CN111111784B - UiO-67 coated Co catalyst and preparation method and application thereof - Google Patents

UiO-67 coated Co catalyst and preparation method and application thereof Download PDF

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CN111111784B
CN111111784B CN201911276234.8A CN201911276234A CN111111784B CN 111111784 B CN111111784 B CN 111111784B CN 201911276234 A CN201911276234 A CN 201911276234A CN 111111784 B CN111111784 B CN 111111784B
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cobalt salt
dicarboxylic acid
catalyst
bipyridyl
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CN111111784A (en
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王曦
麦裕良
蒋婷婷
陈佳志
李媛
陈晓填
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Institute of Chemical Engineering of Guangdong Academy of Sciences
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Guangdong Research Instititute Of Petrochemical And Fine Chemical Engineering
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    • 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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    • B01J31/2208—Oxygen, e.g. acetylacetonates
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    • 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
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    • 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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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/398—Egg yolk like
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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    • B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
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Abstract

The invention discloses a UiO-67 coated Co catalyst, and a preparation method and application thereof. The UiO-67 coated Co catalyst comprises a carrier and an active component; wherein, the carrier is a metal organic framework material UiO-67, and the active component is Co nano particles; co nanoparticles are confined in the pores of UiO-67. In the UiO-67 prepared by the invention, Co nano particles are confined in the pore canal of the UiO-67 in the Co catalyst, and the Co nano particles have uniform particle size and are highly dispersed. The catalyst has very high activity and stability, and shows excellent catalytic performance and recycling performance when being applied to the low-temperature catalytic oxidation reaction of carbon monoxide.

Description

UiO-67 coated Co catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a UiO-67 coated Co catalyst and a preparation method and application thereof.
Background
Metal nanoparticles have gained a great deal of attention in catalytic research because of their excellent physicochemical properties on the nanoscale. Generally, the smaller the particle size of the metal particles, the higher the surface energy thereof and the more thermodynamically unstable. A common solution is to disperse the metal particles on the surface of the solid support to prevent aggregation. However, during the catalytic reaction, the metal particles are difficult to keep stable under the reaction conditions, and adjacent metal nanoparticles still tend to agglomerate to reduce the surface energy. In order to prevent the agglomeration of the metal nanoparticles, a very effective method is to encapsulate the metal nanoparticles inside the pores of a porous material (such as a molecular sieve or a porous carbon material), and disperse and isolate the metal nanoparticles by using the domain-limiting function of the pores, thereby preventing the agglomeration.
The porous material confinement metal nano-particles can be realized by a pre-synthesis method or a post-introduction method. Pre-synthesis refers to pre-synthesis of metal nanoparticles and then building a porous material on the surface. Some specific capping agents, ions or surfactants are usually required in the pre-synthesis process to stabilize the pre-synthesized metal nanoparticles. However, these stabilizers are difficult to remove after synthesis of the composite of the metal nanoparticles and the porous material, which has an adverse effect on mass transfer and diffusion of substances during the catalytic process. Post-introduction refers to the introduction of metal nanoparticles into the pores of the porous material. The latter method generally requires first synthesizing a porous material support, then introducing a metal precursor into the porous material, and finally reducing the metal precursor with a reducing agent to synthesize metal nanoparticles. Methods such as solvent impregnation, microwave, surface grafting, solid milling and chemical vapour deposition have been developed but have not been well applied, mainly due to the different diffusion resistances of the inner and outer surfaces of the porous material, resulting in an uneven distribution of the metal precursor on the porous material. Therefore, developing a versatile and simple method to synthesize highly dispersed and controllable confined metal nanoparticles of porous materials remains a very significant challenge.
The metal organic framework Materials (MOFs) are porous materials which are formed by connecting metal ion centers and oxygen-containing or nitrogen-containing multidentate organic ligands through coordination bonds and self-assemble and have periodic space three-dimensional network structures. The MOFs have the characteristics of high specific surface area and porosity, adjustable pore channel structure and the like. These properties make MOFs very promising for applications as porous supports to confine metal nanoparticles. Compared with other types of porous materials, the MOFs can establish charge transfer interaction through pi-pi bonds of aromatic rings in ligands, so that the stability and the activity of the metal nanoparticles are improved. The problems of metal agglomeration and loss frequently encountered in the catalytic reaction process can be well inhibited in the MOFs (metal organic frameworks) confinement metal nanoparticle composite material, and the pore confinement and the electronic effect provided by the MOFs framework are benefited. CN 108940368A adopts a pre-synthesis method to construct a zeolite-like framework material ZIF-8 on metal nano particles. CN 108452770A the metal oxide was introduced in MIL-101 by a two-solvent method. However, whether pre-synthesis or post-introduction, the precise control of the loading, dispersion and spatial distribution of the metal nanoparticles is still very limited.
Disclosure of Invention
In order to solve the problems of the limited-domain metal nano particles of the existing porous materials, the invention aims at providing a high-dispersion limited-domain UiO-67-coated Co catalyst, aims at providing a preparation method of the UiO-67-coated Co catalyst, and aims at providing application of the UiO-67-coated Co catalyst in catalytic oxidation reaction of carbon monoxide.
The invention concept of the invention is as follows: introducing a metal precursor by adopting a mode of coupling and coordinating a ligand containing a bipyridyl unit and a cobalt salt, synthesizing UiO-67 by utilizing the ligand containing the metal precursor and a zirconium salt, and then carrying out heat treatment in a reducing atmosphere to obtain the high-dispersion limited-area Co @ UiO-67 catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a UiO-67 wrapped Co catalyst. The UiO-67 coated Co catalyst comprises a carrier and an active component; wherein, the carrier is a metal organic framework material UiO-67, and the active component is Co nano particles; co nanoparticles are confined in the pores of UiO-67.
Preferably, in the UiO-67 wrapped Co catalyst, the loading amount of Co nano particles accounts for 0.1-9.7% of the total mass of the catalyst; more preferably, the loading amount of the Co nano particles accounts for 0.9-9.7% of the total mass of the catalyst.
Preferably, in the UiO-67 wrapped Co catalyst, the particle size of Co nanoparticles is 2 nm-5 nm.
The invention also provides a preparation method of the UiO-67 wrapped Co catalyst.
A preparation method of the UiO-67 wrapped Co catalyst comprises the following steps:
1) preparation of (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) cobalt salt: adding cobalt salt and 2,2 '-dipyridyl-5, 5' -dicarboxylic acid dimethyl ester (or named as 2,2 '-dipyridyl-5, 5' -dicarboxylic acid dimethyl ester) into a solvent, and heating to react to obtain (5,5 '-dicarboxylic acid methyl ester-2, 2' -dipyridyl-) cobalt salt;
2) preparation of (5,5 '-dicarboxylic acid-2, 2' -bipyridine-) cobalt salt: mixing (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridyl-) cobalt salt with an alkali-containing solution, heating for reaction, and adjusting the pH value to 0.5-2 after the reaction is finished to obtain (5,5 '-dicarboxylic acid-2, 2' -bipyridyl-) cobalt salt;
3) preparation of UiO-67 immobilized cobalt salt (cobalt salt @ UiO-67): dispersing zirconium salt and a ligand containing a bipyridyl unit in a solvent, heating for reaction, carrying out solvent exchange on the obtained solid product, and drying to obtain UiO-67 immobilized cobalt salt; wherein the ligand containing the bipyridyl unit is (5,5 ' -dicarboxylic acid-2, 2 ' -bipyridyl-) cobalt salt, or (5,5 ' -dicarboxylic acid-2, 2 ' -bipyridyl-) cobalt salt and 4,4 ' -biphenyldicarboxylic acid;
4) preparation of UiO-67 coated Co (Co @ UiO-67): heating and reacting the UiO-67 immobilized cobalt salt under reducing gas to obtain the UiO-67 wrapped Co catalyst.
Preferably, the catalyst is prepared by a method in which, in step 1), the molar ratio of the cobalt salt to dimethyl 2,2 '-bipyridine-5, 5' -dicarboxylate is 1: (0.8 to 1.2); most preferably, the molar ratio of cobalt salt to dimethyl 2,2 '-bipyridine-5, 5' -dicarboxylate is 1: 1.
preferably, in the step 1) of the preparation method of the catalyst, the heating reaction temperature is 50-80 ℃, and the heating reaction time is 12-36 h; further preferably, in the step 1), the temperature of the heating reaction is 60-70 ℃, and the time of the heating reaction is 22-26 h; most preferably, in step 1), the heating reaction is carried out at 65 ℃ for 24 h.
Preferably, in step 1) of the preparation method of the catalyst, the cobalt salt is at least one selected from cobalt chloride, cobalt nitrate, cobalt sulfate and cobalt acetate.
Preferably, in step 1) of the preparation method of the catalyst, the dosage ratio of the cobalt salt to the solvent is 1 mol: (10-30) L.
Preferably, in step 1) of the preparation method of the catalyst, the solvent is at least one selected from acetonitrile, N-dimethylformamide and acetone; most preferably, in step 1), the solvent is acetonitrile.
Preferably, the preparation method of the catalyst in step 1), after the heating reaction, further comprises the steps of filtering, washing and drying the solid product. The drying is preferably carried out for 12 to 48 hours under vacuum at 100 to 200 ℃.
The preparation method of the catalyst comprises the step 1), wherein the (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridyl-) cobalt salt is a complex formed by coordination coupling of 2,2 '-bipyridyl-5, 5' -dicarboxylic acid dimethyl ester and the cobalt salt.
Preferably, in step 2) of the preparation method of the catalyst, the ratio of the (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridyl-) cobalt salt to the alkali-containing solution is 1 mol: (50-150) L; further preferably, the ratio of the amount of (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) cobalt salt to the alkali-containing solution is 1 mol: (80-120) L.
Preferably, in step 2) of the preparation method of the catalyst, the solution containing the alkali is a mixed solution of an aqueous solution of an alkali metal hydroxide and an organic solvent.
Preferably, in the preparation method of the catalyst, in the solution containing the alkali in the step 2), the concentration of the aqueous solution of the alkali metal hydroxide is 2mol/L to 4 mol/L; more preferably, the concentration of the alkali metal hydroxide aqueous solution is 2.5mol/L to 3.5 mol/L; most preferably, the concentration of the aqueous alkali metal hydroxide solution is 3 mol/L.
Preferably, in the preparation method of the catalyst, step 2) of the solution containing the alkali, the alkali metal hydroxide is selected from at least one of sodium hydroxide and potassium hydroxide; most preferably, the alkali metal hydroxide is sodium hydroxide.
Preferably, in the preparation method of the catalyst, step 2) of the alkali-containing solution, the organic solvent is at least one selected from ethanol, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, acetone and diethyl ether; further preferably, the organic solvent is a mixed solvent of ethanol and tetrahydrofuran; in the mixed solvent, the volume ratio of ethanol to tetrahydrofuran is preferably 1 (0.5-2), and more preferably 1: 1.
In some preferred embodiments of the present invention, the alkali-containing solution is a mixed solution of sodium hydroxide, ethanol and tetrahydrofuran in a volume ratio of 1:1: 1; wherein the concentration of the sodium hydroxide aqueous solution is 3 mol/L.
Preferably, in the step 2) of the preparation method of the catalyst, the heating reaction temperature is 60-80 ℃, and the heating reaction time is 5-10 h.
Preferably, in step 2) of the process for preparing such a catalyst, the pH is adjusted to 1 after the end of the reaction. Starting materials and methods for adjusting the pH are common techniques in the art. For example, hydrochloric acid with a concentration of 1mol/L can be optionally used to adjust the pH.
Preferably, the preparation method of the catalyst further comprises the steps of filtering, washing and drying the obtained solid product after adjusting the pH in the step 2). The drying is preferably carried out for 12 to 48 hours under vacuum at 100 to 200 ℃.
The preparation method of the catalyst comprises the step 2), wherein the (5,5 '-dicarboxylic acid-2, 2' -bipyridyl-) cobalt salt is a complex formed by coordination coupling of 2,2 '-bipyridyl-5, 5' -dicarboxylic acid and cobalt salt.
Preferably, in step 3) of the preparation method of the catalyst, the molar ratio of the zirconium salt, the ligand containing the bipyridyl unit and the solvent is 1: (0.8-1.2): (400 to 2500); more preferably, the molar ratio of the zirconium salt, the ligand containing bipyridyl units and the solvent is 1:1: (500-2300).
Preferably, in the preparation method of the catalyst, in step 3), the zirconium salt is at least one selected from the group consisting of zirconium chloride, zirconium nitrate, zirconium sulfate, zirconium oxychloride and zirconium acetate.
Preferably, in the preparation method of the catalyst, in step 3), when the ligands containing the bipyridyl units are (5,5 '-dicarboxylic acid-2, 2' -bipyridyl-) cobalt salt and 4,4 '-biphenyldicarboxylic acid, the molar ratio of the (5, 5' -dicarboxylic acid-2, 2 '-bipyridyl-) cobalt salt to the 4, 4' -biphenyldicarboxylic acid is 1: (0.1 to 10); further preferably, the molar ratio of (5,5 ' -dicarboxylic acid-2, 2 ' -bipyridine-) cobalt salt to 4,4 ' -biphenyldicarboxylic acid is 1: (0.25 to 9).
Preferably, in the preparation method of the catalyst, in step 3), the solvent is at least one selected from the group consisting of N, N-dimethylformamide, methanol, ethanol and water.
Preferably, in the step 3) of the preparation method of the catalyst, the heating reaction temperature is 60-150 ℃, and the heating reaction time is 24-48 h.
Preferably, the preparation method of the catalyst further comprises the steps of filtering, washing and drying the obtained solid product before solvent exchange in the step 3).
Preferably, the preparation method of the catalyst in step 3), after solvent exchange, further comprises the steps of filtering and washing the product obtained by solvent exchange, and then drying. The drying is preferably carried out for 12 to 48 hours under vacuum at 100 to 200 ℃.
Preferably, in step 3) of the preparation method of the catalyst, the solvent exchange is to immerse the obtained solid product in an exchange solvent for treatment. The exchange solvent is preferably at least one selected from ethyl acetate, acetone and chloroform.
Preferably, in step 3) of the preparation method of the catalyst, the impregnation time of the solvent exchange is 12 to 36 hours.
Preferably, in step 4) of the preparation method of the catalyst, the reducing gas comprises at least one of hydrogen and carbon monoxide; further preferably, the reducing gas is at least one selected from hydrogen and carbon monoxide; or a mixed gas composed of at least one of hydrogen and carbon monoxide and at least one of nitrogen, helium, neon and argon. The volume percentage of hydrogen and/or carbon monoxide in the mixed gas is preferably 5% to 10%.
Preferably, in the preparation method of the catalyst, in the step 4), the heating reaction is specifically carried out at 300-400 ℃ for 0.5-2 h.
The invention also provides application of the UiO-67 wrapped Co catalyst.
An application of the UiO-67 wrapped Co catalyst in the catalytic oxidation reaction of carbon monoxide.
In particular, the catalyst can catalytically oxidize carbon monoxide at low temperatures of 0 ℃ or less, such as low as-20 ℃. The UiO-67 wrapped Co catalyst has good catalytic activity in a temperature range of-20 ℃ to 0 ℃.
The invention has the beneficial effects that:
in the UiO-67 prepared by the invention, Co nano particles are confined in the pore canal of the UiO-67 in the Co catalyst, and the Co nano particles have uniform particle size and are highly dispersed. The catalyst has very high activity and stability, and shows excellent catalytic performance and recycling performance when being applied to the low-temperature catalytic oxidation reaction of carbon monoxide.
Specifically, compared with the prior art, the invention has the following advantages:
1) according to the invention, a metal precursor is introduced into the ligand by a ligand modification method before the UiO-67 is synthesized, so that Co nanoparticles can be uniformly distributed in the UiO-67 pore channel. The method for introducing the metal precursor before can avoid the difference of the diffusion resistance inside and outside the UiO-67, so that the metal precursor can be easily deposited inside the pore channel and uniformly distributed in the frame of the UiO-67. During the reduction process, the chelating sites and geometry on the UiO-67 ligand can synergistically limit the growth of metal particles and confine them in the pores.
2) The invention can regulate the Co supporting amount in UiO-67 by regulating the proportion of two ligands, namely (5,5 ' -dicarboxylic acid-2, 2 ' -bipyridyl-) cobalt salt and 4,4 ' -biphenyldicarboxylic acid. The supporting capacity is adjustable between 0.1 percent and 9.7 percent, and the uniform dispersion can be realized under the condition of high supporting capacity due to the limited domain effect of the UiO-67 ligand and the pore channel.
3) The high-dispersion limited-domain Co @ UiO-67 catalyst disclosed by the invention shows excellent catalytic performance and recycling performance in a low-temperature catalytic oxidation carbon monoxide reaction, shows good activity even at a temperature below 0 ℃, and has higher catalytic activity and stability compared with a traditional impregnation method.
Drawings
FIG. 1 is a TEM image of the Co @ UiO-67 catalyst prepared in example 1;
FIG. 2 is a TEM image of the Co/UiO-67 catalyst prepared in comparative example 1;
FIG. 3 is a graph showing the results of performance tests on catalysts prepared in examples and comparative examples;
FIG. 4 is a graph showing the results of the catalytic stability test of the Co @ UiO-67 catalyst prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used in the examples and comparative examples were obtained from conventional commercial sources unless otherwise specified. Unless otherwise indicated, the testing or testing methods are conventional in the art.
Example 1
A preparation method of a high-dispersion limited-domain Co @ UiO-67 catalyst comprises the following steps:
1) preparation of (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) cobalt chloride. 1mmol of cobalt chloride and 1mmol of dimethyl (2,2 '-bipyridine) -5, 5' -dicarboxylate were added to a 15mL acetonitrile solution and stirred at 65 ℃ for 24 h. After the reaction is finished, (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridyl-) cobalt chloride is obtained, filtered, washed and dried in vacuum at 100 ℃ for 12 hours.
2) Preparation of (5,5 '-dicarboxylic acid-2, 2' -bipyridine-) cobalt chloride. 0.5mmol of (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) cobalt chloride was added to an equal volume of a mixed solution of 50mL of tetrahydrofuran, ethanol and 3M aqueous NaOH, and stirred at 70 ℃ for 5 hours. After the reaction is finished, the temperature is reduced to room temperature, and the pH value is adjusted to 1. The precipitated solid was filtered, washed and dried under vacuum at 100 ℃ for 12 h.
3) Preparation of cobalt chloride @ UiO-67. 0.5mmol of zirconium chloride, 0.25mmol of (5,5 ' -dicarboxylic acid-2, 2 ' -bipyridine-) cobalt chloride and 0.25mmol of 4,4 ' -biphenyldicarboxylic acid were dispersed in 20mL of N, N-dimethylformamide and heated at 150 ℃ for 36 h. The obtained solid product is filtered, washed and dried, and is soaked in chloroform for 24 hours, then filtered, washed and dried under vacuum at 150 ℃ for 12 hours.
4) Preparation of Co @ UiO-67. Heating cobalt chloride @ UiO-67 at 300 ℃ for 2h in a hydrogen atmosphere to obtain Co @ UiO-67.
The mass percentage of cobalt in the catalyst of example 1 was found to be 4.5%.
Example 2
A preparation method of a high-dispersion limited-domain Co @ UiO-67 catalyst comprises the following steps:
1) preparation of cobalt (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) nitrate. 1mmol of cobalt nitrate and 1mmol of dimethyl (2,2 '-bipyridine) -5, 5' -dicarboxylate were added to a 15mL acetonitrile solution and stirred at 65 ℃ for 24 h. After the reaction is finished, (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridyl-) cobalt nitrate is obtained, and the obtained product is filtered, washed and dried in vacuum at 150 ℃ for 24 hours.
2) Preparation of (5,5 '-dicarboxylic acid-2, 2' -bipyridine-) cobalt nitrate. 0.5mmol of cobalt (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) nitrate was added to an equal volume of 50mL of a mixed solution of tetrahydrofuran, ethanol and 3M aqueous NaOH, and stirred at 70 ℃ for 10 h. After the reaction is finished, the temperature is reduced to room temperature, and the pH value is adjusted to 1. Filtering and washing the precipitated solid, and drying the solid for 24 hours in vacuum at the temperature of 150 ℃;
3) preparation of cobalt nitrate @ UiO-67. 0.5mmol of zirconium nitrate, 0.05mmol of cobalt (5,5 ' -dicarboxylic acid-2, 2 ' -bipyridine-) nitrate and 0.45mmol of 4,4 ' -biphenyldicarboxylic acid were dispersed in 20mL of methanol and heated at 85 ℃ for 48 hours. Filtering, washing and drying the obtained solid product, putting the solid product into acetone for soaking for 24 hours, then filtering, washing and vacuum-drying at 150 ℃ for 12 hours;
4) preparation of Co @ UiO-67. Heating the cobalt nitrate @ UiO-67 at 350 ℃ for 0.5h in a carbon monoxide atmosphere to obtain the Co @ UiO-67.
The mass percentage of cobalt in the catalyst of example 2 was determined to be 0.9%.
Example 3
A preparation method of a high-dispersion limited-domain Co @ UiO-67 catalyst comprises the following steps:
1) preparation of (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) cobalt sulfate. 1mmol of cobalt sulfate and 1mmol of dimethyl (2,2 '-bipyridine) -5, 5' -dicarboxylate were added to 15mL of acetonitrile solution and stirred at 65 ℃ for 24 h. After the reaction is finished, (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) cobaltous sulfate is obtained, filtered, washed and dried in vacuum at 100 ℃ for 48 hours.
2) Preparation of (5,5 '-dicarboxylic acid-2, 2' -bipyridine-) cobalt sulfate. 0.5mmol of cobalt (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) sulfate was added to an equal volume of a mixed solution of 50mL of tetrahydrofuran, ethanol and 3M aqueous NaOH, and stirred at 70 ℃ for 10 hours. After the reaction is finished, the temperature is reduced to room temperature, and the pH value is adjusted to 1. The precipitated solid was filtered, washed and dried under vacuum at 100 ℃ for 48 h.
3) Preparation of cobalt sulfate @ UiO-67. 0.5mmol of zirconium sulfate, 0.20mmol of (5,5 ' -dicarboxylic acid-2, 2 ' -bipyridine-) cobalt sulfate and 0.30mmol of 4,4 ' -biphenyldicarboxylic acid were dispersed in 20mL of water and heated at 60 ℃ for 48 hours. The obtained solid product is filtered, washed and dried, and is soaked in ethyl acetate for 24 hours, then filtered, washed and dried in vacuum at 100 ℃ for 48 hours.
4) Preparation of Co @ UiO-67. The cobalt sulfate @ UiO-67 was heated at 400 ℃ for 2 hours in a mixed atmosphere of 5% by volume of hydrogen and 95% by volume of nitrogen to produce Co @ UiO-67.
The mass percentage of cobalt in the catalyst of example 3 was found to be 3.8%.
Example 4
A preparation method of a high-dispersion limited-range Co @ UiO-67 catalyst comprises the following steps:
1) preparation of cobalt (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) acetate. 1mmol of cobalt acetate and 1mmol of dimethyl (2,2 '-bipyridine) -5, 5' -dicarboxylate were added to a 15mL acetonitrile solution and stirred at 65 ℃ for 24 h. After the reaction is finished, (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) cobalt acetate is obtained, filtered, washed and dried in vacuum at 200 ℃ for 12 h.
2) Preparing (5,5 '-dicarboxylic acid-2, 2' -bipyridyl-) cobalt acetate. 0.5mmol of cobalt (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) acetate was added to an equal volume of a mixed solution of 50mL of tetrahydrofuran, ethanol and 3M aqueous NaOH, and stirred at 70 ℃ for 8 h. After the reaction is finished, the temperature is reduced to room temperature, and the pH value is adjusted to 1. The precipitated solid was filtered and washed and dried under vacuum at 200 ℃ for 12 h.
3) Preparing cobalt acetate @ UiO-67. 0.5mmol of zirconium acetate, 0.40mmol of cobalt (5,5 ' -dicarboxylic acid-2, 2 ' -bipyridine-) acetate and 0.10mmol of 4,4 ' -biphenyldicarboxylic acid were dispersed in 20mL of ethanol and heated at 90 ℃ for 24 h. The obtained solid product is filtered, washed and dried, and is soaked in chloroform for 24 hours, then filtered, washed and dried under vacuum at 200 ℃ for 12 hours.
4) Preparation of Co @ UiO-67. The cobalt acetate @ UiO-67 is heated for 1h at 400 ℃ in the mixed atmosphere of 10 volume percent of carbon monoxide and 90 volume percent of helium to prepare the Co @ UiO-67.
The mass percent of cobalt in the catalyst of example 4 was determined to be 7.7%.
Example 5
A preparation method of a high-dispersion limited-domain Co @ UiO-67 catalyst comprises the following steps:
1) preparation of (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) cobalt chloride. 1mmol of cobalt chloride and 1mmol of dimethyl (2,2 '-bipyridine) -5, 5' -dicarboxylate were added to a 15mL acetonitrile solution and stirred at 65 ℃ for 24 h. After the reaction is finished, (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridyl-) cobalt chloride is obtained, filtered, washed and dried in vacuum at 100 ℃ for 12 hours.
2) Preparation of (5,5 '-dicarboxylic acid-2, 2' -bipyridine-) cobalt chloride. 0.5mmol of (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) cobalt chloride was added to an equal volume of a mixed solution of 50mL of tetrahydrofuran, ethanol and 3M aqueous NaOH, and stirred at 70 ℃ for 10 hours. After the reaction is finished, the temperature is reduced to room temperature, and the pH value is adjusted to 1. The precipitated solid was filtered and washed, and dried under vacuum at 100 ℃ for 12 hours.
3) Preparation of cobalt chloride @ UiO-67. 0.5mmol of zirconium oxychloride, 0.5mmol of (5,5 '-dicarboxylic acid-2, 2' -bipyridine-) cobalt chloride were dispersed in 20mL of N, N-dimethylformamide and heated at 150 ℃ for 36 h. The obtained solid product is filtered, washed and dried, and is soaked in chloroform for 24 hours, then filtered, washed and dried in vacuum at 100 ℃ for 12 hours.
4) Preparation of Co @ UiO-67. The cobalt chloride @ UiO-67 is heated for 2 hours at 400 ℃ in the mixed atmosphere of 5% hydrogen and 95% argon by volume percentage to prepare the Co @ UiO-67.
The mass percentage of cobalt in the catalyst of example 5 was determined to be 9.7%.
Comparative example 1
A preparation method of a Co/UiO-67 catalyst comprises the following steps:
1) preparation of UiO-67. Dissolving 0.5mmol of zirconium chloride and 0.5mmol of 4, 4' -biphenyldicarboxylic acid in 20mL of N, N-dimethylformamide, reacting for 36h at 150 ℃, filtering and washing the obtained solid product, and drying in vacuum at 150 ℃ for 12h to obtain a metal organic framework carrier material UiO-67;
2) cobalt chloride/UiO-67 was prepared. Fully dissolving 0.25mmol of cobalt chloride in 30mL of acetonitrile, then adding 300mg of UiO-67, soaking at room temperature for 24h, evaporating to remove acetonitrile, and vacuum-drying at 150 ℃ for 12 h;
3) preparation of Co/UiO-67. The cobalt chloride/UiO-67 is heated for 2h at 400 ℃ in the mixed atmosphere of 5% hydrogen and 95% argon by volume percent to prepare Co/UiO-67.
The catalyst of comparative example 1 was found to have a cobalt content of 4.6% by weight.
Characterization analysis
The catalysts prepared in example 1 and comparative example 1 were characterized by field emission transmission electron microscopy, and the attached FIG. 1 and FIG. 2 are TEM images of the Co @ UiO-67 catalyst prepared in example 1 and the Co/UiO-67 catalyst prepared in comparative example 1, respectively. As can be seen from FIG. 1, in the catalyst prepared in example 1, Co nanoparticles are uniformly distributed on UiO-67, and the average size of the Co nanoparticles is about 2-5 nm. Only a small amount of Co particles were observed at the edges of UiO-67, indicating that most of the Co nanoparticles were inside UiO-67. As can be seen from FIG. 2, the average size of Co nanoparticles in the catalyst prepared in comparative example 1 is about 5-10 nm, and serious agglomeration occurs, and many particles are deposited on the outer surface of UiO-67.
Application testing
Firstly, the catalysts prepared in examples 1-5 and comparative example 1 are subjected to carbon monoxide catalytic oxidation performance test. The test conditions were as follows: the reaction raw material gas adopts 0.1 vol.% CO and 20 vol.% O 2 79.9 vol.% He, a total gas flow rate of 25mL/min, a catalyst size of 40-60 meshes, a loading of 200mg, and a space velocity of 7500 mL/g/h. The test method is as follows: the raw material gas passes through a U-shaped quartz tube filled with a catalyst, the U-shaped quartz tube is placed in a salt bath with ice to control the reaction temperature, and after the reaction gas reacts for 20min at a certain temperature,the gas is subjected to gas chromatograph to detect the components of the reaction gas on line. The catalyst activity on carbon monoxide is represented by the conversion of carbon monoxide by the catalyst at each temperature calculated by taking the average of three tests at each temperature. The results of the catalyst performance tests obtained are shown in FIG. 3.
As can be seen from fig. 3: the high-dispersion limited-domain Co @ UiO-67 catalyst prepared by the method has better reaction activity than the supported Co/UiO-67 catalyst in the comparative example 1 under the test conditions. The catalyst prepared in example 1 achieves complete conversion of carbon monoxide at 20 c, whereas the catalyst prepared in comparative example 1 achieves complete conversion of carbon monoxide at 90 c. This is mainly because the preparation method in comparative example 1 is an impregnation method, and the supported Co nanoparticles are mainly concentrated on the surface of the UiO-67 carrier, and are easily migrated during the preparation and reaction processes to undergo agglomeration sintering, thereby resulting in a great reduction in activity.
Secondly, the catalyst prepared in example 1 is applied to a catalytic stability test. The test conditions were the same as the performance test conditions, and the carbon monoxide conversion at the test time from the start of the reaction was recorded by continuously passing the raw material gas through the catalyst at room temperature. The results of the catalytic stability test are shown in FIG. 4.
As can be seen from fig. 4: under these conditions, the catalyst prepared in example 1 was able to continuously convert carbon monoxide into carbon dioxide for 72 hours or more, and the conversion of carbon monoxide did not decrease after the reaction proceeded for 72 hours. The results show that the catalyst prepared in example 1 exhibits very excellent catalytic stability under the test conditions.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A UiO-67 coated Co catalyst comprises a carrier and an active component, and is characterized in that: the carrier is a metal organic framework material UiO-67, and the active component is Co nano particles; the Co nano particles are confined in the pore channel of the UiO-67;
the preparation method of the UiO-67 wrapped Co catalyst comprises the following steps:
1) preparation of (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) cobalt salt: adding cobalt salt and 2,2 '-bipyridyl-5, 5' -dicarboxylic acid dimethyl ester into a solvent, and heating for reaction to obtain (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridyl-) cobalt salt;
2) preparation of (5,5 '-dicarboxylic acid-2, 2' -bipyridine-) cobalt salt: mixing (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridyl-) cobalt salt with an alkali-containing solution, heating for reaction, and adjusting the pH value to 0.5-2 after the reaction is finished to obtain (5,5 '-dicarboxylic acid-2, 2' -bipyridyl-) cobalt salt;
3) preparation of UiO-67 immobilized cobalt salt: dispersing zirconium salt and a ligand containing a bipyridyl unit in a solvent, heating for reaction, carrying out solvent exchange on the obtained solid product, and drying to obtain UiO-67 immobilized cobalt salt; the ligand containing the bipyridyl unit is (5,5 ' -dicarboxylic acid-2, 2 ' -bipyridyl-) cobalt salt, or (5,5 ' -dicarboxylic acid-2, 2 ' -bipyridyl-) cobalt salt and 4,4 ' -biphenyldicarboxylic acid;
4) preparation of UiO-67 coated Co: heating and reacting the UiO-67 immobilized cobalt salt under reducing gas to obtain the UiO-67 wrapped Co catalyst.
2. The UiO-67 encapsulated Co catalyst of claim 1, wherein: the loading amount of the Co nano particles accounts for 0.1-9.7% of the total mass of the catalyst.
3. A method of preparing the UiO-67 coated Co catalyst of claim 1 or 2, wherein: the method comprises the following steps:
1) preparation of (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) cobalt salt: adding cobalt salt and 2,2 '-bipyridine-5, 5' -dicarboxylic acid dimethyl ester into a solvent, and heating for reaction to obtain (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridine-) cobalt salt;
2) preparation of (5,5 '-dicarboxylic acid-2, 2' -bipyridine-) cobalt salt: mixing (5,5 '-dicarboxylic acid methyl ester-2, 2' -bipyridyl-) cobalt salt with an alkali-containing solution, heating for reaction, and adjusting the pH value to 0.5-2 after the reaction is finished to obtain (5,5 '-dicarboxylic acid-2, 2' -bipyridyl-) cobalt salt;
3) preparing UiO-67 immobilized cobalt salt: dispersing zirconium salt and a ligand containing a bipyridyl unit in a solvent, heating for reaction, carrying out solvent exchange on the obtained solid product, and drying to obtain UiO-67 immobilized cobalt salt; the ligand containing the bipyridyl unit is (5,5 ' -dicarboxylic acid-2, 2 ' -bipyridyl-) cobalt salt, or (5,5 ' -dicarboxylic acid-2, 2 ' -bipyridyl-) cobalt salt and 4,4 ' -biphenyldicarboxylic acid;
4) preparation of UiO-67 Encapsulated Co: heating and reacting the UiO-67 immobilized cobalt salt under reducing gas to obtain the UiO-67 wrapped Co catalyst.
4. The production method according to claim 3, characterized in that: in the step 1), the molar ratio of the cobalt salt to the dimethyl 2,2 '-bipyridine-5, 5' -dicarboxylate is 1: (0.8-1.2); the heating reaction temperature is 50-80 ℃, and the heating reaction time is 12-36 h.
5. The production method according to claim 3 or 4, characterized in that: in the step 1), the cobalt salt is at least one selected from cobalt chloride, cobalt nitrate, cobalt sulfate and cobalt acetate.
6. The production method according to claim 3, characterized in that: in the step 2), the alkali-containing solution is a mixed solution of an alkali metal hydroxide aqueous solution and an organic solvent; the alkali metal hydroxide is selected from at least one of sodium hydroxide and potassium hydroxide; the organic solvent is selected from ethanol, tetrahydrofuran,N,N-at least one of dimethylformamide, dimethyl sulfoxide, acetone, diethyl ether; the heating reaction temperature is 60-80 ℃, and the heating reaction time is 5-10 h.
7. The production method according to claim 3, characterized in that:in the step 3), the molar ratio of the zirconium salt, the ligand containing the bipyridyl unit and the solvent is 1: (0.8-1.2): (400 to 2500); the zirconium salt is at least one selected from zirconium chloride, zirconium nitrate, zirconium sulfate, zirconium oxychloride and zirconium acetate; the solvent is selected fromN,N-at least one of dimethylformamide, methanol, ethanol, water; the heating reaction temperature is 60-150 ℃, and the heating reaction time is 24-48 h.
8. The production method according to claim 3, characterized in that: in the step 4), the reducing gas includes at least one of hydrogen and carbon monoxide.
9. The production method according to claim 3, characterized in that: in the step 4), the heating reaction is carried out for 0.5-2 h at the temperature of 300-400 ℃.
10. Use of the UiO-67 coated Co catalyst of claim 1 or 2 in a carbon monoxide catalytic oxidation reaction.
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KR101676442B1 (en) * 2015-07-13 2016-11-16 울산과학기술원 Method for regeneration of metal-organic framework
CN107774331A (en) * 2017-10-25 2018-03-09 宿迁市振兴化工有限公司 A kind of Metal Supported MOFs catalyst and preparation method thereof and the application in PMDPTA synthesis

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