CN113801337B - Metal organic framework material for adsorbing and separating ethylene and ethane and preparation method and application thereof - Google Patents
Metal organic framework material for adsorbing and separating ethylene and ethane and preparation method and application thereof Download PDFInfo
- Publication number
- CN113801337B CN113801337B CN202111202596.XA CN202111202596A CN113801337B CN 113801337 B CN113801337 B CN 113801337B CN 202111202596 A CN202111202596 A CN 202111202596A CN 113801337 B CN113801337 B CN 113801337B
- Authority
- CN
- China
- Prior art keywords
- organic framework
- framework material
- bpz
- ethane
- metal organic
- 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.)
- Active
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
- 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]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a metal organic framework material for adsorbing and separating ethylene and ethane, which has a chemical formula of [ Zn ] 2 (BDC)(H 2 BPZ) 0.5 (HBPZ)(BPZ) 0.5 ]2CH 3 OH·2H 2 O.DMF wherein BDC is a deprotonated divalent negative terephthalate anion ligand, said H 2 BPZ, HBPZ and BPZ are respectively a zero-valent, negative-valent and negative-valent anion ligand of 3,3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -dipyrazole, and the DMF is N, N-dimethylformamide. Meanwhile, the invention also discloses a preparation method and application of the metal organic framework material. The metal organic framework material has an excellent function of adsorbing and separating ethylene and ethane, and has an important application value in the aspect of separation and purification of ethylene in the fields of petroleum, chemical engineering and the like.
Description
Technical Field
The invention belongs to the field of inorganic chemistry and material chemistry science, and particularly relates to a metal organic framework material for adsorbing and separating ethylene and ethane, and a preparation method and application thereof.
Technical Field
Ethylene is one of the most important raw materials for petrochemical industry to manufacture various high-value chemical commodities. Currently ethylene is mainly derived from steam cracking and ethane dehydrogenation, and therefore ethylene inevitably contains a certain amount of ethane impurities, and further purification techniques are required to obtain a high purity ethylene product. Separation of ethylene-ethane mixtures is a huge challenge due to similar physicochemical properties. In summary, the purification of ethylene is of great economic significance and value for the efficient use of ethylene in industry.
A metal organic framework compound, referred to as MOF for short, is a porous material having a periodic network structure formed by connecting a metal center and an organic ligand, and is receiving attention from both academic and industrial fields due to its wide application prospect. Compared with traditional porous carbon, zeolite and other materials, the MOF is characterized by designability of a structure, controllability of pore size and modifiability of a pore surface, so that the MOF has very important application potential in the field of adsorption separation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a metal organic framework material for adsorbing and separating ethylene and ethane, and a preparation method and application thereof.
A metal organic framework material for adsorbing and separating ethylene and ethane has a chemical formula of [ Zn ] 2 (BDC)(H 2 BPZ) 0.5 (HBPZ)(BPZ) 0.5 ] 2 CH 3 OH·2H 2 O.DMF wherein BDC is a deprotonated divalent negative terephthalate anion ligand, said H 2 BPZ, HBPZ and BPZ are respectively a zero-valent, negative-valent and negative-valent anionic ligand of 3,3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -dipyrazole, and the DMF is N, N-dimethylformamide; the BDC and H 2 The structural formulas of BPZ, HBPZ and BPZ are respectively as follows:
preferably, the metal organic framework compound belongs to a trigonal system, the space group is R-3c, and the unit cell parameter is
α ═ β ═ 90 °, cell volume of
The preparation method of the metal organic framework material for adsorbing and separating ethylene and ethane adopts zinc trifluoroacetate tetrahydrate as a metal salt, terephthalic acid, 3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -dipyrazole as an organic ligand, and a mixed solvent of N, N-dimethylformamide, methanol and hydrofluoric acid as a solvent, and adopts a solvothermal method to prepare the metal organic framework material, and comprises the following steps:
(1) sequentially adding zinc trifluoroacetate tetrahydrate, terephthalic acid and 3,3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -bipyrazole into a mixed solvent of N, N-dimethylformamide, methanol and hydrofluoric acid;
(2) placing the mixture into a reaction kettle, heating the mixture to 115-120 ℃ in a sealed manner, keeping the temperature for 65-75 h, and then cooling the mixture to room temperature at the speed of 4-6 ℃/h;
(3) and taking out the reactant to obtain a colorless blocky crystal, namely the metal organic framework material. In the step (1), the adding proportion of the zinc trifluoroacetate tetrahydrate, the terephthalic acid, the 3,3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -bipyrazole N, N-dimethylformamide, the methanol and the hydrofluoric acid is 0.1 mmol: 0.1 mmol: 0.1 mmol: 7mL of: 3.5 mL: 0.05 mL.
The application of the metal organic framework material in the adsorption separation of ethylene and ethane comprises the following steps: and exchanging the metal organic framework material in methanol for 70-80 h, then activating for 4h under vacuum at 100 ℃, and then adsorbing and separating ethylene and ethane.
The invention has the advantages that:
(1) the metal organic framework material for adsorbing and separating ethylene and ethane is prepared by a solvothermal method, the steps are simple, the operation is easy, the equipment requirement is low, and the raw materials are easy to obtain;
(2) the prepared metal organic framework material is a three-dimensional framework containing one-dimensional pore channels, the pore channels have the characteristics of uniform pore size distribution, moderate pore size, nonpolar methyl groups on the surface of the pore channels and the like, have excellent functions of adsorbing and separating ethylene and ethane, and have important application values in the aspect of separating and purifying ethylene in the fields of petroleum, chemical industry and the like.
Drawings
FIG. 1 Zn in Metal organic framework materials 2+ The coordination environment of the ions;
FIG. 2 a ring structure in a metal organic framework material;
FIG. 3 is a three-dimensional framework structure in a metal organic framework material;
FIG. 4 nitrogen adsorption isotherm of a metal-organic framework material at 77K;
FIG. 5 ethylene and ethane adsorption isotherms for a metal-organic framework material at 298K;
FIG. 6 ethane/ethylene adsorption selectivity curve of metal organic framework material at 298K;
fig. 7 volume ratio of metal organic framework material at 298K is 1: 10 ethylene-ethane dynamic breakthrough curve.
Detailed Description
Example 1
Metal for adsorbing and separating ethylene and ethaneAn organic framework material, the chemical formula of the metal organic framework material is [ Zn ] 2 (BDC)(H 2 BPZ) 0.5 (HBPZ)(BPZ) 0.5 ] 2 CH 3 OH·2H 2 O.DMF, wherein BDC is deprotonated divalent negative terephthalate anion ligand, H 2 BPZ, HBPZ and BPZ are respectively a zero-valent, negative-valent and negative-valent anionic ligand of 3,3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -dipyrazole, and the DMF is N, N-dimethylformamide; the BDC and H 2 The structural formulas of BPZ, HBPZ and BPZ are respectively as follows:
the metal organic framework compound belongs to a trigonal system, the space group is R-3c, and the unit cell parameter is
α ═ β ═ 90 °, cell volume of
The preparation method of the metal organic framework material for adsorbing and separating ethylene and ethane adopts zinc trifluoroacetate tetrahydrate as a metal salt, terephthalic acid, 3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -dipyrazole as an organic ligand, and a mixed solvent of N, N-dimethylformamide, methanol and hydrofluoric acid as a solvent, and adopts a solvothermal method to prepare the metal organic framework material, and comprises the following steps:
(1) sequentially adding 0.1mmol of zinc trifluoroacetate tetrahydrate, 0.1mmol of terephthalic acid and 0.1mmol of 3,3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -bipyrazole into a mixed solvent formed by mixing 7mL of N-dimethylformamide, 3.5mL of methanol and 0.05mL of hydrofluoric acid;
(2) placing the mixture into a reaction kettle, heating the mixture to 115-120 ℃ in a sealed manner, keeping the temperature for 65-75 h, and then cooling the mixture to room temperature at the speed of 4-6 ℃/h;
(3) and taking out a reactant, namely the metal organic framework material.
The application of the metal organic framework material in the adsorption separation of ethylene and ethane comprises the following steps: and exchanging the metal organic framework material in methanol for 70-80 h, then activating for 4h at 100 ℃ in vacuum, and then adsorbing and separating ethylene and ethane.
Example 2
A metal organic framework material for adsorbing and separating ethylene and ethane has a chemical formula of [ Zn ] 2 (BDC)(H 2 BPZ) 0.5 (HBPZ)(BPZ) 0.5 ] 2 CH 3 OH·2H 2 O.DMF wherein BDC is a deprotonated divalent negative terephthalate anion ligand, said H 2 BPZ, HBPZ and BPZ are respectively a zero-valent, negative-valent and negative-valent anionic ligand of 3,3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -dipyrazole, and the DMF is N, N-dimethylformamide; the BDC and H 2 The structural formulas of BPZ, HBPZ and BPZ are respectively as follows:
the metal organic framework compound belongs to a trigonal system, the space group is R-3c, and the unit cell parameter is
α ═ β ═ 90 °, cell volume of
The preparation method of the metal organic framework material for adsorbing and separating ethylene and ethane adopts zinc trifluoroacetate tetrahydrate as a metal salt, terephthalic acid, 3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -dipyrazole as an organic ligand, and a mixed solvent of N, N-dimethylformamide, methanol and hydrofluoric acid as a solvent, and adopts a solvothermal method to prepare the metal organic framework material, and comprises the following steps:
(1) sequentially adding 0.1mmol of zinc trifluoroacetate tetrahydrate, 0.1mmol of terephthalic acid and 0.1mmol of 3,3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -bipyrazole into a mixed solvent formed by mixing 7mL of N, N-dimethylformamide, 3.5mL of methanol and 0.05mL of hydrofluoric acid;
(2) placing the mixture into a reaction kettle, sealing and heating the mixture to 115 ℃, keeping the temperature for 75 hours, and then cooling the mixture to room temperature at the speed of 4 ℃/hour;
(3) and taking out the reactant to obtain a colorless blocky crystal, namely the metal organic framework material.
Example 3
A metal organic framework material for adsorbing and separating ethylene and ethane has a chemical formula of [ Zn ] 2 (BDC)(H 2 BPZ) 0.5 (HBPZ)(BPZ) 0.5 ] 2 CH 3 OH·2H 2 O.DMF wherein BDC is a deprotonated divalent negative terephthalate anion ligand, said H 2 BPZ, HBPZ and BPZ are respectively a zero-valent, negative-valent and negative-valent anionic ligand of 3,3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -dipyrazole, and the DMF is N, N-dimethylformamide; the BDC and H 2 The structural formulas of BPZ, HBPZ and BPZ are respectively as follows:
the metal organic framework compound belongs to a trigonal system, the space group is R-3c, and the unit cell parameter is
α ═ β ═ 90 °, cell volume of
The preparation method of the metal organic framework material for adsorbing and separating ethylene and ethane adopts zinc trifluoroacetate tetrahydrate as a metal salt, terephthalic acid, 3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -dipyrazole as an organic ligand, and a mixed solvent of N, N-dimethylformamide, methanol and hydrofluoric acid as a solvent, and adopts a solvothermal method to prepare the metal organic framework material, and comprises the following steps:
(1) sequentially adding 0.1mmol of zinc trifluoroacetate tetrahydrate, 0.1mmol of terephthalic acid and 0.1mmol of 3,3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -bipyrazole into a mixed solvent formed by mixing 7mL of N, N-dimethylformamide, 3.5mL of methanol and 0.05mL of hydrofluoric acid;
(2) placing the mixture into a reaction kettle, sealing and heating the mixture to 120 ℃, keeping the temperature for 65 hours, and then cooling the mixture to room temperature at the speed of 6 ℃/hour;
(3) and taking out the reactant to obtain a colorless blocky crystal, namely the metal organic framework material.
Characterization and analysis of crystal structure
Performing structural characterization and analysis on the metal organic framework material obtained by the invention, wherein the metal organic framework compound belongs to a trigonal system, the space group is R-3c, and the unit cell parameter is
α ═ β ═ 90 °, cell volume of
As shown in FIG. 1, one asymmetric unit of the compound contains two independent Zn 2+ Ion, a BDC organic ligand, an HBPZ ligand, a half H 2 BPZ ligand and half BPZ ligand. Two Zn 2+ The ions have a tetrahedral coordination environment, wherein four coordination atoms of Zn1 come from one carboxylic acid O atom, and the other three come from BPZ, HBPZ and H respectively 2 The N atom of BPZ; and the four coordinating atoms of Zn2 are one carboxylic acid O atom, one N atom from BPZ and two N atoms from HBPZ, respectively. The significant structural features of the compound are the formation of two types of Molecular Building Blocks (MBBs), six Zn1 with three BPZ and three H 2 BPZ is connected to each other by a Zn-N coordination bond to form a triangular cyclic MBB-1 (a in FIG. 2), while six Zn2 and six HBPZ are connected to each other by a Zn-N coordination bond to form a hexagonal cyclic MBB-2 (b in FIG. 2). MBB-1 and MBB-2 are alternately linked by BDC ligands to form a structure with the size of
A one-dimensional (1D) tubular channel. As shown in fig. 3, the tubular channels are interconnected by bipyrazole ligands to form a three-dimensional framework compound with a porosity of up to 44.8% and a surface of the channels containing predominantly aromatic rings of the ligand with nonpolar methyl groups.
Secondly, detecting the adsorption separation performance
The metal organic framework material obtained by the invention is exchanged in methanol for 60 hours and then activated for 4 hours under the vacuum condition of 100 ℃ to obtain the activated metal organic framework material. Then, the adsorption separation performance is detected, and the specific steps are as follows:
(I) adsorption separation test results
The adsorption isotherm of the activated metal-organic framework material at 77K for nitrogen was determined using an ASAP 2020M physical specific surface area analyzer, from which the Langmuir specific surface area was calculated to be 1263.9M as shown in FIG. 4 2 ·g -1 Pore volume of 0.47cm 3 ·g -1 。
Meanwhile, the activated metal organic framework material is used for measuring the adsorption isotherms of the activated metal organic framework material to ethylene and ethane respectively at the temperature of 298K, and the adsorption isotherm is shown in figure 5. From the test results in FIG. 5, it can be found that the adsorption amounts of the metal-organic framework material to ethylene and ethane are 73.0 and 77.8cm, respectively, at 298K and 100kPa 3 g -1 I.e. the adsorption of ethane is slightly higher than the adsorption capacity of ethylene. The selective adsorption of the compound on ethane mainly comes from that the surface of a compound pore channel contains naked nonpolar methyl groups and aromatic rings, and the compounds have adsorption effect on ethane with lower polarity.
According to a gas adsorption isotherm tested at the temperature of 298K, calculating the volume ratio of the activated metal organic framework material under different pressures by using an ideal adsorption solution theory to be 1: separation selectivity of ethane ethylene mixture of 10. As shown in FIG. 6, the ethylene/ethane selectivity values were about 1.69 to 1.45 at pressures ranging from 1 to 100 kPa.
(II) dynamic separation test results
The dynamic penetration test of the activated metal organic framework material to an ethylene-ethane mixture was studied by using QuantachromidNaSorb BT equipment of Congta, USA. Passing a mixed gas of ethane/ethylene/argon at a volume ratio of 1/10/89 through a packed column packed with 1g of the metal-organic framework material at a temperature of 298K, the total flow rate of the mixed gas being 5 mL-min -1 . As shown in fig. 7, the metal-organic framework material can effectively separate ethane and ethylene, wherein ethylene is detected to flow out through the packed column at the first 15 minutes, and ethane is detected to flow out of the packed column after the mixed gas is introduced for 26 minutes, indicating that the metal-organic framework material can effectively separate ethylene and ethane mixture. Therefore, the metal organic framework compound shows an excellent function of separating ethylene and ethane, and has important application value in the aspect of separating and purifying ethylene in the fields of petroleum, chemical engineering and the like.
Claims (4)
1. A metal organic framework material for adsorbing and separating ethylene and ethane is characterized in that: the chemical formula of the metal organic framework material is [ Zn ] 2 (BDC)(H 2 BPZ) 0.5 (HBPZ)(BPZ) 0.5 ] 2 CH 3 OH·2H 2 O.DMF wherein BDC is a deprotonated divalent negative terephthalate anion ligand, said H 2 BPZ, HBPZ and BPZ are respectively a zero-valent, negative-valent and negative-valent anionic ligand of 3,3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -dipyrazole, and the DMF is N, N-dimethylformamide;
the BDC and H 2 The structural formulas of BPZ, HBPZ and BPZ are respectively as follows:
the metal organic framework compound belongs to a trigonal system, and the space group isR-3cThe unit cell parameter is a = b =
、 c = 
，α =β = 
Cell volume of
。
2. A method for preparing a metal organic framework material for adsorptive separation of ethylene and ethane as claimed in claim 1, wherein: the preparation method is characterized in that zinc trifluoroacetate tetrahydrate is used as a metal salt, terephthalic acid, 3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -dipyrazole is used as an organic ligand, a mixed solvent of N, N-dimethylformamide, methanol and hydrofluoric acid is used as a solvent, and the preparation method is carried out by adopting a solvothermal method and comprises the following steps:
(1) sequentially adding zinc trifluoroacetate tetrahydrate, terephthalic acid and 3,3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -bipyrazole into a mixed solvent of N, N-dimethylformamide, methanol and hydrofluoric acid;
(2) placing the mixture into a reaction kettle, heating the mixture to 115-120 ℃ in a sealed manner, keeping the temperature for 65-75 h, and then cooling the mixture to room temperature at the speed of 4-6 ℃/h;
(3) and taking out the reactant to obtain a colorless blocky crystal, namely the metal organic framework material.
3. The method for preparing a metal-organic framework material for adsorptive separation of ethylene and ethane according to claim 2, wherein: in the step (1), the zinc trifluoroacetate tetrahydrate, the terephthalic acid, the 3,3 ', 5, 5' -tetramethyl-1, 1 '-dihydro-4, 4' -bipyrazole, the N, N-dimethylformamide, the methanol and the hydrofluoric acid are added in a ratio of 0.1 mmol: 0.1 mmol: 0.1 mmol: 7mL of: 3.5 mL: 0.05 mL.
4. Use of the metal-organic framework material according to claim 1 for the adsorptive separation of ethylene ethane, characterized in that: and exchanging the metal organic framework material in methanol for 70-80 h, then activating for 4h at 100 ℃ in vacuum, and then adsorbing and separating ethylene and ethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111202596.XA CN113801337B (en) | 2021-10-15 | 2021-10-15 | Metal organic framework material for adsorbing and separating ethylene and ethane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111202596.XA CN113801337B (en) | 2021-10-15 | 2021-10-15 | Metal organic framework material for adsorbing and separating ethylene and ethane and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113801337A CN113801337A (en) | 2021-12-17 |
| CN113801337B true CN113801337B (en) | 2022-09-20 |
Family
ID=78937775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111202596.XA Active CN113801337B (en) | 2021-10-15 | 2021-10-15 | Metal organic framework material for adsorbing and separating ethylene and ethane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113801337B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031632B (en) * | 2021-12-18 | 2023-08-18 | 商丘师范学院 | Double-tooth nitrogen ligand zinc complex with stacked structure and preparation method and application thereof |
| CN115490874B (en) * | 2022-09-21 | 2023-08-04 | 中国矿业大学 | MOF compound with acetylene and ethylene adsorption separation function and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014148482A (en) * | 2013-02-01 | 2014-08-21 | Showa Denko Kk | Method for separating ethylene using metal complex |
| CN108014752A (en) * | 2016-11-03 | 2018-05-11 | 浙江大学 | A kind of separation method for the metal-organic framework material and ethylene-ethane for being used to separate ethane and ethene |
| CN109748770A (en) * | 2019-01-29 | 2019-05-14 | 浙江大学 | A kind of ethylene-ethane adsorption separating method based on ultramicropore metal-organic framework material |
-
2021
- 2021-10-15 CN CN202111202596.XA patent/CN113801337B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014148482A (en) * | 2013-02-01 | 2014-08-21 | Showa Denko Kk | Method for separating ethylene using metal complex |
| CN108014752A (en) * | 2016-11-03 | 2018-05-11 | 浙江大学 | A kind of separation method for the metal-organic framework material and ethylene-ethane for being used to separate ethane and ethene |
| CN109748770A (en) * | 2019-01-29 | 2019-05-14 | 浙江大学 | A kind of ethylene-ethane adsorption separating method based on ultramicropore metal-organic framework material |
Non-Patent Citations (3)
| Title |
|---|
| Lei Hou等.Porous Metal-Organic Framework Based on μ4-oxo Tetrazinc Clusters: Sorption and Guest-Dependent Luminescent Properties.《Inorganic Chemistry》.2008,第47卷(第4期), * |
| Solvent-controlled three families of Zn(II) coordination compounds: synthesis, crystal structure, solvent-induced structural transformation, supramolecular isomerism and photoluminescence;Lu-Lu Han等;《Dalton Trans.》;20150211;第44卷;6052-6061 * |
| Synthesis and Characterization of Polyhedral-Based Metal−Organic Frameworks Using a Flexible Bipyrazole Ligand: Topological Analysis and Sorption Property Studies;Kapil Tomar等;《Crystal Growth & Design》;20150327;第15卷;2732-2741 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113801337A (en) | 2021-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Pore environment engineering in metal–organic frameworks for efficient ethane/ethylene separation | |
| CN113801337B (en) | Metal organic framework material for adsorbing and separating ethylene and ethane and preparation method and application thereof | |
| Wang et al. | Separation of alkane and alkene mixtures by metal–organic frameworks | |
| CN110016145B (en) | Porous metal-organic framework material, preparation method and adsorption separation application thereof | |
| AU2012381962B2 (en) | Metal silicoaluminophosphate molecular sieve having RHO skeleton structure and preparation process therefor | |
| CN107892750B (en) | Metal organic framework material, preparation method and application | |
| CN112592490B (en) | Metal organic framework material of polynuclear cobalt cluster based on two-head pyrazole ligand and application | |
| Lin et al. | Separation of C2/C1 hydrocarbons through a gate-opening effect in a microporous metal–organic framework | |
| KR102011393B1 (en) | Adsorbents for the separation of olefin-paraffin mixtures including C2-C4 hydrocarbons and a separation method of olefin-paraffin gas mixtures using the same | |
| CN113019330A (en) | Preparation of copper-based metal-organic framework material and acetylene/carbon dioxide separation application thereof | |
| CN113621141B (en) | Metal organic framework compound, preparation method and application thereof in adsorption separation | |
| Li et al. | Enhanced gas separation performance of an ultramicroporous pillared-layer framework induced by hanging bare Lewis basic pyridine groups | |
| Duan et al. | A new microporous metal–organic framework with open metal sites and exposed carboxylic acid groups for selective separation of CO 2/CH 4 and C 2 H 2/CH 4 | |
| Li et al. | A Dy 6-cluster-based fcu-MOF with efficient separation of C 2 H 2/C 2 H 4 and selective adsorption of benzene | |
| Jiang et al. | Two Co-based MOFs assembled from an amine-functionalized pyridinecarboxylate ligand: inorganic acid-directed structural variety and gas adsorption properties | |
| Xiang et al. | The diverse structures of Cd (II) coordination polymers with 1, 3, 5-benzenetribenzoate tuned by organic bases | |
| Liu et al. | Linker micro-regulation of a Hofmann-based metal–organic framework for efficient propylene/propane separation | |
| Ding et al. | A pillared-layer framework with high uptake and selective sorption of light hydrocarbons | |
| KR20160045223A (en) | Method for separating and/or purifying mixtures containing olefins and acetylenes using crystalline nano-porous hybrid adsorbent | |
| CN108654564B (en) | Preparation method and application of coordination polymer porous material | |
| CN114031783A (en) | Metal organic framework material and preparation method and application thereof | |
| Xu et al. | Size exclusion propyne/propylene separation in an ultramicroporous yet hydrophobic metal–organic framework | |
| Cheng et al. | Modifying a partial corn-sql layer-based (3, 3, 3, 3, 4, 4)-c topological MOF by substitution of OH− with Cl− and its highly selective adsorption of C2 hydrocarbons over CH 4 | |
| CN113881061B (en) | Metal organic framework porous material and preparation method and application thereof | |
| CN114682231B (en) | Cyano MOFs adsorbent for selectively adsorbing acetylene, preparation method and application |
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 |