CN108636455B - Preparation and application of supported noble metal-based catalyst taking core-shell MOF as reaction vessel - Google Patents

Preparation and application of supported noble metal-based catalyst taking core-shell MOF as reaction vessel Download PDF

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CN108636455B
CN108636455B CN201810361182.3A CN201810361182A CN108636455B CN 108636455 B CN108636455 B CN 108636455B CN 201810361182 A CN201810361182 A CN 201810361182A CN 108636455 B CN108636455 B CN 108636455B
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CN108636455A (en
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李建荣
周阿武
豆义波
谢亚勃
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Beijing University of Technology
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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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    • B01J31/2204—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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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
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    • B01J35/393—Metal or metal oxide crystallite size
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
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    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

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Abstract

Preparation and application of a supported noble metal-based catalyst taking core-shell MOF as a reaction vessel belong to the technical field of catalysts. The bimetallic Ni/Zn-MOF with a core-shell structure is used as a carrier, the precious metal nanoparticles can be encapsulated in a cavity between core shells through regulation, the inner core can be used as the carrier to uniformly disperse the precious metal palladium nanoparticles, the shell can play a role in protection, the precious metal nanoparticles are inhibited from losing, and the Pd @ Ni-MOF with a multilevel structure is constructed. Under the hydrogen atmosphere, the catalytic performance of the catalyst on the selective hydrogenation of carbon-carbon double bonds and carbon-oxygen double bonds is researched. The preparation method is simple, easy to implement and high in yield. The prepared catalyst carrier Ni Zn-MOF has large specific surface area, is beneficial to the uniform dispersion of noble metal nanoparticles, has rich pore channels, is beneficial to the diffusion of reaction substrates and products, and can also play a role in molecular size selection, thereby having excellent catalytic activity and selectivity.

Description

Preparation and application of supported noble metal-based catalyst taking core-shell MOF as reaction vessel
Technical Field
The invention belongs to the technical field of catalysts, and relates to a supported noble metal-based multi-stage catalyst which is constructed by taking a bimetallic organic framework material (Ni Zn-MOFs) with a core-shell structure as a nano reactor as a carrier and is applied to selective hydrogenation reaction of carbon-carbon double bonds and carbon-oxygen double bonds.
Background
The selective catalytic hydrogenation reaction of alpha-beta unsaturated aldehyde is one of the important reactions for synthesizing and preparing fine chemical products, and has wide application in the modern fine organic synthesis, especially in the aspects of preparing medicaments and intermediates thereof, food additives, spices and the like. The catalytic hydrogenation method can greatly reduce the product cost, improve the product quality, increase the yield, shorten the reaction time and reduce the discharge of three wastes, thereby being generally regarded by people. According to literature reports, the catalyst Pd has high C ═ C hydrogenation selectivity, and alpha-beta unsaturated aldehyde can be adsorbed on nanoparticles of metal Pd, so that the probability of C ═ C double bond hydrogenation is greatly increased, and the hydrogenation selectivity of C ═ O double bonds is reduced. However, further improvements in catalytic efficiency and utilization of Pd catalysts remain a very important and challenging research.
Metal-organic frameworks (MOFs) are a new type of porous functional materials, which are porous network framework materials formed by self-assembly of Metal ions or ion clusters and organic ligands. The MOFs have high specific surface area and porosity, adjustable pore size and pore surface function, and have potential application values in the fields of adsorption separation, catalysis, energy storage and the like. Compared with the traditional heterogeneous catalyst, the porous MOFs material has the advantages, and the application of the porous MOFs material in the field of catalysis is more and more favored by researchers. Especially, MOFs have high specific surface area and ordered pore structure, can be used as a carrier of a nanoparticle catalyst, can enable nanoparticles to be uniformly dispersed in or on pore channels of the MOFs, and can greatly improve catalytic activity due to synergistic effect. Currently, there are many reports on the application of MOFs as carriers to support nanoparticles and to catalysis, but in contrast, there are few studies on MOF-based core-shell structures.
Disclosure of Invention
The invention aims to provide a preparation method for constructing a supported noble metal-based catalyst by taking bimetallic Ni/Zn-MOF with a core-shell structure as a carrier and application of the supported noble metal-based catalyst to selective hydrogenation reaction of carbon-carbon double bonds and carbon-oxygen double bonds.
The synthesis method of the composite material mainly comprises the following steps:
(1) preparing a dispersion of noble metal nanoparticles;
(2) preparation of noble metal @ Ni/Zn-MOF:
dissolving terephthalic acid, nickel salt and zinc salt in a mixed solution of N, N-dimethylformamide and ethylene glycol, stirring for 0.5-1 hour, transferring to a polytetrafluoroethylene reaction kettle, reacting at the temperature of 140-160 ℃ for 0-6 hours, adding the dispersion liquid of the noble metal nanoparticles synthesized in the step (1), reacting for 2-12 hours, cooling, centrifuging, washing, activating and drying to obtain the noble metal Ni/Zn-MOF.
In the step (1), the dispersion liquid for preparing the noble metal nano-particles can be prepared according to a conventional method, wherein the noble metal nano-particles are selected from one or more of Pd, Pt, Au and Ag;
such as Pd and Pt nano-particles preparation: dissolving a certain amount of noble metal chloride salt and polyvinylpyrrolidone in a mixed solution of methanol and water, and carrying out condensation reflux for 2-6 h to prepare the noble metal nanoparticles; the concentration of the aqueous solution of the noble metal chloride salt is 0.5-2 mg/mL, wherein the noble metal chloride salt is one of palladium chloride and chloroplatinic acid, and the volume ratio of methanol to water is 5: 1-20: 1.
In the step (2), the molar ratio of the nickel salt to the zinc salt is 4: 1-1: 1, preferably 1: 1. The molar ratio of terephthalic acid to the total of nickel nitrate and zinc nitrate is preferably (1-5):10, more preferably 3: 10. The volume ratio of N, N-dimethylformamide to ethylene glycol is (6-10):5, preferably 8: 5.
In the step (2), the loading capacity of the noble metal nanoparticles can be adjusted according to needs, and the ratio of the volume of the added noble metal nanoparticle dispersion liquid to the total volume of the mixed solution of N, N-dimethylformamide and ethylene glycol is 1: 15-8: 13.
And (3) the Ni/Zn-MOF in the noble metal @ Ni/Zn-MOF obtained in the step (2) is of a peanut-type core-shell structure, and the noble metal is loaded in the core, the shell or/and a cavity between the core and the shell. The noble metal nanoparticles can be dispersed at different parts of a Ni/Zn-MOF peanut type core-shell structure by adjusting the adding time of the dispersion liquid added with the noble metal nanoparticles, namely the reaction time before the dispersion liquid of the noble metal nanoparticles is added, particularly the reaction time is 1-1.5 hours, and then the dispersion liquid of the noble metal nanoparticles synthesized in the step (1) is added, so that the noble metal nanoparticles can be loaded in a cavity between the core shells, the inner core can be used as a carrier, the noble metal palladium nanoparticles are uniformly dispersed, the shell can play a role in protection, and the loss of the noble metal nanoparticles is inhibited.
The supported noble metal-based catalyst with the core-shell MOF as the reaction vessel, namely the noble metal @ Ni/Zn-MOF, is used for the hydrogenation reaction of carbon-carbon double bonds, and is particularly used for the selective hydrogenation reaction of carbon-carbon double bonds in carbon-carbon double bonds and carbon-oxygen double bonds.
The method for the application comprises the following specific steps: hydrogenation of carbon-carbon double bonds in compounds containing both carbon-carbon double bonds and carbon-oxygen double bonds, such as hydrogenation of carbon-carbon double bonds in cinnamaldehyde: 0.5-1 mmol of compound, a small amount of catalyst noble metal @ Ni/Zn-MOF and 5-10 mL of isopropanol are stirred under the condition of hydrogen atmosphere to react for 2-24 hours at the reaction temperature of 25-60 ℃; 10-50 mg of the catalyst is added, preferably 20 mg; the hydrogen pressurization pressure is 0.1-3 MPa.
The prepared bimetallic Ni/Zn-MOF has uniform size and regular morphology, is in a core-shell structure, and has cavities among the core shells, so that the noble metal nanoparticles can be packaged in the cavities, the noble metal nanoparticles are uniformly dispersed and are not easy to run off, the carbon-carbon double bond hydrogenation catalytic activity is improved, and the bimetallic Ni/Zn-MOF has wide application in the field of fine chemical synthesis; the preparation method is simple, easy to implement, high in yield and easy for batch production, and the utilization rate of the noble metal is greatly improved.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of Pd @ Ni/Zn-MOF in example 1 of the present invention.
FIG. 2 is a schematic scanning electron microscope of Pd @ Ni/Zn-MOF in example 1 of the present invention.
FIG. 3 is a graph showing the Pd @ Ni/Zn-MOF catalyzed cinnamaldehyde hydrogenation reaction performance in example 1 of the present invention.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
The first step is as follows: weighing 15mg of palladium chloride and 77mg of polyvinylpyrrolidone, dissolving in a mixed solution of 85mL of methanol and 15mL of deionized water, and carrying out condensation reflux at 70 ℃ for 4h to obtain a Pd nanoparticle solution.
The second step is that: weighing 30mg of terephthalic acid, 60mg of nickel nitrate and 40mg of zinc nitrate, dissolving in a mixed solution of N, N-dimethylformamide (8mL) and ethylene glycol (5mL), stirring for 1 hour, transferring to a polytetrafluoroethylene reaction kettle, reacting at 150 ℃, reacting for 1.5 hours, adding the synthesized Pd nanoparticle solution (3.5mL), reacting for 4 hours, cooling, centrifuging, washing, activating and drying to obtain Pd @ Ni/Zn-MOF, wherein the noble metal Pd nanoparticles are successfully loaded in a cavity (mainly in the cavity) between core shells of the core-shell structure Ni/Zn-MOF.
The third step: weighing 20mg of catalyst Pd @ Ni/Zn-MOF, 5mL of isopropanol and 0.5mmol of cinnamyl aldehyde, transferring the catalyst Pd @ Ni/Zn-MOF into a high-pressure reaction kettle, introducing 0.3MPa of hydrogen, magnetically stirring, reacting for 3 hours at the reaction temperature of 25 ℃.
Example 2
The first step is as follows: 16.6mg polyvinylpyrrolidone was weighed out and dissolved in 45mL of ethanol, and 5.0mL of H was added dropwise2PtCl6And (6.0mM) water solution, and condensing and refluxing for 3h to obtain the Pt nano particle solution.
The second step is that: weighing 30mg of terephthalic acid, 50mg of nickel nitrate and 50mg of zinc nitrate, dissolving in a mixed solution of N, N-dimethylformamide (10mL) and ethylene glycol (5mL), stirring for 1 hour, transferring to a polytetrafluoroethylene reaction kettle, adding the synthesized Pt nanoparticle solution (5mL), reacting at 140 ℃ for 6 hours, cooling, centrifuging, washing, activating and drying to obtain Pt @ Ni/Zn-MOF, wherein the noble metal Pd nanoparticles are successfully loaded in the core (mainly in the core) of the core-shell structure Ni/Zn-MOF.
The third step: weighing 50mg of catalyst Pt @ Ni/Zn-MOF, 5mL of isopropanol and 0.4mmol of cinnamyl aldehyde, transferring the catalyst into a high-pressure reaction kettle, introducing hydrogen gas into the reaction kettle under the pressure of 1.0MPa, magnetically stirring the mixture, and reacting the mixture for 24 hours at the reaction temperature of 30 ℃.
Example 3
The first step is as follows: weigh 100mL of HAuCl4(0.01%) aqueous solution, reflux-condensing, adding 4.5mL of aqueous solution of sodium citrate (1%), reflux-condensing for 20 minutes, cooling to room temperature, adding 20mL of aqueous solution of polyvinylpyrrolidone (0.5g), and stirring at room temperatureAnd stirring for 24 hours to obtain an Au nano-particle solution.
The second step is that: weighing 30mg of terephthalic acid, 60mg of nickel nitrate and 40mg of zinc nitrate, dissolving in a mixed solution of N, N-dimethylformamide (8mL) and ethylene glycol (5mL), stirring for 1 hour, transferring to a polytetrafluoroethylene reaction kettle, reacting at 150 ℃ for 6 hours, adding the synthesized Au nanoparticle solution (3.5mL), stirring at room temperature, centrifuging, washing, activating and drying to prepare Au @ Ni/Zn-MOF, wherein the noble metal Pd nanoparticles are successfully loaded outside the shell (mainly outside the shell) of the core-shell structure Ni/Zn-MOF.
The third step: weighing 50mg of catalyst Au @ Ni/Zn-MOF, 5mL of isopropanol and 0.5mmol of cinnamyl aldehyde, transferring the mixture into a high-pressure reaction kettle, introducing 1MPa of hydrogen, magnetically stirring, reacting for 12 hours at the reaction temperature of 60 ℃.
The test results for the material obtained in example 1 above are the same, as follows:
(1) and (3) characterizing the material morphology:
FIG. 1 is an X-ray powder diffraction pattern of Pd @ Ni/Zn-MOF; FIG. 2 is a scanning electron microscope image of Pd @ Ni Zn-MOF.
(2) And (3) characterization of catalytic performance of the material:
FIG. 3 is a graph of the performance of Pd @ Ni/Zn-MOF, Pt @ Ni/Zn-MOF and Au @ Ni/Zn-MOF catalysts in catalyzing cinnamaldehyde hydrogenation reaction, and the graph shows that the noble metal @ Ni/Zn-MOF catalyst has excellent catalytic activity and selectivity.
The foregoing is a preferred embodiment of the present invention, but the present invention should not be limited to the disclosure of this embodiment. Therefore, equivalents and modifications may be made thereto without departing from the spirit of the disclosure.

Claims (9)

1. A supported noble metal based catalyst noble metal @ Ni/Zn-MOF with core-shell structure MOF as a reaction vessel is characterized in that Ni/Zn-MOF in the noble metal @ Ni/Zn-MOF is in a peanut type core-shell structure and is in a core-shell structure, a cavity is formed between the core shells, and the noble metal is supported in the cavity between the core shells; noble metal nano-particles, wherein one or two of Pd and Ag are selected;
the preparation method comprises the following steps:
(1) preparing a dispersion of noble metal nanoparticles;
(2) preparation of noble metal @ Ni/Zn-MOF:
dissolving terephthalic acid, nickel salt and zinc salt in a mixed solution of N, N-dimethylformamide and ethylene glycol, stirring for 0.5-1 hour, transferring to a polytetrafluoroethylene reaction kettle, reacting at the temperature of 140-160 ℃ for 1-1.5 hours, adding the dispersion liquid of the noble metal nanoparticles synthesized in the step (1), reacting for 2-12 hours, cooling, centrifuging, washing, activating and drying to obtain the noble metal @ Ni/Zn-MOF.
2. The supported noble metal-based catalyst noble metal @ Ni/Zn-MOF taking the core-shell MOF as the reaction vessel according to claim 1, wherein in the step (2), the nickel salt and the zinc salt are one or more of metal nitrate or metal chloride salt.
3. The supported noble metal based catalyst noble metal @ Ni/Zn-MOF with the core-shell MOF as the reaction vessel is characterized in that in the step (2), the molar ratio of nickel nitrate to zinc nitrate is 4: 1-1: 1; the total molar ratio of terephthalic acid to nickel nitrate and zinc nitrate is (1-5): 10; the volume ratio of the N, N-dimethylformamide to the ethylene glycol is (6-10): 5.
4. The supported noble metal-based catalyst noble metal @ Ni/Zn-MOF using core-shell MOF as a reaction vessel according to claim 3, wherein in the step (2), the total molar ratio of terephthalic acid to nickel nitrate and zinc nitrate is 3: 10; the volume ratio of the N, N-dimethylformamide to the ethylene glycol is 8: 5.
5. The supported noble metal based catalyst noble metal @ Ni/Zn-MOF taking MOF with a core-shell structure as a reaction vessel is characterized in that in the step (2), the loading amount of noble metal nanoparticles is adjusted according to needs, and the ratio of the volume of the noble metal nanoparticle dispersion liquid to the total volume of a mixed solution of N, N-dimethylformamide and ethylene glycol is 1: 15-8: 13.
6. Use of the supported noble metal-based catalyst noble metal @ Ni/Zn-MOF with the core-shell MOF as the reaction vessel in any one of claims 1 to 5 for hydrogenation reaction of carbon-carbon double bonds.
7. Use according to claim 6, for the selective hydrogenation of carbon-carbon double bonds in carbon-carbon double bonds and carbon-oxygen double bonds.
8. Use according to claim 7, characterized in that it is as follows: hydrogenation reaction for carbon-carbon double bond in cinnamaldehyde: 0.5-1 mmol of cinnamaldehyde, 10-50 mg of catalyst noble metal @ Ni/Zn-MOF and 5-10 mL of isopropanol are stirred under the condition of hydrogen atmosphere, and react for 2-24 hours at the reaction temperature of 25-60 ℃; the hydrogen pressurization pressure is 0.1-3 MPa.
9. Use according to claim 8, characterized in that the catalyst noble metal @ Ni/Zn-MOF is 20 mg.
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