CN113603897A - Preparation of zinc-based metal organic framework material and selective adsorption application thereof - Google Patents

Preparation of zinc-based metal organic framework material and selective adsorption application thereof Download PDF

Info

Publication number
CN113603897A
CN113603897A CN202110986197.0A CN202110986197A CN113603897A CN 113603897 A CN113603897 A CN 113603897A CN 202110986197 A CN202110986197 A CN 202110986197A CN 113603897 A CN113603897 A CN 113603897A
Authority
CN
China
Prior art keywords
zinc
carbon dioxide
microporous
tcbpe
bpb
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
CN202110986197.0A
Other languages
Chinese (zh)
Other versions
CN113603897B (en
Inventor
陈强
李�一
肖金晟
刘璐
吕杰
谢亚勃
李建荣
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.)
Beijing University of Technology
Original Assignee
Beijing University of Technology
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 Beijing University of Technology filed Critical Beijing University of Technology
Priority to CN202110986197.0A priority Critical patent/CN113603897B/en
Publication of CN113603897A publication Critical patent/CN113603897A/en
Application granted granted Critical
Publication of CN113603897B publication Critical patent/CN113603897B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/104—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B01D2256/245—Methane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

A preparation method of zinc-based metal organic framework material and selective adsorption application thereof belong to the technical field of crystalline state porous material preparation. The MOF material is prepared from an organic ligand of tetra [4- (4' -carboxyphenyl) phenyl]Ethylene (TCBPE) and the organic ligand 1, 4-bis (4-pyridyl) benzene (Bpb) with zinc nitrate (ZnNO)3) Synthesized under solvothermal conditions. The MOF material has a regular pore channel structure, high porosity and specific surface area. The material has different adsorption acting forces for carbon dioxide and methane, so that the material has the performance of selective adsorption of carbon dioxide.

Description

Preparation of zinc-based metal organic framework material and selective adsorption application thereof
Technical Field
The invention belongs to the technical field of crystalline state porous material preparation, and relates to a preparation method and application of a novel zinc-based Metal Organic Framework (MOF).
Background
With the adjustment of energy structures, natural gas is widely used in many fields as a clean energy. Carbon dioxide contained in natural gas reduces the heating value of the fuel and can damage pipeline equipment. Therefore, the removal of carbon dioxide from natural gas is necessary and is a key link in natural gas treatment. The adsorption method has the characteristics of mature process, simple operation and low energy consumption, and is realized based on the difference of adsorption acting forces of the adsorption material on carbon dioxide and methane. The selective capture of carbon dioxide by adsorption separation is widely used as a method for removing carbon dioxide.
The MOFs material is a novel porous crystal material which is formed by metal ions or metal clusters and organic ligands through complexation and has high porosity and high specific surface area. The porous adsorbent has the characteristics of high porosity, high specific surface area, easy modification and adjustment, definite structure and the like, and is very suitable for being used as a porous adsorbent for relevant research. Compared with traditional materials such as activated carbon, zeolite and the like, the MOF material has the characteristics of adjustable pore channels, easiness in modification and the like, and has more active sites, so that the MOF material is easier to adsorb. The invention adopts an organic ligand tetra [4- (4' -carboxyl phenyl) phenyl group under the solvothermal condition]Ethylene (TCBPE) and the organic ligand 1, 4-bis (4-pyridyl) benzene (Bpb) with zinc nitrate (ZnNO)3) Self-assembly forms a microporous MOF material. The MOF material has high specific surface area and porosity and can selectively adsorb carbon dioxide.
Disclosure of Invention
The invention aims to provide a microporous MOF material for selectively adsorbing carbon dioxide, so as to solve the problem of selectively capturing carbon dioxide in methane.
In order to achieve the aim, the invention provides a microporous zinc MOF material for selectively adsorbing carbon dioxide, and the molecular structural formula of the microporous zinc MOF material is Zn2(TCBPE) (Bpb), wherein TCBPE is a planar tetracarboxylic acid ligand and Bpb is a bipyridine ligand.
Preferably, the TCBPE is tetrakis [4- (4' -carboxyphenyl) phenyl ] ethylene and the Bpb is 1, 4-bis (4-pyridyl) benzene.
Preferably, the microporous zinc MOF material belongs to a monoclinic system, the space group is P2/c, and the unit cell parameter is
Figure BDA0003230066260000021
Figure BDA0003230066260000022
α＝90°，β＝112.152(8)°，γ＝90°。
Preferably, the microporous zinc MOF material is in a triple interpenetrating layered column structure, the binuclear metal zinc and the TCBPE ligand form a two-dimensional layered structure, and the binuclear metal zinc in the two-dimensional layered structure is connected with the Bpb ligand to form a three-dimensional microporous structure.
The synthesis method of the microporous zinc MOF material mainly comprises the following steps:
(1) the organic ligands TCBPE, Bpb and zinc nitrate Zn (NO)3)2Dissolving in a mixed solution of N, N-Dimethylformamide (DMF) and methanol (MeOH);
(2) and (2) carrying out solvothermal reaction on the mixed solution in the step (1) to obtain a blocky single crystal, and washing the blocky single crystal with DMF (dimethyl formamide) to obtain the microporous zinc MOF material.
Further, the molar ratio of the organic ligand TCBPE to the organic ligand Bpb is 1:1 to 1: 3. Zinc nitrate Zn (NO) is preferred3)2The total molar ratio to the organic ligands TCBPE and Bpb was 1: 1.
Furthermore, the volume ratio of DMF to MeOH in the mixed solvent is 1:1-2: 1.
Further, the solvothermal reaction temperature is 100-120 ℃, and the reaction time is 48-96 h.
The zinc-based metal organic framework material obtained by the invention is used for selectively adsorbing carbon dioxide gas and is further used for separating carbon dioxide and methane.
The invention discloses a novel MOF material prepared based on an organic ligand tetra [4- (4' -carboxyphenyl) phenyl ] ethylene, an organic ligand 1, 4-di (4-pyridyl) benzene and a metal zinc source. The gas adsorption experiment shows that the carbon dioxide gas can be adsorbed in a large amount, but less methane is adsorbed under the same condition. Therefore, the coordination polymer can be used as a gas separating agent and has good application prospect in the field of material science.
Drawings
FIG. 1 is a schematic representation of the triple interpenetration structure (along the b-axis) of a microporous zinc MOF material of the present invention
FIG. 2 is a plot of the nitrogen adsorption isotherm at 77K for a microporous zinc MOF material of the invention
FIG. 3 is a graph of the adsorption of carbon dioxide and methane at 273K for microporous zinc MOF materials of the invention
FIG. 4 is a graph of the adsorption of carbon dioxide and methane at 298K for a microporous Zinc MOF material of the invention
FIG. 5 is a graph of the selectivity of the microporous zinc MOF material of the present invention at 1/1K for carbon dioxide/methane
FIG. 6 is a graph of the selectivity of carbon dioxide/methane 1/1 at 298K for microporous zinc MOF materials of the invention
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1: preparation of microporous zinc MOF materials
The first step is as follows: dissolving 0.01mmol of TCBPE, 0.01mmol of Bpb and 0.02mmol of zinc nitrate in 2mL of N, N-Dimethylformamide (DMF) and 1mL of methanol (MeOH) to obtain a mixed solution, filling the mixed solution into a reaction bottle or a reaction kettle, and reacting for 72 hours in an oven at 100 ℃ to obtain a crystal sample of the microporous zinc MOF material.
The second step is that: selecting a single crystal sample with proper size and good crystallinity, collecting diffraction data by using a single crystal diffractometer under the condition of 298K, and refining by using structure analysis software Olex2 to obtain a crystal structure. The specific structure is shown in the attached drawings of the specification.
The third step: in order to remove solvent molecules in the material pore channels, the crystalline sample obtained in the above way is soaked in methanol solvent after being washed by DMF solvent, and the solvent exchange lasts for 3-5 times. And degassing the exchanged sample at 120 ℃ for 12h under vacuum to prepare the material for testing gas adsorption.
It can be seen from the table that the microporous zinc MOF material belongs to the monoclinic system, the space group is P2/c, and the unit cell parameter is
Figure BDA0003230066260000041
Figure BDA0003230066260000042
α＝90°，β＝112.152(8)°，γ＝90°。
Wherein the crystal data are as follows:
Figure BDA0003230066260000051
the schematic of the triple interpenetration structure of the microporous zinc MOF material in fig. 1 shows: the binuclear metallic zinc and the TCBPE ligand form a two-dimensional layered structure, and the binuclear metallic zinc in the two-dimensional layered structure is connected with the Bpb ligand to form a three-dimensional microporous structure.
The nitrogen adsorption isotherms in fig. 2 indicate that: the MOF is a microporous material and has a high specific surface area.
The adsorption curves for carbon dioxide and methane in fig. 3 and 4 show that: compared with methane, Zn-TCBPE-Bpb has stronger action on carbon dioxide.
The above results indicate that the microporous zinc MOF material has the property of selective adsorption of carbon dioxide. The invention provides reference for the structure design and gas separation performance of the metal organic framework material, and has application prospect in the field of carbon dioxide selective adsorption.
The above is a preferred embodiment of the present invention, but the present invention should not be limited to the disclosure of this embodiment. Therefore, equivalents and modifications may be made thereto without departing from the spirit of the disclosure.

Claims (10)

1. A microporous zinc MOF material for selective adsorption of carbon dioxide, wherein molecular junctions of the microporous zinc MOF materialStructure formula is Zn2(TCBPE) (Bpb), wherein TCBPE is a planar tetracarboxylic acid ligand and Bpb is a bipyridine ligand.
2. A microporous zinc MOF material for the selective adsorption of carbon dioxide according to claim 1 wherein TCBPE is tetrakis [4- (4' -carboxyphenyl) phenyl ] ethylene and Bpb is 1, 4-bis (4-pyridyl) benzene.
3. A microporous zinc MOF material for the selective adsorption of carbon dioxide according to claim 1, wherein the microporous zinc MOF material belongs to the monoclinic system, space group is P2/c, and unit cell parameter is
Figure FDA0003230066250000011
Figure FDA0003230066250000012
α＝90°，β＝112.152(8)°，γ＝90°。
4. A microporous zinc MOF material for selective adsorption of carbon dioxide according to claim 1, wherein the microporous zinc MOF material is a triple interpenetrating layered column structure, the binuclear metallic zinc and TCBPE ligands form a two-dimensional layered structure, and the binuclear metallic zinc in the two-dimensional layered structure is connected with Bpb ligands to form a three-dimensional microporous structure.
5. A process for preparing a microporous zinc MOF material for selective adsorption of carbon dioxide according to any of claims 1 to 4, comprising the steps of:
(1) the organic ligands TCBPE, Bpb and zinc nitrate Zn (NO)3)2Dissolving in a mixed solution of N, N-Dimethylformamide (DMF) and methanol (MeOH);
(2) and (2) carrying out solvothermal reaction on the mixed solution in the step (1) to obtain a blocky single crystal, and washing the blocky single crystal with DMF (dimethyl formamide) to obtain the microporous zinc MOF material.
6. The process of claim 5 wherein the molar ratio of said organic ligand TCBPE to said organic ligand Bpb is from 1:1 to 1: 3; zinc nitrate Zn (NO) is preferred3)2The total molar ratio to the organic ligands TCBPE and Bpb was 1: 1.
7. The process of claim 5, wherein the volume ratio of DMF to MeOH in the mixed solvent is from 1:1 to 2: 1.
8. The method as claimed in claim 5, wherein the solvothermal reaction temperature is 100 ℃ and the reaction time is 48 to 96 hours.
9. Use of a microporous zinc MOF material according to any one of claims 1 to 4 for the selective adsorption of carbon dioxide, a zinc-based metal organic framework material for the selective adsorption of carbon dioxide gas.
10. Use according to claim 9 for separating carbon dioxide and methane.
CN202110986197.0A 2021-08-25 2021-08-25 Preparation of zinc-based metal organic framework material and selective adsorption application thereof Active CN113603897B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110986197.0A CN113603897B (en) 2021-08-25 2021-08-25 Preparation of zinc-based metal organic framework material and selective adsorption application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110986197.0A CN113603897B (en) 2021-08-25 2021-08-25 Preparation of zinc-based metal organic framework material and selective adsorption application thereof

Publications (2)

Publication Number Publication Date
CN113603897A true CN113603897A (en) 2021-11-05
CN113603897B CN113603897B (en) 2022-06-07

Family

ID=78342067

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110986197.0A Active CN113603897B (en) 2021-08-25 2021-08-25 Preparation of zinc-based metal organic framework material and selective adsorption application thereof

Country Status (1)

Country Link
CN (1) CN113603897B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115490875A (en) * 2022-09-28 2022-12-20 北京工业大学 Zinc-based microporous metal organic framework material, preparation method and application in saccharin detection
CN115536857A (en) * 2022-09-28 2022-12-30 北京工业大学 Zinc-organic framework material for selectively adsorbing carbon dioxide and synthesis method
CN116082657A (en) * 2023-02-14 2023-05-09 北京工业大学 Zinc-based metal organic framework material, preparation method thereof and ethylene separation application

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101069836A (en) * 2007-02-16 2007-11-14 南开大学 Microporous zinc coordination polymer material and preparing method and use
CN108623816A (en) * 2018-07-06 2018-10-09 陕西理工大学 A kind of micropore zinc (II) coordination polymer crystal and the preparation method and application thereof
US20190217270A1 (en) * 2016-08-29 2019-07-18 Cornell University Metal organic frameworks and methods of making and using same
CN110862404A (en) * 2019-04-02 2020-03-06 云南农业大学 Metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl and preparation method thereof
CN111484628A (en) * 2020-06-03 2020-08-04 福建师范大学 MOFs-zinc material and preparation method and application thereof
WO2021002982A1 (en) * 2019-07-03 2021-01-07 Exxonmobil Research And Engineering Company Metal-organic framework materials comprising a pyrazolylbenzoate ligand and methods for production thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101069836A (en) * 2007-02-16 2007-11-14 南开大学 Microporous zinc coordination polymer material and preparing method and use
US20190217270A1 (en) * 2016-08-29 2019-07-18 Cornell University Metal organic frameworks and methods of making and using same
CN108623816A (en) * 2018-07-06 2018-10-09 陕西理工大学 A kind of micropore zinc (II) coordination polymer crystal and the preparation method and application thereof
CN110862404A (en) * 2019-04-02 2020-03-06 云南农业大学 Metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl and preparation method thereof
WO2021002982A1 (en) * 2019-07-03 2021-01-07 Exxonmobil Research And Engineering Company Metal-organic framework materials comprising a pyrazolylbenzoate ligand and methods for production thereof
CN111484628A (en) * 2020-06-03 2020-08-04 福建师范大学 MOFs-zinc material and preparation method and application thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115490875A (en) * 2022-09-28 2022-12-20 北京工业大学 Zinc-based microporous metal organic framework material, preparation method and application in saccharin detection
CN115536857A (en) * 2022-09-28 2022-12-30 北京工业大学 Zinc-organic framework material for selectively adsorbing carbon dioxide and synthesis method
CN115536857B (en) * 2022-09-28 2023-07-14 北京工业大学 Zinc-organic framework material capable of selectively adsorbing carbon dioxide and synthesis method
CN116082657A (en) * 2023-02-14 2023-05-09 北京工业大学 Zinc-based metal organic framework material, preparation method thereof and ethylene separation application
CN116082657B (en) * 2023-02-14 2024-04-05 北京工业大学 Zinc-based metal organic framework material, preparation method thereof and ethylene separation application

Also Published As

Publication number Publication date
CN113603897B (en) 2022-06-07

Similar Documents

Publication Publication Date Title
CN113603897B (en) Preparation of zinc-based metal organic framework material and selective adsorption application thereof
CN110496604B (en) Cobalt-nickel bimetallic organic framework carbon dioxide adsorption material and preparation method and application thereof
CN113019330B (en) Preparation of copper-based metal-organic framework material and acetylene/carbon dioxide separation application thereof
CN110938213B (en) Preparation method of copper-based microporous metal organic framework material and gas separation application thereof
CN107353412B (en) Preparation method and application of metal organic framework material
CN109776252B (en) Propylene propane separation method
CN109420479B (en) Ion hybrid porous material and preparation method and application thereof
CN115536857B (en) Zinc-organic framework material capable of selectively adsorbing carbon dioxide and synthesis method
KR101707821B1 (en) Preparation of Mg-MOF and its amine-functionalization
CN111375385A (en) Preparation method and application of bimetallic organic framework adsorbent
CN112827470A (en) Selective air water-absorbing MOFs material with high stability and preparation method thereof
CN115028850B (en) Metal organic framework material for adsorbing and separating acetylene/ethylene mixed gas and preparation method thereof
CN108654564B (en) Preparation method and application of coordination polymer porous material
CN113214493A (en) Preparation of cobalt-based metal organic framework material and low-carbon hydrocarbon separation application thereof
CN110563957A (en) Preparation method and application of three-dimensional iron-based metal-organic framework
CN114031788B (en) Microporous zinc coordination polymer for propyne propylene separation and preparation method thereof
CN109400891B (en) Cadmium-based metal organic framework and preparation method and application thereof
CN115678024B (en) Fluorosilicate MOF material and preparation method and application thereof
CN113769715B (en) Yttrium-based metal organic framework material and preparation method and application thereof
CN114805838A (en) Porous coordination polymer and green preparation method and application thereof
CN114558546A (en) Cu (I)/molecular sieve adsorbent and preparation method and application thereof
CN110394161B (en) Application of cobalt complex as greenhouse gas adsorption material
CN114989442B (en) For CO 2 Preparation method of adsorption-captured ultra-microporous porous coordination polymer
CN114085386B (en) Large-scale synthesis method of low-cost Cu (BDC) and application of large-scale synthesis method in ethane-ethylene separation
CN114479095B (en) Cu-based metal-organic framework material and preparation method and application thereof

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