CN112642487A - UiO-67 packaged metal nanoparticle catalyst and preparation method and application thereof - Google Patents

UiO-67 packaged metal nanoparticle catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN112642487A
CN112642487A CN202011432771.XA CN202011432771A CN112642487A CN 112642487 A CN112642487 A CN 112642487A CN 202011432771 A CN202011432771 A CN 202011432771A CN 112642487 A CN112642487 A CN 112642487A
Authority
CN
China
Prior art keywords
uio
pdco
salt
nanoparticle catalyst
metal nanoparticle
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202011432771.XA
Other languages
Chinese (zh)
Other versions
CN112642487B (en
Inventor
王曦
麦裕良
蒋婷婷
陈佳志
陈晓填
李媛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Chemical Engineering of Guangdong Academy of Sciences
Original Assignee
Institute of Chemical Engineering of Guangdong Academy of Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Chemical Engineering of Guangdong Academy of Sciences filed Critical Institute of Chemical Engineering of Guangdong Academy of Sciences
Priority to CN202011432771.XA priority Critical patent/CN112642487B/en
Publication of CN112642487A publication Critical patent/CN112642487A/en
Application granted granted Critical
Publication of CN112642487B publication Critical patent/CN112642487B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • B01J35/23—
    • B01J35/394—
    • B01J35/397—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/06—Polluted air
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium

Abstract

The invention discloses a UiO-67 packaged metal nanoparticle catalyst and a preparation method and application thereof. The UiO-67 encapsulated metal nanoparticle catalyst comprises a carrier and an active component; wherein the carrier is a metal organic framework material UiO-67, and the active component is PdCo alloy nano particles; the PdCo alloy nanoparticles are encapsulated in the inner cavity of the UiO-67. In the UiO-67 encapsulated metal nanoparticle catalyst prepared by the invention, PdCo alloy nanoparticles are encapsulated in the inner cavity of the UiO-67, the particle size of the PdCo alloy nanoparticles is uniform and highly dispersed, the PdCo alloy nanoparticles have very high activity, and the PdCo alloy nanoparticles show excellent catalytic performance when applied to the catalytic oxidation reaction of acetaldehyde.

Description

UiO-67 packaged metal nanoparticle catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a UiO-67 encapsulated metal nanoparticle catalyst and a preparation method and application thereof.
Background
With the continuous improvement of the living standard of people and the rapid development of the automobile industry, automobiles have entered the daily life of common people, and the problem of air quality pollution in automobiles, which is directly related to physical and mental health, is increasingly concerned due to the continuous improvement of the environmental protection consciousness and the self-protection consciousness of people. It has been recognized that air pollution in vehicles has become a stealth killer, and Volatile Organic Compounds (VOCs) are the most significant of the air pollution and seriously harm human health.
At present, each whole vehicle factory mainly uses green materials through development aiming at the management and control of VOCs in vehicles, reduces the direct addition of each object substance in materials and parts used in the vehicles, and further reduces the release amount of VOCs of the whole vehicles. However, acetaldehyde is not a direct additive in materials and parts, but is generated by decomposition of other substances in the use process, is greatly influenced by seasons and environment, is also a substance which is easy to exceed standards of the whole vehicle, and the generation mechanism and influencing factors of acetaldehyde are always hot spots and control difficulties of research in the automobile industry. Of the eight substances controlled by the in-vehicle VOCs specified in the national standard GB/T27630-2011, acetaldehyde is the most difficult substance to control, and the overall average value in the industry is 0.078mg/m3Seriously exceeds the specified limit value of 0.050mg/m3. Acetaldehyde content of main interior trim parts in a vehicle, such as a seat, a door guard plate, a ceiling, a carpet, a front wall, an instrument panel, a secondary instrument panel, a spare tire cover plate and the like, is a main reason for over standard of acetaldehyde content of the whole vehicle.
Acetaldehyde is an irritant gas pollutant, and symptoms such as headache, nausea, immunity reduction, allergy and the like can occur after long-term inhalation of acetaldehyde gas, and deformity, cancer and the like can be caused seriously. Therefore, the research on the technical means for effectively degrading the acetaldehyde gas is shownThis is particularly important. At present, the treatment of acetaldehyde mainly comprises methods of adsorbing by an adsorbent, photocatalysis by a photocatalyst, thermal catalytic oxidation for removing acetaldehyde and the like. For the adsorption method, when the adsorption saturation of adsorbents such as activated carbon/molecular sieve is reached, the adsorbents become invalid, and if the adsorbents are not replaced in time, the adsorbents can desorb acetaldehyde to generate secondary pollution. The photocatalytic method uses photocatalyst (TiO)2) Acetaldehyde is degraded, but an additional ultraviolet light source is usually needed, and the degradation efficiency under visible light is low, so that the wide application of the acetaldehyde is limited. The thermal catalytic oxidation method can completely oxidize acetaldehyde into CO2And H2O, does not produce secondary pollution, is the most thorough method for removing acetaldehyde, and has important practical application value. However, the single catalysts developed at present have the defects of unsatisfactory adsorptivity, incapability of enriching on the surface and low catalytic efficiency; in most cases, the temperature at which acetaldehyde is completely converted is relatively high, in some cases even above 200 ℃. These problems have been the stigmation of the development of catalytic purification materials, and it is required to improve the preparation method and process, prepare porous materials and the like to increase the specific surface area of the catalyst, or prepare composite catalysts by doping, loading, modifying and the like to improve the catalytic efficiency for acetaldehyde.
Disclosure of Invention
In order to solve the problems of the prior acetaldehyde catalytic purification material, the invention aims to provide a UiO-67 encapsulated metal nanoparticle catalyst PdCo @ UiO-67, a second aim of the invention is to provide a preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, and a third aim of the invention is to provide application of the UiO-67 encapsulated metal nanoparticle catalyst in acetaldehyde catalytic oxidation reaction.
The invention concept of the invention is as follows: the metal organic framework material UiO-67 is prepared by adopting zirconium salt and an organic ligand containing a bipyridine unit through a solvothermal method, then the bipyridine unit is utilized to be coupled and coordinated with Pd salt and Co salt, and then the thermal treatment is carried out under a reducing atmosphere, so that the nano-particle catalyst of the UiO-67 encapsulated PdCo alloy is prepared.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a UiO-67 encapsulated metal nanoparticle catalyst, which comprises a carrier and an active component; the carrier is a metal organic framework material UiO-67, and the active component is PdCo alloy nano particles; the PdCo alloy nanoparticles are confined in the lumen of the UiO-67 frame.
Preferably, in the UiO-67 encapsulated metal nanoparticle catalyst, the loading amount of the PdCo alloy nanoparticles is 0.1-5% of the mass of the UiO-67; further preferably, the loading amount of the PdCo alloy nanoparticles is 0.5-3% of the mass of UiO-67.
Preferably, the mole ratio of Pd/Co in the PdCo alloy nanoparticles is 9: 1-1: 9; further preferably, the mole ratio of Pd/Co in the PdCo alloy nanoparticles is 2: 1-1: 2.
The invention also provides a preparation method of the UiO-67 encapsulated metal nanoparticle catalyst.
A preparation method of the UiO-67 encapsulated metal nanoparticle catalyst comprises the following steps:
1) preparing a metal organic framework material UiO-67: dissolving zirconium salt and a polydentate carboxylic acid ligand in a solvent, and carrying out a solvothermal reaction to obtain a metal organic framework material UiO-67; the polydentate carboxylic acid ligand comprises bipyridyl units;
2) preparing a UiO-67 immobilized PdCo salt material: dissolving palladium salt and cobalt salt in a solvent, then adding the UiO-67, heating for reaction, carrying out solvent exchange on the obtained solid product, and drying to obtain a UiO-67 immobilized PdCo salt material;
3) preparation of the UiO-67 encapsulated metal nanoparticle catalyst: and carrying out heating reaction on the UiO-67 immobilized PdCo salt material under reducing gas to obtain the UiO-67 encapsulated metal nanoparticle catalyst.
Preferably, in step 1) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the molar ratio of the zirconium salt, the polydentate carboxylic acid ligand and the solvent is 1: (1-1.2): (400 to 1800); further preferably, the molar ratio of the zirconium salt, the polydentate carboxylic acid ligand and the solvent is 1: 1: (500-1700).
Preferably, in step 1) of this method for preparing a UiO-67 encapsulated metal nanoparticle catalyst, the zirconium salt includes at least one of zirconium chloride, zirconium nitrate, zirconium sulfate, zirconium oxychloride, zirconium acetate; further preferably, the zirconium salt is selected from at least one of zirconium chloride, zirconium nitrate, and zirconium oxychloride.
Preferably, in step 1) of this method of preparing a uo-67 encapsulated metal nanoparticle catalyst, the polydentate carboxylic acid ligands are selected from 2,2 ' -bipyridine-5, 5 ' -dicarboxylic acid, or the polydentate carboxylic acid ligands are a combination of 2,2 ' -bipyridine-5, 5 ' -dicarboxylic acid and 4,4 ' -biphenyldicarboxylic acid. When the polydentate carboxylic acid ligand is selected from the group consisting of 2,2 '-bipyridine-5, 5' -dicarboxylic acid and 4,4 '-biphenyldicarboxylic acid, the molar ratio of 2, 2' -bipyridine-5, 5 '-dicarboxylic acid to 4, 4' -biphenyldicarboxylic acid is preferably 1: (1-1.5).
Preferably, in step 1) of this method for preparing a UiO-67 encapsulated metal nanoparticle catalyst, the solvent includes at least one of N, N-dimethylformamide, methanol, ethanol, isopropanol, tetrahydrofuran, dimethyl sulfoxide, acetone, diethyl ether, and water; further preferably, the solvent is at least one selected from the group consisting of N, N-dimethylformamide, ethanol, and water.
Preferably, in step 1) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the temperature of the solvothermal reaction is 60-150 ℃, and the time of the solvothermal reaction is 24-48 h; more preferably, the solvent thermal reaction is carried out for 24 to 48 hours at a temperature of between 100 and 120 ℃.
Preferably, the method for preparing the UiO-67 encapsulated metal nanoparticle catalyst in step 1) further comprises the steps of filtering, washing and drying the obtained solid product after the solvothermal reaction. The drying is vacuum drying for 12 to 48 hours at the temperature of between 100 and 200 ℃; further preferably, the drying is vacuum drying at 100 ℃ to 150 ℃ for 12 h.
Preferably, in step 2) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the palladium salt comprises at least one of palladium chloride, palladium nitrate, bis-acetonitrile palladium chloride and palladium acetylacetonate; the cobalt salt comprises at least one of cobalt chloride, cobalt nitrate, cobalt sulfate and cobalt acetate.
Preferably, in step 2) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the solvent used for dissolving the metal salt comprises at least one of acetonitrile, N-dimethylformamide and acetone; most preferably, the solvent used to dissolve the metal salt in step 2) is acetonitrile.
Preferably, in the step 2) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the heating reaction temperature is 50-80 ℃, and the heating reaction time is 12-36 h; further preferably, the temperature of the heating reaction is 60-70 ℃, and the time of the heating reaction is 22-26 h; most preferably, the heating reaction is at 65 ℃ for 24 h.
Preferably, the method for preparing the UiO-67 encapsulated metal nanoparticle catalyst in step 2) further comprises the steps of filtering and washing the obtained solid product before solvent exchange.
Preferably, in step 2) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the solvent exchange is to immerse the washed solid product in an exchange solvent. The time for solvent exchange is preferably 3 days, with solvent exchange every 24 h. The exchange solvent is preferably at least one of ethyl acetate, acetone, and chloroform.
Preferably, the method for preparing the UiO-67 encapsulated metal nanoparticle catalyst in step 2) further comprises the steps of filtering and washing a product obtained by solvent exchange before drying.
Preferably, in the step 2) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the drying is carried out for 12 to 48 hours under the vacuum drying at the temperature of between 100 and 200 ℃; most preferably, the drying is vacuum drying at 150 ℃ for 12 h.
Preferably, in step 3) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the reducing gas comprises at least one of hydrogen and carbon monoxide; further preferably, the reducing gas is selected from at least one of 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 step 3) of the preparation method of the UiO-67 encapsulated metal nanoparticle catalyst, the heating reaction is specifically carried out at 300-400 ℃ for 0.5-2 h.
The invention also provides application of the UiO-67 encapsulated metal nanoparticle catalyst in acetaldehyde catalytic oxidation reaction.
The reaction temperature of the acetaldehyde catalytic oxidation reaction is 20-250 ℃, and preferably 80-220 ℃.
The invention has the beneficial effects that:
in the UiO-67 packaged metal nanoparticle catalyst, PdCo alloy nanoparticles are confined in the inner cavity of the pore channel of the UiO-67, and are uniform in particle size and highly dispersed. The catalyst has very high activity and stability, and shows excellent catalytic performance when being applied to acetaldehyde catalytic oxidation reaction.
Compared with the prior art, the invention has the following advantages:
1) the metal organic framework material UiO-67 is used as a carrier, the bipyridyl units in the ligands are coordinated with metal ions, and N atoms exposed out of the bipyridyl units are coupled and coordinated with the active component PdCo, so that the interaction force is strong. The method can ensure that different metal precursors are uniformly distributed in the UiO-67 framework, so that alloy particles are easier to form, and the interaction force of different metals in the alloy particles is stronger. During the reduction process, the chelating sites and geometry on the UiO-67 ligand can synergistically limit the growth of alloy nanoparticles and confine them in the channels.
2) The high-dispersion limited-domain PdCo @ UiO-67 catalyst disclosed by the invention has excellent catalytic performance in an acetaldehyde catalytic oxidation reaction, acetaldehyde can be completely catalytically converted at low temperature, and the catalyst shows better synergistic effect and higher catalytic activity compared with a single metal or PdCo alloy particles deposited on the outer surface of the UiO-67.
Drawings
FIG. 1 is Pd obtained in example 12Co1TEM image of @ UiO-67 catalyst;
FIG. 2 is a graph showing the results of performance tests of catalysts prepared in examples and comparative examples.
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 UiO-67 encapsulated PdCo alloy nanoparticle catalyst PdCo @ UiO-67 comprises the following steps:
1) preparation of metal organic framework support material UiO-67
Dissolving 1mmol of zirconium chloride and 1mmol of 2,2 '-bipyridine-5, 5' -dicarboxylic acid in 60mL of N, N-dimethylformamide, reacting at 120 ℃ for 24h, filtering and washing the obtained solid product, and drying at 150 ℃ in vacuum for 12h to obtain the metal organic framework support material UiO-67.
2) Preparation of UiO-67 immobilized PdCo salt material
Fully dissolving a certain amount of diacetonitrile palladium chloride and cobalt nitrate in 30mL of acetonitrile, then adding a metal organic framework carrier material UiO-67, and controlling Pd2+/Co2+In a molar ratio of 2:1, with a total metal content (Pd)2++Co2+) The mass ratio of the support material UiO-67 was controlled to 2 wt%. Reacting at the constant temperature of 65 ℃ for 24h, cooling to room temperature, filtering and washing, soaking the solid in 30mL ethyl acetate, replacing the ethyl acetate once every 24h, continuously exchanging for 3 days, filtering and washing, and vacuum drying at 150 ℃ for 12h to obtain the metal organic framework material immobilized PdCo salt material.
3) Preparation of PdCo @ UiO-67 catalyst
The UiO-67 immobilized PdCo salt material is placed in a hydrogen atmosphere and heated for 2 hours at 300 ℃ to prepare Pd2Co1@UiO-67(2％)。
FIG. 1 shows Pd obtained in example 12Co1TEM image of @ UiO-67 catalyst.FIG. 1 shows a schematic view of aShows that the catalyst is uniformly dispersed with sodium with the particle size of 2-6 nmRice granules.
Example 2
A preparation method of a UiO-67 encapsulated PdCo alloy nanoparticle catalyst PdCo @ UiO-67 comprises the following steps:
1) preparation of metal organic framework support material UiO-67
Dissolving 1mmol of zirconium chloride and 1mmol of 2,2 '-bipyridine-5, 5' -dicarboxylic acid in 60mL of N, N-dimethylformamide, reacting at 120 ℃ for 24h, filtering and washing the obtained solid product, and drying at 150 ℃ in vacuum for 12h to obtain the metal organic framework support material UiO-67.
2) Preparation of UiO-67 immobilized PdCo salt material
Fully dissolving a certain amount of diacetonitrile palladium chloride and cobalt acetate in 30mL of acetonitrile, then adding a metal organic framework carrier material UiO-67, and controlling Pd2+/Co2+In a molar ratio of 2:1, with a total metal content (Pd)2++Co2+) The mass ratio of the support material UiO-67 was controlled to 0.5 wt%. Reacting at the constant temperature of 65 ℃ for 24h, cooling to room temperature, filtering and washing, soaking the solid in 30mL ethyl acetate, replacing the ethyl acetate once every 24h, continuously exchanging for 3 days, filtering and washing, and vacuum drying at 150 ℃ for 12h to obtain the metal organic framework material immobilized PdCo salt material.
3) Preparation of PdCo @ UiO-67 catalyst
The UiO-67 immobilized PdCo salt material is placed in a carbon monoxide atmosphere and heated for 0.5h at 350 ℃ to prepare Pd2Co1@UiO-67(0.5％)。
Example 3
A preparation method of a UiO-67 encapsulated PdCo alloy nanoparticle catalyst PdCo @ UiO-67 comprises the following steps:
1) preparation of metal organic framework support material UiO-67
Dissolving 1mmol of zirconium chloride and 1mmol of 2,2 '-bipyridine-5, 5' -dicarboxylic acid in 60mL of N, N-dimethylformamide, reacting at 120 ℃ for 24h, filtering and washing the obtained solid product, and drying at 150 ℃ in vacuum for 12h to obtain the metal organic framework support material UiO-67.
2) Preparation of UiO-67 immobilized PdCo salt material
Fully dissolving a certain amount of palladium nitrate and cobalt chloride in 30mL of acetonitrile, then adding a metal organic framework carrier material UiO-67, and controlling Pd2+/Co2+In a molar ratio of 2:1, with a total metal content (Pd)2++Co2+) The mass ratio of the support material UiO-67 was controlled to 5 wt%. Reacting at the constant temperature of 65 ℃ for 24h, cooling to room temperature, filtering and washing, soaking the solid in 30mL ethyl acetate, replacing the ethyl acetate once every 24h, continuously exchanging for 3 days, filtering and washing, and vacuum drying at 150 ℃ for 12h to obtain the metal organic framework material immobilized PdCo salt material.
3) Preparation of PdCo @ UiO-67 catalyst
Placing the UiO-67 immobilized PdCo salt material in a mixed atmosphere of 5% hydrogen and 95% nitrogen by volume percent, and heating at 400 ℃ for 2h to prepare the Pd2Co1@UiO-67(5％)。
Example 4
A preparation method of a UiO-67 encapsulated PdCo alloy nanoparticle catalyst PdCo @ UiO-67 comprises the following steps:
1) preparation of metal organic framework support material UiO-67
Dissolving 1mmol of zirconium oxychloride, 0.5mmol of 2,2 ' -bipyridine-5, 5 ' -dicarboxylic acid and 0.5mmol of 4,4 ' -biphenyldicarboxylic acid in 30mL of water, reacting for 36h at 100 ℃, filtering and washing the obtained solid product, and drying for 12h at 100 ℃ in vacuum to obtain the metal organic framework support material UiO-67.
2) Preparation of UiO-67 immobilized PdCo salt material
Fully dissolving a certain amount of palladium acetylacetonate and cobalt sulfate in 30mL of acetonitrile, adding a metal organic framework carrier material UiO-67, and controlling Pd2+/Co2+In a molar ratio of 1:1, with a total metal content (Pd)2++Co2+) The mass ratio of the support material UiO-67 was controlled to 2 wt%. Reacting at the constant temperature of 65 ℃ for 24h, cooling to room temperature, filtering and washing, soaking the solid in 30mL of acetone, replacing the acetone once every 24h, continuously exchanging for 3 days, filtering and washing, and vacuum drying at 150 ℃ for 12h to obtain the metal organic framework material immobilized PdA Co salt material.
3) Preparation of PdCo @ UiO-67 catalyst
Placing the UiO-67 immobilized PdCo salt material in a mixed atmosphere of 10 volume percent of carbon monoxide and 90 volume percent of helium, and heating at 400 ℃ for 1h to prepare the Pd1Co1@UiO-67(2％)。
Example 5
A preparation method of a UiO-67 encapsulated PdCo alloy nanoparticle catalyst PdCo @ UiO-67 comprises the following steps:
1) preparation of metal organic framework support material UiO-67
Dissolving 1mmol of zirconium nitrate, 0.4mmol of 2,2 ' -bipyridine-5, 5 ' -dicarboxylic acid and 0.6mmol of 4,4 ' -biphenyldicarboxylic acid in 30mL of ethanol, reacting for 48h at 100 ℃, filtering and washing the obtained solid product, and drying for 12h at 100 ℃ in vacuum to obtain the metal organic framework support material UiO-67.
2) Preparation of UiO-67 immobilized PdCo salt material
Fully dissolving a certain amount of palladium chloride and cobalt chloride in 30mL of acetonitrile, then adding a metal organic framework carrier material UiO-67, and controlling Pd2+/Co2+In a molar ratio of 1:2, with a total metal content (Pd)2++Co2+) The mass ratio of the support material UiO-67 was controlled to 2 wt%. Reacting at the constant temperature of 65 ℃ for 24h, cooling to room temperature, filtering and washing, soaking the solid in 30mL of chloroform, replacing the chloroform every 24h, continuously exchanging for 3 days, filtering and washing, and vacuum drying at 150 ℃ for 12h to obtain the metal organic framework material immobilized PdCo salt material.
3) Preparation of PdCo @ UiO-67 catalyst
Placing the UiO-67 immobilized PdCo salt material in a mixed atmosphere of 5% hydrogen and 95% argon by volume, and heating at 400 ℃ for 2h to prepare the Pd1Co2@UiO-67(2％)。
Comparative example 1
A preparation method of a UiO-67 encapsulated Pd nanoparticle catalyst Pd @ UiO-67 comprises the following steps:
1) preparation of metal organic framework support material UiO-67
Dissolving 1mmol of zirconium nitrate, 0.45mmol of 2,2 ' -bipyridine-5, 5 ' -dicarboxylic acid and 0.55mmol of 4,4 ' -biphenyldicarboxylic acid in 30mL of ethanol, reacting for 48h at 100 ℃, filtering and washing the obtained solid product, and drying for 12h at 100 ℃ in vacuum to obtain the metal organic framework support material UiO-67.
2) Preparation of UiO-67 immobilized Pd salt material
Fully dissolving a certain amount of diacetone palladium chloride in 30mL of acetonitrile, and then adding a metal organic framework carrier material UiO-67 with metal content Pd2+The mass ratio of the support material UiO-67 was controlled to 2 wt%. Reacting at the constant temperature of 65 ℃ for 24h, cooling to room temperature, filtering and washing, soaking the solid in 30mL of chloroform, replacing the chloroform every 24h, continuously exchanging for 3 days, filtering and washing, and vacuum drying at 150 ℃ for 12h to obtain the metal organic framework material immobilized Pd salt material.
3) Preparation of Pd @ UiO-67 catalyst
The UiO-67 immobilized Pd salt material is heated at 400 ℃ for 2h under the mixed atmosphere of 5% hydrogen and 95% argon by volume percent to prepare Pd @ UiO-67 (2%).
Comparative example 2
A preparation method of a UiO-67 encapsulated Co nanoparticle catalyst Co @ UiO-67 comprises the following steps:
1) preparation of metal organic framework support material UiO-67
Dissolving 1mmol of zirconium nitrate, 0.6mmol of 2,2 ' -bipyridine-5, 5 ' -dicarboxylic acid and 0.4mmol of 4,4 ' -biphenyldicarboxylic acid in 30mL of ethanol, reacting for 48 hours at 100 ℃, filtering and washing an obtained solid product, and drying for 12 hours at 100 ℃ in vacuum to obtain a metal organic framework carrier material UiO-67;
2) preparation of UiO-67 solid-carried Co salt material
Fully dissolving a certain amount of cobalt nitrate in 30mL of acetonitrile, and then adding a metal organic framework carrier material UiO-67 with metal content Co2+The mass ratio of the support material UiO-67 was controlled to 2 wt%. Reacting at constant temperature of 65 deg.C for 24h, cooling to room temperature, filtering, washing, soaking the solid in 30mL chloroform, changing chloroform every 24h for 3 days, filtering, and washing at 150 deg.CAnd (5) drying for 12h in vacuum to obtain the metal organic framework material supported Co salt material.
3) Preparation of Co @ UiO-67 catalyst
The UO-67 immobilized Co salt material is placed in a mixed atmosphere of 5% hydrogen and 95% argon by volume and heated at 400 ℃ for 2h to prepare Co @ UO-67 (2%).
Comparative example 3
A preparation method of a catalyst PdCo/UiO-67 with PdCo alloy nanoparticles deposited on the outer surface of the UiO-67 comprises the following steps:
1) preparation of metal organic framework support material UiO-67
Dissolving 1mmol of zirconium chloride and 1mmol of 4, 4' -biphenyldicarboxylic acid in 60mL of N, N-dimethylformamide, reacting at 120 ℃ for 24h, filtering and washing the obtained solid product, and drying at 150 ℃ in vacuum for 12h to obtain the metal organic framework support material UiO-67.
2) Preparation of metal organic framework material UiO-67 loaded PdCo salt material
Fully dissolving a certain amount of diacetonitrile palladium chloride and cobalt nitrate in 30mL of acetonitrile, then adding a metal organic framework carrier material UiO-67, and controlling Pd2+/Co2+In a molar ratio of 2:1, with a total metal content (Pd)2++Co2+) The mass ratio of the support material UiO-67 was controlled to 2 wt%. Dipping for 24h at room temperature, evaporating to remove acetonitrile, and vacuum drying for 12h at 150 ℃ to obtain the UiO-67 PdCo-loaded salt material.
3) Preparation of PdCo/UiO-67
Placing the UiO-67 PdCo salt material in a mixed atmosphere of 5% hydrogen and 95% argon by volume, and heating at 400 ℃ for 2h to obtain PdCo/UiO-67.
Application testing
Firstly, acetaldehyde catalytic oxidation performance test is carried out on the catalysts prepared in examples 1-5 and comparative examples 1-3.
The test conditions were as follows: the reaction raw material gas has a concentration of 10mg/m3The total flow rate of the acetaldehyde simulation gas is 25mL/min, the size of the catalyst is 40-60 meshes, the loading amount is 100mg, and the space velocity is 15000 mL/g/h.
The test method is as follows: the reaction raw material gas passes through a quartz tube reactor filled with a catalyst, the quartz tube reactor is placed in a temperature control furnace to control the reaction temperature, and after the reaction gas reacts for 20min at a certain temperature, the gas passes through a gas chromatograph to detect the concentration of acetaldehyde at an outlet on line. The acetaldehyde conversion of the catalyst at each temperature was calculated as the catalytic activity of the catalyst on acetaldehyde by taking the average of three tests at each temperature.
The results of the catalyst performance tests obtained are shown in FIG. 2.
As can be seen from fig. 2: the reaction activity of the UiO-67 encapsulated PdCo alloy nanoparticle catalyst prepared by the method is superior to that of the single-metal catalyst in the comparative examples 1-2 under the test conditions. The catalyst prepared in example 1 can realize complete conversion of acetaldehyde at 100 ℃, while the catalyst prepared in comparative example 1 can realize complete conversion of acetaldehyde at 150 ℃, and the catalyst prepared in comparative example 2 has complete conversion temperature of acetaldehyde even higher than 200 ℃. This is mainly due to the lack of intermetallic synergy in single metal catalysts.
It can also be seen from FIG. 2 that: the reaction activity of the UiO-67 packaged PdCo alloy nanoparticle catalyst prepared by the method is superior to that of the supported PdCo/UiO-67 catalyst in the comparative example 3 under the test conditions. The catalyst prepared in comparative example 3 was allowed to completely convert acetaldehyde at 180 ℃. This is mainly because the preparation method in comparative example 3 is an impregnation method, and the supported PdCo alloy nanoparticles are mainly deposited on the surface of the UiO-67 carrier, and are easily migrated during the preparation and reaction processes, causing agglomeration sintering, resulting in a great decrease in activity.
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 encapsulated metal nanoparticle 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 PdCo alloy nanoparticles; the PdCo alloy nanoparticles are confined in the lumen of the UiO-67 frame.
2. The UiO-67 encapsulated metal nanoparticle catalyst of claim 1, wherein: the loading capacity of the PdCo alloy nano particles is 0.1-5% of the mass of UiO-67; preferably, the mole ratio of Pd/Co in the PdCo alloy nanoparticles is 9: 1-1: 9.
3. A method of preparing the uo-67 encapsulated metal nanoparticle catalyst of claim 1 or 2, wherein: the method comprises the following steps:
1) preparing a metal organic framework material UiO-67: dissolving zirconium salt and a polydentate carboxylic acid ligand in a solvent, and carrying out a solvothermal reaction to obtain a metal organic framework material UiO-67; the polydentate carboxylic acid ligand comprises bipyridyl units;
2) preparing a UiO-67 immobilized PdCo salt material: dissolving palladium salt and cobalt salt in a solvent, then adding the UiO-67,
heating for reaction, and carrying out solvent exchange and drying on the obtained solid product to obtain a UiO-67 immobilized PdCo salt material;
3) preparation of the UiO-67 encapsulated metal nanoparticle catalyst: and carrying out heating reaction on the UiO-67 immobilized PdCo salt material under reducing gas to obtain the UiO-67 encapsulated metal nanoparticle catalyst.
4. The production method according to claim 3, characterized in that: in the step 1), the molar ratio of the zirconium salt, the polydentate carboxylic acid ligand and the solvent is 1: (1-1.2): (400-1800).
5. The production method according to claim 3 or 4, characterized in that: in the step 1), the zirconium salt comprises at least one of zirconium chloride, zirconium nitrate, zirconium sulfate, zirconium oxychloride and zirconium acetate; preferably, the polydentate carboxylic acid ligand is selected from 2,2 ' -bipyridine-5, 5 ' -dicarboxylic acid, or the polydentate carboxylic acid ligand is a combination of 2,2 ' -bipyridine-5, 5 ' -dicarboxylic acid and 4,4 ' -biphenyldicarboxylic acid; preferably, the solvent comprises at least one of N, N-dimethylformamide, methanol, ethanol, isopropanol, tetrahydrofuran, dimethyl sulfoxide, acetone, diethyl ether, water.
6. The production method according to claim 3, characterized in that: in the step 1), the temperature of the solvothermal reaction is 60-150 ℃, and preferably, the solvothermal reaction time is 24-48 h.
7. The production method according to claim 3, characterized in that: in the step 2), the palladium salt comprises at least one of palladium chloride, palladium nitrate, bis-acetonitrile palladium chloride and palladium acetylacetonate; preferably, the cobalt salt comprises at least one of cobalt chloride, cobalt nitrate, cobalt sulfate and cobalt acetate.
8. The production method according to claim 3, characterized in that: in the step 2), the temperature of the heating reaction is 50-80 ℃, and preferably, the time of the heating reaction is 12-36 h.
9. The production method according to claim 3, characterized in that: in the step 3), the reducing gas comprises at least one of hydrogen and carbon monoxide; preferably, in the step 3), the heating reaction is specifically carried out at 300-400 ℃ for 0.5-2 h.
10. Use of the UiO-67 encapsulated metal nanoparticle catalyst of claim 1 or 2 in the catalytic oxidation of acetaldehyde.
CN202011432771.XA 2020-12-09 2020-12-09 UiO-67 encapsulated metal nanoparticle catalyst and preparation method and application thereof Active CN112642487B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011432771.XA CN112642487B (en) 2020-12-09 2020-12-09 UiO-67 encapsulated metal nanoparticle catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011432771.XA CN112642487B (en) 2020-12-09 2020-12-09 UiO-67 encapsulated metal nanoparticle catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112642487A true CN112642487A (en) 2021-04-13
CN112642487B CN112642487B (en) 2023-07-18

Family

ID=75350642

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011432771.XA Active CN112642487B (en) 2020-12-09 2020-12-09 UiO-67 encapsulated metal nanoparticle catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112642487B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114405518A (en) * 2021-12-30 2022-04-29 广东省科学院化工研究所 Solid acid-bimetal nanoparticle composite material and preparation method and application thereof
CN115970662A (en) * 2023-02-17 2023-04-18 中南大学 UiO-67 loaded nano copper oxide material and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104646029A (en) * 2015-02-24 2015-05-27 中山大学惠州研究院 Metal alloy catalyst for formaldehyde purification and preparation method thereof
CN105214682A (en) * 2015-05-08 2016-01-06 北京工业大学 Three-dimensional ordered macroporous CeO 2 supporting Co-Pd nanometer alloy catalyst, preparation method and application
US20170182486A1 (en) * 2014-03-28 2017-06-29 The University Of Chicago Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations
CN108187690A (en) * 2017-12-07 2018-06-22 广东省石油与精细化工研究院 A kind of cobalt manganese composite oxide loaded catalyst that formaldehyde is removed for room temperature and preparation method thereof
CN108786921A (en) * 2018-04-26 2018-11-13 上海理工大学 A kind of monatomic Pd@UiO-66 catalyst and its preparation method and application
CN111111784A (en) * 2019-12-12 2020-05-08 广东省石油与精细化工研究院 UiO-67 coated Co catalyst and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170182486A1 (en) * 2014-03-28 2017-06-29 The University Of Chicago Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations
CN104646029A (en) * 2015-02-24 2015-05-27 中山大学惠州研究院 Metal alloy catalyst for formaldehyde purification and preparation method thereof
CN105214682A (en) * 2015-05-08 2016-01-06 北京工业大学 Three-dimensional ordered macroporous CeO 2 supporting Co-Pd nanometer alloy catalyst, preparation method and application
CN108187690A (en) * 2017-12-07 2018-06-22 广东省石油与精细化工研究院 A kind of cobalt manganese composite oxide loaded catalyst that formaldehyde is removed for room temperature and preparation method thereof
CN108786921A (en) * 2018-04-26 2018-11-13 上海理工大学 A kind of monatomic Pd@UiO-66 catalyst and its preparation method and application
CN111111784A (en) * 2019-12-12 2020-05-08 广东省石油与精细化工研究院 UiO-67 coated Co catalyst and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHENG HAO WU等: "Bimetallic synergy in cobalt–palladium nanocatalysts for CO oxidation", 《NATURE CATALYSIS》 *
PETER HESTER等: "On thermal stability and catalytic reactivity of Zr-based metal–organic framework (UiO-67) encapsulated Pt catalysts", 《JOURNAL OF CATALYSIS》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114405518A (en) * 2021-12-30 2022-04-29 广东省科学院化工研究所 Solid acid-bimetal nanoparticle composite material and preparation method and application thereof
CN114405518B (en) * 2021-12-30 2023-12-05 广东省科学院化工研究所 Solid acid-bimetallic nanoparticle composite material and preparation method and application thereof
CN115970662A (en) * 2023-02-17 2023-04-18 中南大学 UiO-67 loaded nano copper oxide material and preparation method and application thereof

Also Published As

Publication number Publication date
CN112642487B (en) 2023-07-18

Similar Documents

Publication Publication Date Title
US9931623B2 (en) Method for producing metal nanoparticle complex, and metal nanoparticle complex produced by said method
CN109201048A (en) A kind of monatomic catalyst and preparation method thereof
CN110433838B (en) Preparation method of transition metal-loaded integral nitrogen-doped mesoporous carbon atom-level active site catalyst
CN112642487B (en) UiO-67 encapsulated metal nanoparticle catalyst and preparation method and application thereof
CN102198405A (en) Composite catalyst for purifying indoor formaldehyde and preparation method of composite catalyst
CN109317210B (en) Bimetallic organic framework material and preparation method and application thereof
KR20120085079A (en) Complex metal oxide catalyst, filter module and air cleaner comprising this catalyst
CN101362072A (en) Absorbent for removing trace benzene in carbon dioxide and preparation method thereof
CN114618589B (en) Preparation method and application of ozone degradation catalyst based on iron-based organic framework
CN111468147A (en) Porous carbon composite titanium dioxide-oxyhalide photocatalyst and preparation method thereof
CN109621962B (en) Metal oxide catalyst with regular morphology for eliminating formaldehyde and preparation method and application thereof
CN112044401A (en) Porous organic cage adsorbing material and preparation method thereof
CN106861626B (en) Adsorption-photocatalysis dual-function material, preparation method thereof and application thereof in volatile organic gas treatment process
Hussain et al. Synthesis of functionalized mesoporous Ni-SBA-16 decorated with MgO nanoparticles for Cr (VI) adsorption and an effective catalyst for hydrodechlorination of chlorobenzene
CN111111784B (en) UiO-67 coated Co catalyst and preparation method and application thereof
CN113976109A (en) Method for in-situ constructing multi-stage porous carbon material in porous mineral and synchronously loading noble metal nano catalyst
CN112642486B (en) MOF-253 encapsulated metal nanoparticle catalyst and preparation method and application thereof
CN112973437B (en) Formaldehyde removal master batch for air purification device and preparation method thereof
CN114409917A (en) Moisture-resistant iron-based metal organic framework material with catalytic ozonolysis capability and preparation method and application thereof
CN111068666A (en) Sepiolite supported noble metal formaldehyde room-temperature oxidation catalyst and preparation method thereof
CN110314685A (en) A kind of catalyst with core-casing structure preparation method for toluene low-temperature catalytic oxidation
CN110605118B (en) Integral Pd/K for degrading formaldehyde at room temperature2Ti6O13-NWs catalyst, preparation method and application
CN110433854B (en) Composite catalyst for degrading formaldehyde at room temperature and preparation method and application thereof
CN111013574A (en) Preparation method of noble metal/carbon sphere composite catalytic material for removing formaldehyde from air
CN103055949B (en) Preparation method of macroporous alumina support

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant