CN110947428A - UiO @ Pd @ UiO catalyst and preparation method and application thereof - Google Patents

UiO @ Pd @ UiO catalyst and preparation method and application thereof Download PDF

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CN110947428A
CN110947428A CN201811122069.6A CN201811122069A CN110947428A CN 110947428 A CN110947428 A CN 110947428A CN 201811122069 A CN201811122069 A CN 201811122069A CN 110947428 A CN110947428 A CN 110947428A
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uio
carrier
catalyst
dimethylformamide
mixed solution
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CN110947428B (en
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崔光学
郑奉斌
李国栋
唐智勇
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Beijing Institute of Nanoenergy and Nanosystems
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Beijing Institute of Nanoenergy and Nanosystems
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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
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • 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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    • C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
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Abstract

The invention provides a UiO @ Pd @ UiO catalyst, and a preparation method and application thereof. The UiO @ Pd @ UiO catalyst takes UiO as a carrier and Pd as an active component; the catalyst is of a sandwich structure and sequentially comprises a UiO crystal with a regular octahedral structure, a Pd nanoparticle material and a UiO porous material from inside to outside. The UiO @ Pd @ UiO catalyst provided by the invention has the advantages of good stability, high conversion rate and selectivity and good mechanical strength, and can be used for preparing styrene by high-efficiency catalytic selective hydrogenation of phenylacetylene.

Description

UiO @ Pd @ UiO catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, relates to a catalyst, a preparation method and application thereof, and particularly relates to a UiO @ Pd @ UiO catalyst, a preparation method and application thereof.
Background
Styrene is a very important chemical intermediate raw material, and is widely used for producing high polymer materials such as polystyrene and synthetic rubber (such as ABS, SB latex and the like). With the strong growth of downstream product consumption of styrene, the annual yield of styrene is also continuously increasing to meet market demand.
Currently, the industrial production methods of styrene mainly include ethylbenzene dehydrogenation and propylene oxide-styrene co-production, but in order to meet the increasing market demand, the development of new styrene production approaches becomes the focus of attention.
Although the recovery of styrene from a pyrolysis gasoline C8 fraction, which is a by-product of a steam ethylene cracking apparatus, by extractive distillation has been proposed as a route for producing styrene, the presence of phenylacetylene in the C8 fraction not only destroys the performance of polystyrene but also deactivates the catalyst for styrene polymerization. The most common commercial alkyne selective hydrogenation catalyst is Pd/Al2O3The carrier of the supported catalyst is gamma-Al2O3However, the conversion rate and selectivity of olefin are seriously affected by the high specific surface area and strong surface acidity, and the traditional catalyst is unstable, the load component is easy to fall off after being recycled for many times, the service life of the catalyst is shortened, and the TOF (number of converted reactant molecules per unit active center in unit time) value is also smaller, so that the catalytic efficiency is low.
The selective hydrogenation of phenylacetylene to styrene is an effective method, which not only can remove a small amount of phenylacetylene in styrene in C8 fraction, but also can be used as a new way for producing styrene, therefore, the research of a high-efficiency selective hydrogenation catalyst of phenylacetylene is imperative.
A Metal-Organic framework compound (MOFs for short) is a highly ordered low-density crystal material with an infinitely expanded network structure, which is formed by self-assembly and connection of transition Metal ions and Organic ligands through coordination bonds, and is a novel porous material. Over the past decade, research on MOFs has advanced greatly and has gained important applications in the fields of catalysis and adsorption. Among various MOFs, the structure of the UiO series compound has very good thermal stability, and meanwhile, the UiO series compound has the advantages of structural diversity, adjustable pore volume, functional pore channels and the like, and has attracted extensive attention of researchers.
CN107790184A discloses a Pd/UiO-66 catalyst with a Pd metal nanocrystalline core with controllable morphology and a preparation method thereof, wherein the preparation method comprises the following steps: s1: dissolving terephthalic acid in dimethylformamide to obtain a solution A, dissolving palladium salt in dimethylformamide to obtain a solution B, and dissolving zirconium tetrachloride in dimethylformamide to obtain a solution C for later use; s2: mixing and stirring the solution A and the solution B, mixing the solution A and the solution B with the solution C, and then adding the micromolecular acid into the mixed solution; s3: and sealing the mixed solution obtained in the step S2, heating and stirring for 20-26 h, and after the reaction is finished, centrifuging, washing and drying the mixed solution to obtain the Pd/UiO-66 catalyst with the controllable-morphology Pd metal nanocrystal inner core. The Pd/UiO-66 catalyst prepared by the one-step method has controllable Pd nano-crystal morphology, and the morphology of the controllable Pd nano-particles is spherical or tetrahedral; in addition, the prepared Pd/UiO-66 catalyst also has a good UiO-66 crystalline state and a high specific surface area, but the stability of the catalyst needs to be further improved.
CN106902842A discloses a preparation method and application of a supported palladium catalyst using MOFs derived carbon-based materials as a carrier, the preparation method comprises the following steps: (1) reduction of palladium (Pd) nanoparticles: dissolving palladium chloride and polyvinylpyrrolidone into a mixed solution of methanol and water, heating, condensing and refluxing for 3-6 h, and preparing a Pd nanoparticle solution; (2) preparation of Pd @ ZIF-67: dissolving 2-methylimidazole, cobalt nitrate hexahydrate and polyvinylpyrrolidone in methanol under the condition of stirring at room temperature, placing the Pd nanoparticle solution obtained in the step (1) in the mixed solution, magnetically stirring for 2 hours, standing at room temperature for 12-36 hours, then centrifugally washing with methanol, activating, and drying in vacuum to obtain Pd @ ZIF-67; (3) and (2) carbonizing Pd @ ZIF-67: and (3) placing the Pd @ ZIF-67 obtained in the step (2) in a mortar, grinding for 10min, heating to 700-900 ℃ at a heating rate of 2-5 ℃/min under the protection of argon, and carbonizing for 2-6 h to prepare the nitrogen-doped carbon nanotube-coated supported palladium metal nano porous composite material Pd @ Co/CNT. The catalyst prepared by the method maintains the characteristics of high specific surface area and rich pore structure of the precursor ZIF-67 to a great extent, and is favorable for uniform dispersion of palladium nanoparticles, so that the catalyst has excellent catalytic activity. However, the conversion rate and mechanical strength of the catalyst prepared by the method are to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a UiO @ Pd @ UiO catalyst, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
one purpose of the invention is to provide a UiO @ Pd @ UiO catalyst, wherein the catalyst takes UiO as a carrier and Pd as an active component; the catalyst is of a sandwich structure and sequentially comprises a UiO crystal with a regular octahedral structure, a Pd nanoparticle material and a UiO porous material from inside to outside.
The UiO @ Pd @ UiO catalyst is designed into a sandwich structure by selecting a UiO crystal with a regular octahedral structure as a carrier and Pd as a load component, and the UiO crystal, the Pd nano-particle material and the UiO porous material with the regular octahedral structure are sequentially arranged from inside to outside; the catalyst has the advantages that the inner layer is made of the UiO crystal material, the outer layer is made of the UiO porous material, the interlayer is made of the Pd nano particles, the combination of the UiO crystal material and the Pd nano particles ensures high conversion rate and selectivity of the catalyst, the catalyst can better meet the actual requirements of industrial application, the UiO porous material coated on the outer layer ensures the stability of the catalyst, the mechanical strength of the catalyst is increased, and the wear rate of the catalyst is reduced.
The UO series MOFs were originally a new class of MOFs based on Zr (IV) metals reported by Oslo university, more typically UO-66, UO-67, UO-68 and various derivatives obtained by modifying the groups contained in the organic ligands.
The load capacity of the load component Pd in the UiO @ Pd @ UiO catalyst provided by the invention can be flexibly adjusted by changing the amount of the precursor added with the Pd nanoparticles according to the requirement; preferably, the loading amount of the active component Pd is 0.1-1% by mass of the UiO carrier, for example, the loading amount of the active component Pd is 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1% by mass of the UiO carrier.
Preferably, the mass of the UiO porous material accounts for 0.1-0.5% of the mass of the UiO crystal layer, for example, the mass of the UiO porous material accounts for 0.1%, 0.2%, 0.3%, 0.4%, 0.5% of the mass of the UiO crystal layer.
The invention also aims to provide a preparation method of the UiO @ Pd @ UiO catalyst, which comprises the following steps:
1) preparation of the UiO carrier:
zirconium chloride, phthalic acid, biphenyldicarboxylic acid, terphenyldicarboxylic acid, N-dimethylformamide, acetic acid and triethylamine are used as raw materials, and a UiO carrier is prepared after reaction;
2) ultrasonically dispersing the UiO carrier prepared in the step 1) by using methanol, adding a Pd nanoparticle prepolymer, adding a methanol solution of sodium borohydride for reaction, and preparing the UiO @ Pd with a core-shell structure after the reaction is finished;
3) ultrasonically dispersing the UiO @ Pd core-shell structure prepared in the step 2) by using N, N-dimethylformamide, adding the prepolymer zirconium chloride, phthalic acid, biphenyldicarboxylic acid, terphenyldicarboxylic acid, N-dimethylformamide, acetic acid and triethylamine of the UiO carrier prepared in the step 1) for reacting, and preparing the UiO @ Pd @ UiO catalyst with a sandwich structure after the reaction is finished.
The preparation method of the UiO @ Pd @ UiO catalyst provided by the invention is easy to operate, simple in equipment, high in production efficiency, free from increasing the production cost of the catalyst, and high in industrial application level.
In the step 1), the UiO carrier is a UiO-67 carrier, and the dosage of the raw materials of the UiO-67 carrier is as follows: 18-24 mg of zirconium chloride, 16-22 mg of biphenyldicarboxylic acid, 8-12 mL of N, N-dimethylformamide, 2-4 mL of acetic acid and 200-150 muL of triethylamine.
Preferably, in the step 1), the UiO carrier is a UiO-66 carrier, and the dosage of the raw materials of the UiO-66 carrier is as follows: 30-36 mg of zirconium chloride, 22-27 mg of phthalic acid, 8-12 mL of N, N-dimethylformamide and 0.5-1.0 mL of acetic acid.
Preferably, in step 1), the UiO carrier is a UiO-68 carrier, and the dosage of the raw materials of the UiO-68 carrier is as follows: 42-47 mg of zirconium chloride, 58-63 mg of terphenyl dicarboxylic acid, 2-5 mL of N, N-dimethylformamide and 0.8-1.5 mL of acetic acid.
In the step 1), the reaction temperature is 100-130 ℃, for example, the reaction temperature is 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃ and 130 ℃; the reaction time is 22-26 h, for example, 22h, 23h, 24h, 25h and 26 h.
In the step 2), the amount of the methanol is 8-12 mL, for example, the amount of the methanol is 8mL, 9mL, 10mL, 11mL, 12 mL.
Preferably, the amount of the Pd nanoparticle precursor polymer is 40-50 μ L, for example, the amount of the Pd nanoparticle precursor polymer is 40 μ L, 41 μ L, 42 μ L, 43 μ L, 44 μ L, 45 μ L, 46 μ L, 47 μ L, 48 μ L, 49 μ L, 50 μ L.
Preferably, the Pd nanoparticle prepolymer is chloropalladate (H) with the concentration of 20-80 mM/L2PdCl4) For example, the concentration of the Pd nanoparticle pre-polymer is 20mM/L, 40mM/L, 50mM/L, 60mM/L, 70mM/L, or 80 mM/L. Preferably, the mass concentration of the methanol solution of sodium borohydride is 1mg/mL, the dosage of the methanol solution of sodium borohydride is 2-4 mL, for example, the dosage of the methanol solution of sodium borohydride is 2mL, 2.5mL, 3mL, 3.5mL, 4 mL.
In step 3), the amount of N, N-dimethylformamide is 4 to 6mL, for example, 4mL, 4.1mL, 4.2mL, 4.3mL, 4.4mL, 4.5mL, 4.6mL, 4.7mL, 4.8mL, 4.9mL, 5mL, 5.1mL, 5.2mL, 5.3mL, 5.4mL, 5.5mL, 5.6mL, 5.7mL, 5.8mL, 5.9mL, 6 mL.
Preferably, in the step 3), the amount of the precursor for synthesizing the UiO carrier is 8 to 10% of the amount of the raw materials of zirconium chloride, phthalic acid, biphenyldicarboxylic acid, terphenyldicarboxylic acid, N-dimethylformamide, acetic acid and triethylamine in the step 1), for example, the amount of the precursor for synthesizing the UiO-67 carrier is 8%, 8.5%, 9%, 9.5% and 10% of the amount of the raw materials of zirconium chloride, biphenyldicarboxylic acid, N-dimethylformamide, acetic acid and triethylamine in the step 1); namely, the usage amount of zirconium chloride for synthesizing the UiO-67 carrier in the step 3) is 8-10% of that of zirconium chloride in the step 1), the usage amount of diphenic acid for synthesizing the UiO-67 carrier in the step 3) is 8-10% of that of diphenic acid in the step 1), the usage amount of N, N-dimethylformamide for synthesizing the UiO-67 carrier in the step 3) is 8-10% of that of N, N-dimethylformamide in the step 1), the usage amount of acetic acid for synthesizing the UiO-67 carrier in the step 3) is 8-10% of that of acetic acid in the step 1), and the usage amount of triethylamine for synthesizing the UiO-67 carrier in the step 3) is 8-10% of that of triethylamine in the step 1).
In the step 3), the reaction temperature is 110-130 ℃, for example, the reaction temperature is 110 ℃, 115 ℃, 120 ℃, 125 ℃ and 130 ℃; the reaction time is 4-6 h, for example, the reaction time is 4h, 4.5h, 5h, 5.5h, 6 h.
As a preferred embodiment of the invention, the preparation method of the UiO-67@ Pd @ UiO-67 catalyst comprises the following steps:
1) preparation of UiO-67 Carrier:
a) weighing 18-24 mg of zirconium chloride, adding 4-6 mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 1-2 mL of acetic acid and 100-150 mu L of triethylamine, and mixing to obtain a mixed solution A;
b) weighing 16-22 mg of biphenyldicarboxylic acid, adding 4-6 mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 1-2 mL of acetic acid and 100-150 mu L of triethylamine, and mixing to obtain a mixed solution B;
c) mixing the mixed solution A and the mixed solution B, transferring the mixed solution A and the mixed solution B into a reaction kettle, putting the reaction kettle into an oven, and reacting for 22-26 hours at the temperature of 100-130 ℃ to prepare the UiO-67 carrier;
2) ultrasonically dispersing the UiO-67 carrier prepared in the step 1) by using 8-12 mL of methanol, adding 40-50 mu L of Pd nanoparticle prepolymer, reacting at room temperature for 4-6 h, adding 2-4 mL of sodium borohydride methanol solution with the mass concentration of 1mg/mL, and reacting at room temperature for 1-2 h to prepare the UiO-67@ Pd with the core-shell structure;
3) ultrasonically dispersing the UiO-67@ Pd with the core-shell structure obtained in the step 2) by using 4-6 mL of N, N-dimethylformamide, adding 8-10% of a prepolymer for synthesizing the UiO-67 carrier, and carrying out oil bath reaction at 110-130 ℃ for 4-6 h to prepare the UiO-67@ Pd @ UiO-67 catalyst with a sandwich structure.
The catalyst can be prepared into different 'sandwich' structure UiO @ Pd @ UiO catalysts according to actual needs, namely different 'sandwich' structure UiO @ Pd @ UiO catalysts can be prepared by changing the types of materials of a carrier and an outermost layer, such as UiO-67@ Pd @ UiO-66 catalyst, UiO-67@ Pd @ UiO-68 catalyst, UiO-66@ Pd @ UiO-66 catalyst, UiO-66@ Pd @ UiO-67 catalyst, UiO-66@ Pd @ UiO-68 catalyst, UiO-68@ Pd @ UiO-66 catalyst, UiO-68@ Pd @ UiO-67 catalyst and UiO-68@ Pd @ UiO-68 catalyst.
The invention also aims to provide an application of the UiO @ Pd @ UiO catalyst, and the UiO @ Pd @ UiO catalyst is used for preparing styrene by selectively hydrogenating phenylacetylene.
In addition, the UiO @ Pd @ UiO catalyst provided by the invention can also be suitable for selective hydrogenation reactions of other alkynes, such as selective hydrogenation reactions of 1-ethynylcyclohexene, ethynylcyclopropane and the like, and has high conversion rate and selectivity.
Compared with the prior art, the invention has the beneficial effects that:
(1) the catalyst of the invention has high catalytic efficiency, and when the catalyst is used for catalyzing the selective hydrogenation of phenylacetylene to prepare styrene, the conversion rate is up to 97%, the selectivity is up to 94%, and the TOF value is 13000h-1(ii) a The stability is good, and the conversion rate and the selectivity are basically kept unchanged after 5 times of recycling.
(2) The preparation method of the UiO @ Pd @ UiO catalyst has the advantages of easy operation of the synthesis method, simple equipment, easy realization and high efficiency, and can not cause obvious increase of the production cost of the catalyst.
(3) The UiO @ Pd @ UiO catalyst provided by the invention can be widely used for preparing styrene by selective hydrogenation of phenylacetylene, and can also be applied to selective hydrogenation reaction of other alkynes such as 1-ethynylcyclohexene, ethynylcyclopropane and the like.
Drawings
FIG. 1 is a scanning electron microscope image of a UiO-67 carrier of the UiO-67@ Pd @ UiO-67 catalyst of the present invention;
FIG. 2 is a scanning electron microscope image of UiO-67@ Pd having a core-shell structure of the UiO-67@ Pd @ UiO-67 catalyst of the present invention;
FIG. 3 is a scanning electron microscope image of UiO-67@ Pd @ UiO-67 having a "sandwich" structure of the UiO-67@ Pd @ UiO-67 catalyst of the present invention;
FIG. 4 is a flow diagram of a process for preparing the UiO-67@ Pd @ UiO-67 catalyst of the present invention;
FIG. 5 is a scanning electron micrograph of a UiO-67 carrier prepared according to comparative example 5 of the present invention;
FIG. 6 is a scanning electron micrograph of a UiO-67@ Pd @ UiO-67 catalyst prepared according to comparative example 4 of the present invention;
FIG. 7 is a scanning electron micrograph of a UiO-67@ Pd @ UiO-67 catalyst prepared according to comparative example 5 of the present invention;
FIG. 8 is a scanning electron micrograph of the UiO-67@ Pd @ UiO-66 catalyst prepared in example 6 according to the present invention;
FIG. 9 is a scanning electron micrograph of the UiO-67@ Pd @ UiO-68 catalyst prepared in example 7 according to the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments with reference to the accompanying fig. 1-9.
The catalyst takes UO as a carrier and Pd as an active component; the catalyst is of a sandwich structure and sequentially comprises a UiO crystal with a regular octahedral structure, a Pd nanoparticle material and a UiO porous material from inside to outside.
Example 1
The preparation method of the UiO-67@ Pd @ UiO-67 catalyst of this example comprises the following steps:
1) preparation of UiO-67 Carrier:
a) weighing 18.64mg of zirconium chloride, adding 5mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 1.38mL of acetic acid, and mixing to obtain a mixed solution A;
b) weighing 19.36mg of biphenyldicarboxylic acid, adding 5mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 120 mu L of triethylamine, and mixing to obtain a mixed solution B;
c) mixing the mixed solution A and the mixed solution B, transferring the mixed solution A and the mixed solution B into a reaction kettle, putting the mixture into an oven, and reacting for 24 hours at 120 ℃ to prepare the UiO-67 carrier;
2) ultrasonically dispersing the UiO-67 carrier prepared in the step 1) by using 10mL of methanol, adding 44 mu L of Pd nanoparticle prepolymer, reacting for 5h at room temperature, adding 2mL of sodium borohydride methanol solution with the mass concentration of 1mg/mL, and reacting for 1h at room temperature to prepare the UiO-67@ Pd with the core-shell structure;
3) ultrasonically dispersing the UiO-67@ Pd with the core-shell structure obtained in the step 2) by using 4mL of N, N-dimethylformamide, adding 10% of prepolymer for synthesizing the UiO-67 carrier, and carrying out oil bath reaction at 120 ℃ for 5h to prepare the UiO-67@ Pd @ UiO-67 catalyst with a sandwich structure.
Wherein, the scanning electron microscope image of the UiO-67 carrier is shown in figure 1, and as can be seen from figure 1, the UiO-67 carrier is a UiO-67 crystal with a regular octahedral structure. The scanning electron microscope image of UiO-67@ Pd with a core-shell structure is shown in FIG. 2, and as can be seen from FIG. 2, a Pd nanoparticle material layer is loaded on the outer side of the UiO-67 carrier. The scanning electron microscope image of the UiO-67@ Pd @ UiO-67 with a sandwich structure is shown in figure 3, and a layer of UiO-67 porous material is coated outside the UiO-67@ Pd with a core-shell structure.
The flow chart of the preparation method of the UiO-67@ Pd @ UiO-67 catalyst is shown in figure 4, and the preparation method comprises the steps of preparing a UiO-67 carrier; loading an active component Pd on a UiO-67 carrier to prepare the UiO-67@ Pd with a core-shell structure; the UiO-67@ Pd @ UiO-67 with a sandwich structure is prepared from a UiO-67@ Pd @ UiO-67 porous material with a core-shell structure.
Example 2
The preparation method of the UiO-67@ Pd @ UiO-67 catalyst of this example comprises the following steps:
1) preparation of UiO-67 Carrier:
a) weighing 19mg of zirconium chloride, adding 4mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 1mL of acetic acid, and mixing to obtain a mixed solution A;
b) weighing 16mg of biphenyldicarboxylic acid, adding 4mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 100 mu L of triethylamine, and mixing to obtain a mixed solution B;
c) mixing the mixed solution A and the mixed solution B, transferring the mixed solution A and the mixed solution B into a reaction kettle, putting the reaction kettle into an oven, and reacting for 22 hours at 100 ℃ to prepare the UiO-67 carrier;
2) ultrasonically dispersing the UiO-67 carrier prepared in the step 1) with 8mL of methanol, adding 40 mu L of Pd nanoparticle prepolymer, reacting for 4h at room temperature, adding 2mL of methanol solution of sodium borohydride with the mass concentration of 1mg/mL, and reacting for 1h at room temperature to prepare the UiO-67@ Pd with the core-shell structure;
3) ultrasonically dispersing the UiO-67@ Pd with the core-shell structure obtained in the step 2) by using 4mL of N, N-dimethylformamide, adding 8% of prepolymer for synthesizing the UiO-67 carrier, and carrying out oil bath reaction at 110 ℃ for 4h to prepare the UiO-67@ Pd @ UiO-67 catalyst with a sandwich structure.
Example 3
The preparation method of the UiO-67@ Pd @ UiO-67 catalyst of this example comprises the following steps:
1) preparation of UiO-67 Carrier:
a) weighing 20mg of zirconium chloride, adding 4.5mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 1.3mL of acetic acid, and mixing to obtain a mixed solution A;
b) weighing 18mg of biphenyldicarboxylic acid, adding 4.8mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 120 mu L of triethylamine, and mixing to obtain a mixed solution B;
c) mixing the mixed solution A and the mixed solution B, transferring the mixed solution A and the mixed solution B into a reaction kettle, putting the reaction kettle into an oven, and reacting for 23.5 hours at 110 ℃ to prepare the UiO-67 carrier;
2) ultrasonically dispersing the UiO-67 carrier prepared in the step 1) with 9.5mL of methanol, adding 44 mu L of Pd nanoparticle prepolymer, reacting for 4.5h at room temperature, adding 2.5mL of sodium borohydride methanol solution with the mass concentration of 1mg/mL, and reacting for 1.5h at room temperature to prepare the UiO-67@ Pd with the core-shell structure;
3) ultrasonically dispersing the UiO-67@ Pd with the core-shell structure obtained in the step 2) by using 4.5mL of N, N-dimethylformamide, adding 8.5% of prepolymer for synthesizing the UiO-67 carrier, and carrying out oil bath reaction at 120 ℃ for 4.5h to prepare the UiO-67@ Pd @ UiO-67 catalyst with a sandwich structure.
Example 4
The preparation method of the UiO-67@ Pd @ UiO-67 catalyst of this example comprises the following steps:
1) preparation of UiO-67 Carrier:
a) weighing 22mg of zirconium chloride, adding 5.5mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 1.6mL of acetic acid, and mixing to obtain a mixed solution A;
b) weighing 20mg of biphenyldicarboxylic acid, adding 5.5mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 135 mu L of triethylamine, and mixing to obtain a mixed solution B;
c) mixing the mixed solution A and the mixed solution B, transferring the mixed solution A and the mixed solution B into a reaction kettle, putting the mixture into an oven, and reacting for 24.5 hours at 120 ℃ to prepare the UiO-67 carrier;
2) ultrasonically dispersing the UiO-67 carrier prepared in the step 1) by using 10.5mL of methanol, adding 46 mu L of Pd nano particle prepolymer, reacting for 5.5h at room temperature, then adding 3.5mL of sodium borohydride methanol solution with the mass concentration of 1mg/mL, and reacting for 2h at room temperature to prepare the UiO-67@ Pd with the core-shell structure;
3) ultrasonically dispersing the UiO-67@ Pd with the core-shell structure obtained in the step 2) by using 5.5mL of N, N-dimethylformamide, adding 9.5% of prepolymer for synthesizing the UiO-67 carrier, and carrying out oil bath reaction at 125 ℃ for 5.5h to prepare the UiO-67@ Pd @ UiO-67 catalyst with a sandwich structure.
Example 5
The preparation method of the UiO-67@ Pd @ UiO-67 catalyst of this example comprises the following steps:
1) preparation of UiO-67 Carrier:
a) weighing 24mg of zirconium chloride, adding 6mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 2mL of acetic acid, and mixing to obtain a mixed solution A;
b) weighing 22mg of biphenyldicarboxylic acid, adding 6mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 150 mu L of triethylamine, and mixing to obtain a mixed solution B;
c) mixing the mixed solution A and the mixed solution B, transferring the mixed solution A and the mixed solution B into a reaction kettle, putting the mixture into an oven, and reacting for 26 hours at 130 ℃ to prepare the UiO-67 carrier;
2) ultrasonically dispersing the UiO-67 carrier prepared in the step 1) by using 12mL of methanol, adding 50 mu L of Pd nanoparticle prepolymer, reacting for 6h at room temperature, adding 4mL of methanol solution of sodium borohydride with the mass concentration of 1mg/mL, and reacting for 2h at room temperature to prepare the UiO-67@ Pd with the core-shell structure;
3) ultrasonically dispersing the UiO-67@ Pd with the core-shell structure obtained in the step 2) by using 6mL of N, N-dimethylformamide, adding 10% of prepolymer for synthesizing the UiO-67 carrier, and carrying out oil bath reaction at 130 ℃ for 6h to prepare the UiO-67@ Pd @ UiO-67 catalyst with a sandwich structure.
Example 6
The preparation method of the UiO-67@ Pd @ UiO-66 catalyst of this example comprises the following steps:
1) preparation of UiO-67 Carrier:
a) weighing 18.64mg of zirconium chloride, adding 5mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 1.38mL of acetic acid, and mixing to obtain a mixed solution A;
b) weighing 19.36mg of biphenyldicarboxylic acid, adding 5mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 120 mu L of triethylamine, and mixing to obtain a mixed solution B;
c) mixing the mixed solution A and the mixed solution B, transferring the mixed solution A and the mixed solution B into a reaction kettle, putting the mixture into an oven, and reacting for 24 hours at 120 ℃ to prepare the UiO-67 carrier;
2) ultrasonically dispersing the UiO-67 carrier prepared in the step 1) by using 10mL of methanol, adding 44 mu L of Pd nanoparticle prepolymer, reacting for 5h at room temperature, adding 2mL of sodium borohydride methanol solution with the mass concentration of 1mg/mL, and reacting for 1h at room temperature to prepare the UiO-67@ Pd with the core-shell structure;
3) ultrasonically dispersing the UiO-67@ Pd with the core-shell structure obtained in the step 2) by using 4mL of N, N-dimethylformamide, adding 2% of prepolymer for synthesizing the UiO-66 carrier, and carrying out oil bath reaction at 120 ℃ for 5h to prepare the UiO-67@ Pd @ UiO-66 catalyst with a sandwich structure, wherein a scanning electron microscope image of the catalyst is shown in FIG. 8.
Example 7
The preparation method of the UiO-67@ Pd @ UiO-68 catalyst of this example comprises the following steps:
1) preparation of UiO-67 Carrier:
a) weighing 18.64mg of zirconium chloride, adding 5mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 1.38mL of acetic acid, and mixing to obtain a mixed solution A;
b) weighing 19.36mg of biphenyldicarboxylic acid, adding 5mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 120 mu L of triethylamine, and mixing to obtain a mixed solution B;
c) mixing the mixed solution A and the mixed solution B, transferring the mixed solution A and the mixed solution B into a reaction kettle, putting the mixture into an oven, and reacting for 24 hours at 120 ℃ to prepare the UiO-67 carrier;
2) ultrasonically dispersing the UiO-67 carrier prepared in the step 1) by using 10mL of methanol, adding 44 mu L of Pd nanoparticle prepolymer, reacting for 5h at room temperature, adding 2mL of sodium borohydride methanol solution with the mass concentration of 1mg/mL, and reacting for 1h at room temperature to prepare the UiO-67@ Pd with the core-shell structure;
3) ultrasonically dispersing the UiO-67@ Pd with the core-shell structure obtained in the step 2) by using 4mL of N, N-dimethylformamide, adding 5% of a prepolymer for synthesizing the UiO-68 carrier, and carrying out oil bath reaction at 120 ℃ for 5h to prepare the UiO-67@ Pd @ UiO-68 catalyst with a sandwich structure, wherein a scanning electron microscope picture of the catalyst is shown in figure 9.
Comparative example 1
Comparative example Pd/Al2O3The preparation method of the catalyst comprises the following steps:
1) 0.5 wt.% of Al2O3Adding the solution into a pre-synthesized Pd nano particle solution, and stirring and reacting for 48 hours at room temperature;
2) filtering the solid obtained after the reaction is finished, and washing the solid with 5mL of ethanol and 5mL of deionized water for three times respectively;
3) drying the solid at 110 ℃ for 12 h;
4) calcining at 450 deg.C for 3h in air.
The obtained Pd/Al2O3The catalyst is used for preparing styrene by selectively hydrogenating phenylacetylene, and the test conditions and the experimental results are shown in table 1.
TABLE 1
Number of cycles Reaction time/min Reaction temperature/. degree.C Conversion rate/% Selectivity/%)
1 30 50 96.21 70.05
2 30 50 94.36 72.11
3 30 50 91.44 75.39
4 30 50 85.28 78.22
5 30 50 80.56 79.49
Comparative example 2
The comparative example UiO-67 catalyst was prepared as in 1) of example 1;
the experimental result shows that the conversion rate and the selectivity of selective hydrogenation of phenylacetylene catalyzed by UiO-67 are both zero, which indicates that the UiO-67 has no catalytic action.
Comparative example 3
The comparative example UiO-67@ Pd catalyst was prepared as in 2) of example 1;
the results of the experiment are shown in table 2.
TABLE 2
Number of cycles Reaction time/min Reaction temperature/. degree.C Conversion rate/% Selectivity/%)
1 20 9 98.13 87.35
2 20 9 94.87 87.76
3 20 9 70 92.39
4 20 9 58.87 92.9
5 20 9 47.8 93.12
Comparative example 4
The preparation method of the UiO-67@ Pd @ UiO-67 catalyst of the comparative example comprises the following steps:
1) preparation of UiO-67 Carrier:
a) weighing 16mg of zirconium chloride, adding 2mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 0.5mL of acetic acid, and mixing to obtain a mixed solution A;
b) weighing 15mg of biphenyldicarboxylic acid, adding 2mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 90 mu L of triethylamine, and mixing to obtain a mixed solution B;
c) mixing the mixed solution A and the mixed solution B, transferring the mixed solution A and the mixed solution B into a reaction kettle, putting the reaction kettle into an oven, and reacting for 20 hours at 90 ℃ to prepare the UiO-67 carrier;
2) ultrasonically dispersing the UiO-67 carrier prepared in the step 1) by using 6mL of methanol, adding 30 mu L of Pd nanoparticle prepolymer, reacting for 3h at room temperature, adding 1mL of methanol solution of sodium borohydride with the mass concentration of 1mg/mL, and reacting for 0.5h at room temperature to prepare the UiO-67@ Pd with the core-shell structure;
3) ultrasonically dispersing the UiO-67@ Pd with the core-shell structure obtained in the step 2) by using 2mL of N, N-dimethylformamide, adding 6% of prepolymer for synthesizing the UiO-67 carrier, and carrying out oil bath reaction at 120 ℃ for 3h to prepare the UiO-67@ Pd @ UiO-67 catalyst with a sandwich structure.
Comparative example 5
The preparation method of the UiO-67@ Pd @ UiO-67 catalyst of the comparative example comprises the following steps:
1) preparation of UiO-67 Carrier:
a) weighing 25mg of zirconium chloride, adding 8mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 3mL of acetic acid, and mixing to obtain a mixed solution A;
b) weighing 24mg of biphenyldicarboxylic acid, adding 8mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 160 mu L of triethylamine, and mixing to obtain a mixed solution B;
c) mixing the mixed solution A and the mixed solution B, transferring the mixed solution A and the mixed solution B into a reaction kettle, putting the mixture into an oven, and reacting for 28 hours at 140 ℃ to prepare the UiO-67 carrier;
2) ultrasonically dispersing the UiO-67 carrier prepared in the step 1) by using 14mL of methanol, adding 60 mu L of Pd nanoparticle prepolymer, reacting for 8h at room temperature, adding 5mL of sodium borohydride methanol solution with the mass concentration of 1mg/mL, and reacting for 3h at room temperature to prepare the UiO-67@ Pd with the core-shell structure;
3) ultrasonically dispersing the UiO-67@ Pd with the core-shell structure obtained in the step 2) by using 8mL of N, N-dimethylformamide, adding 12% of prepolymer for synthesizing the UiO-67 carrier, and carrying out oil bath reaction at 120 ℃ for 8h to prepare the UiO-67@ Pd @ UiO-67 catalyst with a sandwich structure.
The scanning electron microscope image of the UiO-67@ Pd @ UiO-67 catalyst prepared in comparative example 4 is shown in FIG. 6, the scanning electron microscope image of the UiO-67 carrier prepared in comparative example 5 and the scanning electron microscope image of the UiO-67 carrier prepared in comparative example 67@ Pd @ UiO-67 are shown in FIGS. 5 and 7, respectively, and it can be seen from FIG. 5 that the crystals of the UiO-67 carrier prepared in comparative example 5 have poor morphology and cannot undergo catalytic reaction. FIGS. 6 and 7 also show that the UiO-67@ Pd @ UiO-67 catalysts prepared in comparative examples 4 and 5 have poor morphology and do not catalyze the reaction.
The catalyst UiO-67@ Pd @ UiO-67 prepared in example 1 and the catalyst prepared in comparative examples 1-3 are used for preparing styrene by selectively hydrogenating phenylacetylene, and the specific reaction conditions are as follows: the reaction temperature is 9 ℃, the hydrogen pressure is 0.5MPa, and the reaction time is 27 min.
The results of the experiment are shown in table 3.
TABLE 3
Selectivity/%) Conversion rate/%
Example 1 94.30 97.40
Comparative example 1 64.58 60.35
Comparative example 2 0 0
Comparative example 3 85.45 98.87
As can be seen from Table 3, both the conversion and the selectivity of the UiO-67@ Pd @ UiO-67 catalyst are higher than those of the other catalysts.
The UiO-67@ Pd @ UiO-67 catalyst obtained in example 1 was recycled for 5 times to test the conversion and selectivity of the catalyst, and the results are shown in Table 4.
TABLE 4
Number of cycles Reaction time/min Reaction temperature/. degree.C Selectivity/%) Conversion rate/%
1 27 9 94.30 97.40
2 27 9 93.67 96.50
3 27 9 94.13 96.04
4 27 9 93.85 97.20
5 27 9 93.80 96.31
As can be seen from tables 1 and 4, the UiO-67@ Pd @ UiO-67 catalyst prepared by the method has better stability than that of the traditional catalyst, and the conversion rate and the selectivity basically remain unchanged after 5 times of recycling.
The above examples are only intended to illustrate the detailed process of the present invention, and the present invention is not limited to the above detailed process, i.e., it is not intended that the present invention necessarily depends on the above detailed process for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The catalyst is characterized in that the catalyst takes UiO as a carrier and Pd as an active component; the catalyst is of a sandwich structure and sequentially comprises a UiO crystal with a regular octahedral structure, a Pd nanoparticle material and a UiO porous material from inside to outside.
2. The UiO @ Pd @ UiO catalyst as claimed in claim 1, wherein the loading amount of the active component Pd is 0.1-1% by mass of the UiO carrier;
preferably, the mass percentage of the UiO porous material in the UiO carrier is 0.1-0.5%;
preferably, the UiO is UiO-66, UiO-67 or UiO-68.
3. A process for the preparation of the uo @ Pd @ uo catalyst as defined in claim 1 or 2, wherein the process comprises the steps of:
1) preparation of the UiO carrier: zirconium chloride, phthalic acid, biphenyldicarboxylic acid, terphenyldicarboxylic acid, N-dimethylformamide, acetic acid and triethylamine are used as raw materials, and a UiO carrier is prepared after reaction;
2) ultrasonically dispersing the UiO carrier prepared in the step 1) by using methanol, adding a Pd nanoparticle prepolymer, adding a methanol solution of sodium borohydride for reaction, and preparing the UiO @ Pd with a core-shell structure after the reaction is finished;
3) ultrasonically dispersing the UiO @ Pd core-shell structure prepared in the step 2) by using N, N-dimethylformamide, adding the prepolymer zirconium chloride, phthalic acid, biphenyldicarboxylic acid, terphenyldicarboxylic acid, N-dimethylformamide, acetic acid and triethylamine of the UiO carrier prepared in the step 1) for reacting, and preparing the UiO @ Pd @ UiO catalyst with a sandwich structure after the reaction is finished.
4. The preparation method according to claim 3, wherein in step 1), the UO carrier is a UO-67 carrier, and the amount of the raw materials of the UO-67 carrier is as follows: 18-24 mg of zirconium chloride, 16-22 mg of biphenyldicarboxylic acid, 8-12 mL of N, N-dimethylformamide, 2-4 mL of acetic acid and 200-150 muL of triethylamine;
preferably, in the step 1), the UiO carrier is a UiO-66 carrier, and the dosage of the raw materials of the UiO-66 carrier is as follows: 30-36 mg of zirconium chloride, 22-27 mg of phthalic acid, 8-12 mL of N, N-dimethylformamide and 0.5-1.0 mL of acetic acid;
preferably, in step 1), the UiO carrier is a UiO-68 carrier, and the dosage of the raw materials of the UiO-68 carrier is as follows: 42-47 mg of zirconium chloride, 58-63 mg of terphenyl dicarboxylic acid, 2-5 mL of N, N-dimethylformamide and 0.8-1.5 mL of acetic acid.
5. The preparation method according to claim 3 or 4, wherein in the step 1), the reaction temperature is 100-130 ℃, and the reaction time is 22-26 h.
6. The preparation method according to any one of claims 3 to 5, wherein in the step 2), the amount of the methanol is 8 to 12 mL;
preferably, the dosage of the Pd nanoparticle prepolymer is 40-50 mu L;
preferably, the Pd nanoparticle prepolymer is chloropalladate with the concentration of 20-80 mM/L;
preferably, the mass concentration of the methanol solution of sodium borohydride is 1mg/mL, and the dosage of the methanol solution of sodium borohydride is 2-4 mL.
7. The preparation method according to any one of claims 3 to 6, wherein in the step 3), the amount of the N, N-dimethylformamide is 4 to 6 mL;
in the step 3), the dosage of the prepolymer of the UiO carrier is 8-10% of the dosage of zirconium chloride, phthalic acid, biphenyldicarboxylic acid, terphenyldicarboxylic acid, N-dimethylformamide, acetic acid and triethylamine in the step 1).
8. The method according to any one of claims 4 to 7, wherein the reaction temperature in step 3) is 110 to 130 ℃ and the reaction time is 4 to 6 hours.
9. The method according to any one of claims 4 to 8, wherein the method comprises the steps of:
1) preparation of UiO-67 Carrier:
a) weighing 18-24 mg of zirconium chloride, adding 4-6 mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 1-2 mL of acetic acid and 100-150 mu L of triethylamine, and mixing to obtain a mixed solution A;
b) weighing 16-22 mg of biphenyldicarboxylic acid, adding 4-6 mL of N, N-dimethylformamide for ultrasonic dissolution, then adding 1-2 mL of acetic acid and 100-150 mu L of triethylamine, and mixing to obtain a mixed solution B;
c) mixing the mixed solution A and the mixed solution B, transferring the mixed solution A and the mixed solution B into a reaction kettle, putting the reaction kettle into an oven, and reacting for 22-26 hours at the temperature of 100-130 ℃ to prepare the UiO-67 carrier;
2) ultrasonically dispersing the UiO-67 carrier prepared in the step 1) by using 8-12 mL of methanol, adding 40-50 mu L of Pd nanoparticle prepolymer, reacting at room temperature for 4-6 h, adding 2-4 mL of sodium borohydride methanol solution with the mass concentration of 1mg/mL, and reacting at room temperature for 1-2 h to prepare the UiO-67@ Pd with the core-shell structure;
3) ultrasonically dispersing the UO-67 @ Pd with the core-shell structure obtained in the step 2) by using 4-6 mL of N, N-dimethylformamide, adding 8-10% of the prepolymer for synthesizing the UO-67 carrier, and carrying out oil bath reaction at 110-130 ℃ for 4-6 h to prepare the UO-67 @ Pd @ UO-67 catalyst with a sandwich structure.
10. Use of the uo @ Pd @ uo catalyst according to claim 1 or 2, wherein the uo @ Pd @ uo catalyst is used for the selective hydrogenation of phenylacetylene to styrene.
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