CN114887662B - Metal organic framework material-molecular sieve composite material and preparation method and application thereof - Google Patents
Metal organic framework material-molecular sieve composite material and preparation method and application thereof Download PDFInfo
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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
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—Ozone
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—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
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/70—Non-metallic catalysts, additives or dopants
- B01D2255/705—Ligands for metal-organic catalysts
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- 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
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention relates to a metal organic framework material-molecular sieve composite material, a preparation method and application thereof, belonging to the field of composite materials. The method utilizes a surface modifier to carry out surface modification on a molecular sieve, and then a surface functional group induces metal ions and organic ligands to grow a metal organic framework material on the surface of the molecular sieve in situ, so that a composite material of the metal organic framework material and the molecular sieve is obtained. The composite material prepared by the method has high specific surface area, large pore volume and high mechanical strength, and the metal organic framework material is uniformly and stably distributed on the pore canal and the surface of the molecular sieve to form rich metal active sites, acid sites and interface defects.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a metal organic framework material-molecular sieve composite material, and a preparation method and application thereof.
Background
The molecular sieve is a porous material with a specific pore structure, has the characteristics of high specific surface area, regular and ordered pore structure, narrow pore diameter distribution, continuous and adjustable pore diameter size and the like, is commonly used for sieving molecules with different sizes, realizes high-efficiency separation effect, and shows certain catalytic performance in ozone catalytic decomposition, however, the current molecular sieve is used as an ozone catalytic decomposition catalyst, and has low catalytic performance and water resistance due to low number of active sites and high polarity. Metal Organic Frameworks (MOFs) are microporous crystal materials with periodic network structures formed by self-assembly of transition metal ions and organic ligands, and have the advantages of high specific surface area, uniform pore size distribution and multifunction. The angel. Chem. Int. Ed.2018,57, 16416-16420 article reports that the iron-based metal-organic framework material exhibits efficient ozone catalytic decomposition performance for low concentrations of ozone, but its ozone catalytic decomposition performance is significantly reduced under low humidity conditions. The metal organic framework material and the molecular sieve are organically compounded, and the problems of low catalytic performance and poor water resistance of a single molecular sieve or the metal organic framework material are improved by utilizing the pore channel structure, the multi-level pore diameter and rich high-performance interface defects of the metal organic framework material. However, how to organically combine the metal organic framework material and the molecular sieve into a porous composite material, so as to realize high-efficiency ozone catalytic decomposition performance, and the method becomes the difficulty of current research.
Disclosure of Invention
Aiming at the problems, the invention utilizes the surface modifier to carry out organic functional group modification treatment on the molecular sieve, and then induces and grows a metal organic framework material on the surface of the surface modified molecular sieve in situ to obtain the metal organic framework material-molecular sieve composite material. The metal organic framework material-molecular sieve composite material prepared by the method has high specific surface area, multistage pore structure, rich surface interface defects and high mechanical strength, and the metal organic framework material is uniformly and stably distributed on the pore channels and the surface of the molecular sieve, so that the metal organic framework material has potential application value in preparation of porous composite materials and promotion of catalytic performance.
The invention provides a metal organic framework material-molecular sieve composite material, a preparation method and application thereof aiming at the technical problems.
The aim of the invention can be achieved by the following technical scheme:
the invention aims to provide a metal organic framework material-molecular sieve composite material, a preparation method and application thereof aiming at the problems. According to the invention, the molecular sieve is modified by using the surface modifier to obtain the modified molecular sieve, then the organic functional groups on the surface of the molecular sieve promote the metal ions and ligands to grow the metal organic framework material on the surface and pore channels in situ through induction, so that the metal organic framework material-molecular sieve composite material is prepared, and the composite material has high specific surface area, large pore volume, multi-stage pore channel structure, rich metal active sites, acid sites and interface defects and high mechanical strength, and has important application value for preparing the porous composite material and improving the catalytic performance.
A method for preparing a metal-organic framework-molecular sieve composite material, which comprises the following steps:
(1) Adding a surface modifier into a solvent for dissolution, then adding a molecular sieve, and uniformly dispersing to obtain a mixed solution 1;
(2) Sequentially adding metal salt and an organic ligand into the mixed solution 1 obtained in the step (1), and stirring for 0.5-1.5 h to obtain a mixed solution 2;
(3) Transferring the mixed solution 2 obtained in the step (2) into a reaction kettle, and reacting for 5-48 hours at the temperature of 120-180 ℃ to obtain a mixed solution 3;
(4) And (3) sequentially centrifuging, washing and drying the mixed solution 3 obtained in the step (3) to obtain the metal-organic framework material-molecular sieve composite material.
The method comprises the following steps: the surface modifier in the step (1) is one or more of 3-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, gamma-aminopropyl methyl diethoxysilane and 3-mercaptopropyl triethoxysilane.
The method comprises the following steps: the solvent in the step (1) is one or more of water, methanol, ethanol, DMF and chloroform.
The method comprises the following steps: the molecular sieve in the step (1) is one of a Y-type microporous molecular sieve, a ZSM-5 microporous molecular sieve, a Beta microporous molecular sieve and an SBA-15 mesoporous molecular sieve.
The method comprises the following steps: the mass ratio of the surface modifier to the molecular sieve in the step (1) is 1:0.1-10; preferably: the mass ratio of the surface modifier to the molecular sieve in the step (1) is 1:0.3-5.
The method comprises the following steps: the metal salt in the step (2) is one of zinc salt, ferric salt, cobalt salt and copper salt; the metal salt is in the form of chloride, nitrate or acetate.
The method comprises the following steps: the organic ligand in the step (2) is 2-methylimidazole, terephthalic acid, 2-amino terephthalic acid or trimesic acid.
The method comprises the following steps: in the step (2), the mixture is reacted for 6 to 24 hours at the temperature of 130 to 170 ℃ to obtain the mixed solution 3.
The method comprises the following steps: the mass ratio of the metal salt to the molecular sieve is 1:0.5-3; the molar ratio of metal salt to organic ligand is 1:0.5-10.
The metal organic framework material-molecular sieve composite material is prepared by the method.
The technical scheme of the invention is as follows: the application of the metal organic framework-molecular sieve composite material as a catalyst for catalyzing ozonolysis; preferably: ozone concentration of 40-100ppm and volume space velocity of 40000-60000h -1 The reaction time is 3 days, the granularity is 60-80 meshes, and the catalytic ozonolysis capability of the catalyst is tested under the room temperature condition.
The invention has the beneficial effects that:
the preparation method is simple and convenient; the prepared metal-organic framework-molecular sieve composite material has high specific surface area, large pore volume, multi-stage pore structure, rich surface interface defects and high mechanical strength, and the metal-organic framework material is uniformly and stably distributed on the pore channels and the surfaces of the molecular sieve, so that the metal-organic framework-molecular sieve composite material is suitable for industrial application and has potential application prospects in the field of catalysis.
Drawings
FIG. 1 is a scanning electron microscope image of a copper terephthalic acid metal organic framework material/ZSM-5 molecular sieve composite material.
Detailed Description
The invention is further illustrated below with reference to examples, but the scope of the invention is not limited thereto: example 1:
(1) 1.0g of 3-aminopropyl triethoxysilane is weighed and added into a mixed solvent formed by mixing 15g of water, 15g of ethanol and 15g of DMF to be uniformly dispersed, then 1.0g of ZSM-5 zeolite molecular sieve is added, and the mixture is uniformly stirred and modified for 12 hours at room temperature;
(2) Respectively weighing 1.88g of copper nitrate and 1.66g of terephthalic acid (the molar ratio of the copper nitrate to the terephthalic acid is 1:0.5), sequentially adding the copper nitrate to the mixed solution obtained in the step (1), and stirring for 1h at 30 ℃;
(3) Transferring the mixed solution obtained in the step (2) into a reaction kettle, and reacting for 24 hours at the temperature of 130 ℃;
(4) And (3) washing and drying the mixed solution obtained in the step (3) to obtain the copper terephthalic acid metal organic framework material/ZSM-5 molecular sieve composite material, as shown in figure 1.
(5) The catalytic ozonolysis performance of the copper terephthalic acid metal organic framework material-ZSM-5 molecular sieve composite material is tested, the initial concentration of ozone is 50ppm, and the volume space velocity is 40000h -1 The reaction time is 3 days, and the ozone conversion rate is 99% under the condition of 60-80 meshes of granularity.
Example 2:
(1) 1.0g of gamma-aminopropyl trimethoxysilane is weighed and added into 40g of methanol solvent to be uniformly dispersed, then 2.0g Y type zeolite molecular sieve is added, and the mixture is uniformly stirred and modified for 12 hours at room temperature;
(2) Respectively weighing 0.91g of cobalt nitrate and 3.28g of 2-methylimidazole (the molar ratio of the cobalt nitrate to the 2-methylimidazole is 1:8), sequentially adding the cobalt nitrate to the mixed solution obtained in the step (1), and stirring for 1h at 25 ℃;
(3) Transferring the mixed solution obtained in the step (2) into a reaction kettle, and reacting for 45h at the temperature of 125 ℃;
(4) And (3) washing and drying the mixed solution obtained in the step (3) to obtain the cobalt-2-methylimidazole metal organic framework material/Y-type molecular sieve composite material.
(5) Testing the catalytic ozonolysis performance of the cobalt-2 methylimidazole metal organic framework material/Y-type molecular sieve composite material, wherein the initial concentration of ozone is 90ppm, and the volume space velocity is 50000h -1 The reaction time is 3 days, and the ozone conversion rate is 98% under the condition of 60-80 meshes of granularity.
Example 3:
(1) 1.0g of gamma-aminopropyl methyl diethoxy silane is weighed and added into 50g of ethanol solvent to be uniformly dispersed, then 2.0g of Beta zeolite molecular sieve is added, and the mixture is uniformly stirred and modified for 12 hours at room temperature;
(2) Respectively weighing 1.84g of zinc acetate and 4.11g of 2-methylimidazole (the molar ratio of the zinc acetate to the 2-methylimidazole is 1:5), sequentially adding into the mixed solution obtained in the step (1), and stirring for 1h at 25 ℃;
(3) Transferring the mixed solution obtained in the step (2) into a reaction kettle, and reacting for 6 hours at 170 ℃;
(4) And (3) washing and drying the mixed solution obtained in the step (3) to obtain the zinc-2-methylimidazole metal organic framework material/Beta type molecular sieve composite material.
(5) Testing the catalytic ozonolysis performance of the zinc-2-methylimidazole metal organic framework material/Beta molecular sieve composite material, wherein the initial concentration of ozone is 60ppm, and the volume airspeed is 55000h -1 Under the condition of 60-80 meshes, the reaction time is 3 days, and the ozone conversion rate is 98%.
Example 4:
(1) Weighing 0.5g of 3-mercaptopropyl triethoxysilane, adding the 3-mercaptopropyl triethoxysilane into 40g of DMF solvent for uniform dispersion, then adding 1.0g of SBA-15 mesoporous molecular sieve, stirring uniformly, and modifying at room temperature for 12h;
(2) Weighing 0.81g of ferric chloride and 3.15g of trimesic acid (the molar ratio of the ferric chloride to the trimesic acid is 1:3), sequentially adding the ferric chloride to the mixed solution obtained in the step (1), and stirring for 1h at 40 ℃;
(3) Transferring the mixed solution obtained in the step (2) into a reaction kettle, and reacting for 12 hours at the temperature of 150 ℃;
(4) And (3) washing and drying the mixed solution obtained in the step (3) to obtain the iron-trimesic acid metal organic framework material/SBA-15 molecular sieve composite material.
(5) Testing the catalytic ozonolysis performance of the iron-trimesic acid metal organic framework material/SBA-15 molecular sieve composite material, wherein the initial concentration of ozone is 70ppm, and the volume space velocity is 45000h -1 The reaction time is 3 days, and the ozone conversion rate is 99% under the condition of 60-80 meshes of granularity.
Comparative example 1:
(1) 1.0g of ZSM-5 zeolite molecular sieve is weighed and added into a mixed solvent formed by mixing 15g of water, 15g of ethanol and 15g of DMF, and the mixture is stirred uniformly and stirred continuously for 12 hours at room temperature;
(2) Respectively weighing 1.88g of copper nitrate and 1.66g of terephthalic acid, sequentially adding the copper nitrate and the terephthalic acid into the mixed solution obtained in the step (1), and stirring for 1h at 30 ℃;
(3) Transferring the mixed solution obtained in the step (2) into a reaction kettle, and reacting for 24 hours at the temperature of 100 ℃;
(4) And (3) washing and drying the mixed solution obtained in the step (3) to obtain the copper terephthalic acid metal organic framework material/ZSM-5 molecular sieve composite material.
(5) The catalytic ozonolysis performance of the copper terephthalic acid metal organic framework material/ZSM-5 molecular sieve composite material is tested, the initial concentration of ozone is 50ppm, and the volume space velocity is 40000h -1 The reaction time is 3 days, and the ozone conversion rate is 35% under the condition of 60-80 meshes of granularity.
Comparative example 2:
(1) Weighing 2.0g Y zeolite molecular sieve, adding the zeolite molecular sieve into 40g of methanol solvent, uniformly dispersing, uniformly stirring, and continuously stirring at room temperature for 12 hours;
(2) Respectively weighing 0.91g of cobalt nitrate and 3.28g of 2-methylimidazole, sequentially adding the cobalt nitrate and the 3.28g of 2-methylimidazole into the mixed solution obtained in the step (1), and stirring for 1h at 25 ℃;
(3) Transferring the mixed solution obtained in the step (2) into a reaction kettle, and reacting for 45h at the temperature of 25 ℃;
(4) And (3) washing and drying the mixed solution obtained in the step (3) to obtain the cobalt-2-methylimidazole metal organic framework material/Y-type molecular sieve composite material.
(5) Testing the catalytic ozonolysis performance of the cobalt-2 methylimidazole metal organic framework material/Y-type molecular sieve composite material, wherein the initial concentration of ozone is 90ppm, and the volume space velocity is 50000h -1 The reaction time is 3 days, and the ozone conversion rate is 21% under the condition of 60-80 meshes of granularity.
Claims (5)
1. The preparation method of the metal-organic framework-molecular sieve composite material is characterized by comprising the following steps of:
(1) Adding a surface modifier into a solvent for dissolution, then adding a molecular sieve, and uniformly dispersing to obtain a mixed solution 1;
(2) Sequentially adding metal salt and an organic ligand into the mixed solution 1 obtained in the step (1), and stirring for 0.5-1.5 h to obtain a mixed solution 2;
(3) Transferring the mixed solution 2 obtained in the step (2) into a reaction kettle, and reacting for 5-48 hours at the temperature of 120-180 ℃ to obtain a mixed solution 3;
(4) Sequentially centrifuging, washing and drying the mixed solution 3 obtained in the step (3) to obtain a metal organic framework material-molecular sieve composite material;
the surface modifier in the step (1) is one or more of 3-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, gamma-aminopropyl methyl diethoxysilane and 3-mercaptopropyl triethoxysilane; the mass ratio of the surface modifier to the molecular sieve is 1:0.1-10;
the molecular sieve in the step (1) is one of a Y-type microporous molecular sieve, a ZSM-5 microporous molecular sieve, a Beta microporous molecular sieve and an SBA-15 mesoporous molecular sieve;
the metal salt in the step (2) is one of zinc salt, ferric salt, cobalt salt and copper salt; the metal salt is in the form of chloride, nitrate or acetate;
the organic ligand in the step (2) is 2-methylimidazole, terephthalic acid, 2-amino terephthalic acid or trimesic acid;
the mass ratio of the metal salt to the molecular sieve is 1:0.5-3; the molar ratio of metal salt to organic ligand is 1:0.5-10.
2. The method according to claim 1, characterized in that: the solvent in the step (1) is one or more of water, methanol, ethanol, DMF and chloroform.
3. The method according to claim 1, characterized in that: the mass ratio of the surface modifier to the molecular sieve in the step (1) is 1:0.3-5.
4. A metal organic framework material-molecular sieve composite material, characterized in that: the material is prepared by the method of claim 1.
5. The application of the metal organic framework-molecular sieve composite material prepared by the method of claim 1 as a catalyst for catalyzing ozonolysis, which is characterized in that: ozone concentration of 40-100ppm and volume space velocity of 40000-60000h -1 The reaction time is 3 days, the granularity is 60-80 meshes, and the catalytic ozonolysis capability of the catalyst is tested under the room temperature condition.
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