prepared on a large scale; and Cu is 2+ 、Ni 2+ Synergistic effect of bimetallic ions prolongs charge life and promotes CO 2 Is adsorbed and activated, and the functional material of MOF-303-CuNi is used for photocatalytic reduction of CO 2 The activity is high; can still keep higher catalytic activity after multiple circulating experiments, and has good stability.
Description
Technical Field
The invention belongs to the preparation of functional materials and the photocatalysis of CO 2 The technical field of reduction, in particular to a functional material for forming a bimetal site by chelating Cu and Ni bimetal at a double pyrazole site in a metal organic framework MOF-303, and a preparation method and application thereof.
Background
With the rapid development of industry and the massive combustion of fossil fuels, CO 2 The emission of the carbon dioxide is increased year by year, the greenhouse effect problem causes the rise and climate change of the global air temperature, and the carbon emission reduction and temperature control are not slow. CO is processed by 2 Selective reduction to fuel is an effective strategy that helps to alleviate environmental and energy problems and achieve the strategic goals of "carbon peaking, carbon neutralization". Photocatalytic CO 2 The reduction process is to simulate natural photosynthesis by using solar energy and photocatalyst to convert CO 2 And H 2 O is subjected to catalytic conversion. The technology can not only reduce CO 2 And can produce fuel and high added value chemicals to realize CO 2 And (5) recycling.
In recent years, bimetallic sites have been used for photocatalytic reduction of CO 2 Is of interest to many researchers. It was found that the synergistic effect of the bimetallic sites can promote CO 2 Molecular adsorption, stabilization of critical intermediate species, CO 2 The photocatalytic conversion efficiency and the product selectivity of the catalyst are obviously improved. Thus, constructing bimetallic sites in catalytic materials for photocatalytic reduction of CO 2 Is an effective strategy. However, bimetallic materials are generally unstable, and therefore, an appropriate support must be selected as the site-stabilizing metal.
The Metal Organic Frameworks (MOFs) are ideal catalytic material carriers because of the characteristics of large specific surface area, high porosity, unsaturated coordination metal sites and the like. Wherein the MOF-303 with xhh topology is composed of alternating cistron AlO 6 Octahedral composition, linked by 1-H-3, 5-pyrazoledicarboxylic acid, with adjacent and mutually oriented pyrazole functional groups present in the arrangement. The adjacent N atom pair of the pyrazole dicarboxylic acid in the MOF-303 structure has electrons with lone pairs, can effectively and accurately chelate metal ions, and is an ideal material for constructing double metal sites.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide a method for constructing a bimetal functional material by using bipyrazole-position chelate Cu and Ni bimetal 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 photocatalytic reduction of CO 2 Is used in the field of applications.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for constructing a functional material of Cu and Ni bimetallic sites by utilizing a metal organic framework MOF-303, which comprises the following steps:
1) Dissolving 1-H-3, 5-pyrazole dicarboxylic acid monohydrate in NaOH aqueous solution, stirring until the solution is clear, adding aluminum chloride hexahydrate into the solution, stirring until the solution is completely dissolved, heating in an oil bath, filtering after the reaction is complete to obtain a precipitate, washing the precipitate with deionized water and methanol for multiple times respectively, and vacuum drying to obtain the 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 2:1:1 3 ) 2 And Ni (NO) 3 ) 2 Acetonitrile solution was added and stirred until Cu (NO) 3 ) 2 、Ni(NO 3 ) 2 Completely dissolving, placing in a constant-temperature preheating oven for reaction, naturally cooling to room temperature after the reaction is finished, filtering to obtain precipitate, washing the precipitate with acetonitrile for multiple times until the supernatant is colorless, and vacuum drying to obtain the MOF-303-CuNi functional material.
Further, in step 1), the temperature of the oil bath was 100 ℃, and the time of heating the oil bath was 24 hours.
Further, in the step 2), the precipitate is washed with deionized water and methanol for 3 to 5 times, respectively.
Further, in the step 1), the temperature of the vacuum drying is 50-60 ℃, and the time of the 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 3 to 5 times with acetonitrile to colorless supernatant.
Further, in the step 2), the temperature of the vacuum drying is 50-60 ℃, and the time of the vacuum drying is 2 hours.
The MOF-303-CuNi functional material prepared by the method.
The prepared MOF-303-CuNi functional material reduces CO in photocatalysis 2 Is used in the field of applications.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method, raw materials are low, sources are wide, environment is friendly, the preparation process is simple, and the MOF-303-CuNi functional material can be prepared on a large scale;
(2) The MOF-303-CuNi functional material prepared by the invention, cu 2+ 、Ni 2+ Synergistic action of bimetallic ions to extend charge life and promote CO 2 Is adsorbed and activated, and the functional material of MOF-303-CuNi is used for photocatalytic reduction of CO 2 The activity is high, and compared with MOF-303 carrier performance is improved by about 3 times; can still keep higher catalytic activity after multiple circulating experiments, and has good stability.
Drawings
FIG. 1 is an XRD spectrum of a MOF-303-CuNi functional material prepared by the invention;
FIG. 2 is a FTIR spectrum of the MOF-303-CuNi functional material prepared by the invention;
FIG. 3 is an SEM image of a MOF-303 support and a MOF-303-CuNi functional material prepared according to the present invention; in the figure, a and b are SEM pictures of MOF-303, and c and d are SEM pictures of MOF-303-CuNi functional materials;
FIG. 4 is a UV-vis DRS spectrum of MOF-303 carrier and MOF-303-CuNi functional material prepared by the invention;
FIG. 5 shows the photocatalytic reduction of CO by the MOF-303-CuNi functional material and the MOF-303 carrier prepared by the invention 2 An activity comparison graph;
FIG. 6 is a graph showing the cycling stability of the MOF-303-CuNi functional material prepared according to the present invention.
Detailed Description
The invention is further described below in connection with specific embodiments. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit and nature of the invention are intended to be within the scope of the present invention. In the following examples, unless otherwise indicated, all technical means used in the examples are conventional means well known to those skilled in the art.
Example 1 preparation of MOF-303 catalyst
2.60g NaOH was weighed and dissolved in 750mL deionized water; 7.50g of 1-H-3, 5-pyrazole dicarboxylic acid monohydrate are weighed outDissolving in NaOH solution; the resulting mixture was stirred until the solution was clear. Subsequently 10.4g of AlCl was added to the solution 3 ·6H 2 O, stir until 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. Vacuum drying at 60deg.C in a vacuum drying oven for 6h to obtain MOF-303.
EXAMPLE 2 preparation of MOF-303-CuNi catalyst
The prepared MOF-303 was placed in a vacuum oven at 150℃for activation for 12 hours. 100mg of activated sample was weighed and transferred to a 10mL screw plug glass bottle, and 50mg of Cu (NO 3 ) 2 And Ni (NO) 3 ) 2 Transfer to glass bottles. To the flask was added 10mL of acetonitrile and stirred until the metal salt was completely dissolved. The glass vials were placed in a pre-heat oven at 70 ℃ for 48h. Collecting the precipitate, washing the precipitate with acetonitrile solution for three times to obtain colorless supernatant, and vacuum drying at 60 ℃ for 2 hours to obtain the MOF-303-CuNi catalyst.
FIG. 1 is an XRD pattern for MOF-303 and MOF-303-CuNi. As can be seen from the graph, the XRD diffraction peak of the MOF-303 does not change obviously after Cu and Ni are chelated, which indicates that the Cu and Ni bimetal modified MOF-303 material does not change the crystal structure.
FIG. 2 is a FT-IR spectrum of MOF-303 and MOF-303-CuNi. As can be seen from the figure, 1002cm -1 The vibration peak of N=N-H, and the peak intensity is obviously reduced after Cu and Ni are chelated by coordination unsaturated N site; at the same time at 435cm -1 There appears a vibrational peak attributed to the coordination of N and the metal ion. The variation of the FT-IR oscillation peaks described above demonstrates that Cu, ni are sequestered in the MOF-303 material by N-coordination to the pyrazole.
FIGS. 3a and 3b are SEM electron micrographs of MOF-303, and FIGS. 3c and 3d are SEM electron micrographs of MOF-303-CuNi, where we can see that MOF-303 and MOF-303-CuNi are both sheet-like structures with no change in morphology before and after adsorption.
FIG. 4 is a UV-vis DRS profile 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 MOF-303, and the absorption range is extended to the visible region. The above-described change in light absorption further demonstrates successful chelation of the Cu, ni bimetallic species in the MOF-303 material. Meanwhile, the MOF-303-CuNi material can effectively improve the light utilization rate, and generate more photo-generated charges for photocatalytic reaction.
Tables 1 and 2 are inductively coupled plasma-emission spectroscopy (ICP-OES) and BET specific surface area test results for MOF-303 and MOF-303-CuNi, respectively. The results show that the MOF-303-CuNi contains Cu and Ni ions, and Cu and Ni bimetallic is successfully chelated in the MOF-303 material. Meanwhile, compared with MOF-303, the specific surface area of MOF-303-CuNi is greatly reduced, and the adsorption is proved to be positioned in the pore canal of MOF-303.
ICP-OES results for samples prepared in Table 1
Note that: the unit is mg/g.
Table 2 BET specific surface area test results of samples prepared
Note that: the unit is (m) 2 /g)。
EXAMPLE 3 preparation of UiO-66-NH 2 CuNi catalyst
Weighing up 362mg of 2-aminoterephthalic acid in 20mL of N, N-dimethylformamide and formic acid (v 1 ∶v 2 =9:1) in the mixed solution; 233mg of zirconium chloride was weighed out and dissolved in the above mixed solution, and the above mixed solution was transferred to a 20mL screw-plug glass bottle. Placing the above mixed solution in an oven at 120deg.C for 24 hr, filtering to obtain precipitate, and washing with N, N-dimethylformamide and methanol solution respectively three times to obtain UiO-66-NH 2 A solid.
The UiO-66-NH is prepared 2 Placing the sample in a vacuum drying oven at 120deg.CActivated for 12h. 100mg of the activated sample was weighed and transferred to a 10mL screw plug glass bottle, and 50mg of Cu (NO 3 ) 2 And Ni (NO) 3 ) 2 Into glass bottles. 10mL of acetonitrile was added and stirred until the metal salt was completely dissolved. The glass vials were placed in a pre-heat oven at 70 ℃ for 48 hours. Collecting precipitate, washing the precipitate with acetonitrile solution for three times to obtain supernatant, and vacuum drying at 60deg.C for 2 hr to obtain UiO-66-NH 2 -CuNi catalyst.
EXAMPLE 4 photocatalytic CO by MOF-303-CuNi functional Material 2 Reduction performance
Photocatalytic reduction of Co 2 The reaction tests were carried out in a closed reactor. 10mg of catalyst was weighed and uniformly dispersed on 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 opening window having a diameter of 4.5 cm. High-purity CO of 0.4MPa 2 Introducing gas into a reactor, turning on a 280W xenon lamp to perform 4h photocatalytic reaction, detecting and analyzing a product every 2h by using an online gas chromatograph GC-7920, and calculating the CO yield of the product according to the following formula:
in which A t A is the peak area of CO at a certain moment CO And [ CO ]] s Peak area and concentration (ppm) of CO standard gas, respectively. P, V, T the internal pressure (Pa), volume (m) 3 ) Temperature (K). R represents a universal gas constant. m is the mass (g) of the photocatalyst.
FIG. 5 is a schematic representation of MOF-303, MOF-303-CuNi and a conventional photocatalytic MOF-UiO-66-NH 2 Reduction of CO by CuNi under full spectrum irradiation 2 Catalytic performance diagram of (2). MOF-303-CuNi has more excellent photocatalytic CO than MOF-303 2 Reduction properties, and most common photocatalytic MOF-UiO-66-NH 2 UiO-66-NH loaded with Cu and Ni bimetallic 2 MOF-303-CuNi has more excellent photocatalytic CO than CuNi 2 Reduction performance. FIG. 6 is a photo-reduced C0 of MOF-303-CuNi 2 Is a cyclic experimental activity graph of (2).As can be seen from the figure, the MOF-303-CuNi has good reaction stability.
Claims (9)
1. A method for constructing a functional material of Cu and Ni bimetallic sites by utilizing a metal organic framework MOF-303, which is characterized by comprising the following steps of:
1) Dissolving 1-H-3, 5-pyrazole dicarboxylic acid monohydrate in NaOH aqueous solution, stirring until the solution is clear, adding aluminum chloride hexahydrate into the solution, stirring until the solution is completely dissolved, heating in an oil bath, filtering after the reaction is complete to obtain a precipitate, washing the precipitate with deionized water and methanol for multiple times respectively, and vacuum drying to obtain the 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) at 150 ℃ for 12h, and weighing the activated MOF-303 carrier and Cu (NO) according to the mass ratio of 2:1:1 3 ) 2 And Ni (NO) 3 ) 2 Acetonitrile solution was added and stirred until Cu (NO) 3 ) 2 、Ni(NO 3 ) 2 Completely dissolving, placing in a constant-temperature preheating oven for reaction, naturally cooling to room temperature after the reaction is finished, filtering to obtain precipitate, washing the precipitate with acetonitrile for multiple times until the supernatant is colorless, and vacuum drying to obtain the MOF-303-CuNi functional material.
2. The method for constructing a functional material of Cu and Ni bi-metallic sites using a metal organic framework MOF-303 as recited in claim 1, wherein in step 1), the temperature of the oil bath is 100 ℃, and the time of heating the oil bath is 24h.
3. The method for constructing a functional material of Cu and Ni bimetallic sites by utilizing a metal organic framework MOF-303, as claimed in claim 1, wherein in the step 1), deionized water and methanol are used for washing and precipitating for 3-5 times respectively.
4. The method for constructing a functional material of Cu and Ni bimetallic sites by utilizing a metal organic framework MOF-303, as claimed in claim 1, wherein in the step 1), the temperature of vacuum drying is 50-60 ℃, and the time of vacuum drying is 6h.
5. The method for constructing a functional material of Cu and Ni bi-metallic sites by using a metal organic framework MOF-303 as claimed in claim 1, wherein the temperature of the constant temperature preheating oven is 70 ℃ and the reaction time is 48h in the step 2).
6. The method for constructing a functional material of Cu and Ni bimetallic sites by utilizing a metal organic framework MOF-303, which is characterized in that in the step 2), acetonitrile is used for washing and precipitating for 3-5 times, and the supernatant is colorless.
7. The method for constructing a functional material of Cu and Ni bimetallic sites by utilizing a metal organic framework MOF-303, as claimed in claim 1, wherein in the step 2), the temperature of vacuum drying is 50-60 ℃, and the time of vacuum drying is 2h.
8. The 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 for photocatalytic reduction of CO 2 Is used in the field of applications.
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| 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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