CN113416314B - Copper frame material and preparation method and application thereof - Google Patents
Copper frame material and preparation method and application thereof Download PDFInfo
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- CN113416314B CN113416314B CN202110621089.3A CN202110621089A CN113416314B CN 113416314 B CN113416314 B CN 113416314B CN 202110621089 A CN202110621089 A CN 202110621089A CN 113416314 B CN113416314 B CN 113416314B
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- 239000000463 material Substances 0.000 title claims abstract description 97
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000010949 copper Substances 0.000 title claims abstract description 66
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 35
- 239000003446 ligand Substances 0.000 claims abstract description 31
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005977 Ethylene Substances 0.000 claims abstract description 12
- 238000010276 construction Methods 0.000 claims abstract description 12
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 150000003852 triazoles Chemical group 0.000 claims description 4
- RAMPDACRJWTXEV-UHFFFAOYSA-N methyl 2-cyanobenzoate Chemical compound COC(=O)C1=CC=CC=C1C#N RAMPDACRJWTXEV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 14
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 9
- 239000007789 gas Substances 0.000 description 18
- 239000012621 metal-organic framework Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- KKZMIDYKRKGJHG-UHFFFAOYSA-N methyl 4-cyanobenzoate Chemical compound COC(=O)C1=CC=C(C#N)C=C1 KKZMIDYKRKGJHG-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
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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
- 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]
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Abstract
The invention particularly relates to a copper frame material and a preparation method and application thereof, belonging to the technical field of gas separation, wherein the copper frame material has a chemical formula as follows: [ Cu ]18I18(H2O)9(L)9]nWherein L is 4-amino-3, 5-dibenzoic acid-1, 2, 4-triazole, and n is a positive integer; the copper metal organic framework material has excellent gas separation performance and can realize the selective separation of ethylene and acetylene. Different from the traditional copper metal organic framework material with a single two-level construction element, the material has two-level construction elements and forms a three-dimensional framework pore channel structure through ligand connection. The two multi-connection metal cluster elements and the multi-connection mode of the ligand increase the overall chemical stability of the material. Through the connection of the metal cluster elements and the ligand, a one-dimensional pore channel structure is reserved in the three-dimensional structure, and the pore size is about 0.8 nm. The copper metal organic framework material can show obvious separation effect.
Description
Technical Field
The invention belongs to the technical field of gas separation, and particularly relates to a copper frame material and a preparation method and application thereof.
Background
As one of the current popular research materials, metal-organic framework Materials (MOFs) show unique application prospects in multiple fields by virtue of specific framework structures and channel effects. In view of the good structure-activity relationship of MOFs, research has begun to explore the potential of MOFs as gas adsorption and separation materials. Compared with the traditional inorganic porous molecular sieve and activated carbon materials, the MOFs material has the advantages of adjustable pore channel size, adjustable pore channel surface, selectivity of adsorbed gas molecules and the like. The gas adsorption and separation performance of the material can be effectively improved by modifying or optimizing the connecting body or the node. The separation process of ethylene and acetylene is always a difficult problem in the industrial production process. The existing separation technology is always a high-energy consumption process flow. Therefore, the development of efficient and low-energy-consumption ethylene and acetylene separation materials by using MOFs materials as substrates becomes a sustainable separation method.
However, the existing MOFs gas separation materials are mainly concentrated in a plurality of star MOF systems and are mostly concentrated in metals such as iron, cobalt, copper and the like.
Disclosure of Invention
The applicant finds in the course of the invention that: the MOFs material of the copper ion substrate has the advantage of stable structure, and the related copper metal organic framework material can reserve larger pore channel volume and show higher chemical stability. Although the separation performance of ethylene and acetylene by taking a copper metal organic framework material as a substrate has been reported, the research on the framework material containing two copper cluster secondary building units as a gas separation material is relatively deficient. Therefore, it is necessary to prepare a novel copper metal organic framework material containing a plurality of secondary building units and explore the application possibility of the series of copper metal organic framework materials in the aspects of gas adsorption and separation performance.
The application aims to provide a copper frame material and a preparation method and application thereof, and aims to solve the problem that the existing frame material containing two copper cluster secondary building units is relatively deficient as a gas separation material.
The embodiment of the invention provides a copper frame material, which has a chemical formula as follows: [ Cu ]18I18(H2O)9(L)9]nWherein L is 4-amino-3, 5-dibenzoic acid-1, 2, 4-triazole, and n is a positive integer.
Optionally, the structural formula of the copper frame material is as follows:
wherein n is a positive integer.
Optionally, the copper frame material belongs to a trigonal system; the space group is R-3; having a cell parameter of
α ═ β ═ 90 °, γ ═ 120 °, β ═ 93.965 °; having a cell volume of
Optionally, the copper frame material includes a first building unit and a second building unit, and the first building unit is: paddle-wheel [ Cu ]2(COO)4](ii) a The second construction unit is as follows: [ Cu ]2I4(tra)]Wherein tra represents triazole.
Based on the same inventive concept, the embodiment of the invention also provides a preparation method of the copper frame material, which is characterized by comprising the following steps:
dissolving CuI and a dicarboxylic acid ligand in a solvent to obtain a mixed solution; the dicarboxylic acid ligand has the formula: h2L, wherein L is 4-amino-3, 5-dibenzoic acid-1, 2, 4-triazole;
and reacting the mixed solution at 110-130 ℃ to obtain the copper frame material.
Optionally, the CuI and the dicarboxylic acid ligand are dissolved in a solvent to obtain a mixed solution, and 25mg to 35mg of the CuI is mixed and dissolved in every 5mL to 7mL of the solvent.
Optionally, in the mixed solution, the molar concentration of the dicarboxylic acid ligand is 0.04mol/L-0.05 mol/L.
Optionally, the solvent is N, N' -dimethylformamide.
Optionally, the preparation method of the dicarboxylic acid ligand comprises the following steps:
dissolving methyl cyanobenzoate, hydrazine hydrate and hydrazine monohydrochloride in ethylene glycol, and then reacting to obtain a white solid;
and washing the white solid, and reacting with methanol and NaOH solution to obtain the dicarboxylic acid ligand.
Based on the same inventive concept, the embodiment of the invention also provides an application of the copper frame material, wherein the copper frame material is the copper frame material, and the application comprises the following steps: the copper frame material is applied to separation of acetylene/ethylene mixed gas.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the copper frame material provided by the embodiment of the invention has a chemical formula as follows: [ Cu ]18I18(H2O)9(L)9]nWherein L is 4-amino-3, 5-dibenzoic acid-1, 2, 4-triazole, and n is a positive integer; the copper metal organic framework material has excellent gas separation performance and can realize the selective separation of ethylene and acetylene. Different from the traditional copper metal organic framework material with a single two-level construction element, the material has two-level construction elements and forms a three-dimensional framework pore channel structure through ligand connection. The two multi-connection metal cluster elements and the multi-connection mode of the ligand increase the overall chemical stability of the material. Through the connection of the metal cluster elements and the ligand, a one-dimensional pore channel structure is reserved in the three-dimensional structure, and the pore size is about 0.8 nm. The copper metal organic framework material can show obvious separation effect.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a copper frame material according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a two-stage construction element of a copper frame material provided by an embodiment of the present invention;
FIG. 3 is an XRD spectrum of a copper frame material provided by an embodiment of the present invention;
FIG. 4 is a schematic illustration of a copper frame material for ethylene/acetylene gas separation according to an embodiment of the present invention;
fig. 5 is a schematic diagram of a method provided by an embodiment of the invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
according to an exemplary embodiment of the present invention, there is provided a copper frame material having a chemical formula of: [ Cu ]18I18(H2O)9(L)9]nWherein L is 4-amino-3, 5-dibenzoic acid-1, 2, 4-triazole, and n is a positive integer.
As an alternative embodiment, the copper frame material comprises two secondary building element metal clusters, namely [ Cu ] respectively2(COO)4]And [ Cu ]2I4(tra)]And tra represents triazole, one ligand is connected with three secondary units to form a three-dimensional integral framework structure, and two pore channel structures are shown. The copper metal organic frame material belongs to a trigonal system, the space group is R-3, and the unit cell parameter is
α ═ β ═ 90 °, γ ═ 120 °, unit cell volume
The structure schematic diagram is as follows:
according to another exemplary embodiment of the present invention, there is provided a method of preparing a chromium metal organic framework material as described above, the method including:
s1, dissolving CuI and a dicarboxylic acid ligand in a solvent to obtain a mixed solution; the dicarboxylic acid ligand has the formula: h2L, wherein L is 4-amino-3, 5-dibenzoic acid-1, 2, 4-triazole.
The dicarboxylic acid ligand can be obtained by a purchased mode or a self-made mode, and the preparation method comprises the following steps: firstly, a reflux device is built on a vacuum operation line platform, and vacuumizing and air exchange are carried out for three times. About 2.5g of methyl p-cyanobenzoate, 2.2g of hydrazine hydrate and about 2.1g of hydrazine monohydrochloride are weighed by a split balance into a two-neck round-bottom flask, 50mL of diethylene glycol is added, and a stirrer is added. After stirring at 130 ℃ for 72 hours, heating was stopped and cooled, and a white solid was obtained by filtration and washed with a large amount of deionized water. Placing the dried white solid in a solution of 50mL methanol and 2g NaOH, stirring at 80 ℃ for 12 hours, filtering, and dropwise adding 2mol L of the filtrate-1The hydrochloric acid is neutralized, and the filtered white solid is the final product.
As an alternative embodiment, the CuI and the dicarboxylic acid ligand are dissolved in a solvent to obtain a mixed solution, and 25mg to 35mg of the CuI is mixed and dissolved in every 5mL to 7mL of the solvent; the molar concentration of the dicarboxylic acid ligand is 0.04-0.05 mol/L.
As an alternative embodiment, the solvent may be selected from N, N' -dimethylformamide.
S2, reacting the mixed solution at the temperature of 110-130 ℃ to obtain the copper frame material.
Specifically, the mixed solution is placed in a stainless steel reaction kettle at 120 ℃, and a large amount of copper metal organic framework blue crystals are prepared after 2 days.
The copper frame material of the present application, and the preparation method and application thereof will be described in detail below with reference to examples, comparative examples and experimental data.
Example 1
Preparation of the dicarboxylic acid ligand:
firstly, a reflux device is built on a vacuum operation line platform, and vacuumizing and air exchange are carried out for three times. About 2.5g of methyl p-cyanobenzoate, 2.2g of hydrazine hydrate and about 2.1g of hydrazine monohydrochloride are weighed by a split balance into a two-neck round-bottom flask, 50mL of diethylene glycol is added, and a stirrer is added. After stirring at 130 ℃ for 72 hours, heating was stopped and cooled, and a white solid was obtained by filtration and washed with a large amount of deionized water. Placing the dried white solid in a solution of 50mL methanol and 2g NaOH, stirring at 80 ℃ for 12 hours, filtering, and dropwise adding 2mol L of the filtrate-1The hydrochloric acid is neutralized, and the filtered white solid is the final product.
Preparing a copper frame material:
weighing 25-35mg of CuI and 15-25mg of dicarboxylic acid ligand by using an analytical body balance, placing the weighed CuI and the dicarboxylic acid ligand in a mixed solution of 5-7mL of N, N' -dimethylformamide and 1-2mL of water, and carrying out ultrasonic treatment for 5 minutes. And (3) placing the mixed solution in a 25mL stainless steel reaction kettle, heating at 120 ℃ for 2 days, and cooling to room temperature to obtain a blue blocky copper metal organic framework material crystal which can be used for analyzing the specific structure of the complex by single crystal structure analysis.
Characterization of properties of the copper framework material:
1) structural determination of iron metal organic framework:
single crystal size of Compound 1 was 0.2X 0.1mm, on Bruker Venture with Cu-Ka ((R))
) And (6) obtaining. Single crystal data were measured at 100K. Empirical absorption correction of all data is done by the software of the program itself. The structure analysis and refinement are carried out by obtaining all non-hydrogen atoms by using a shell-X-2014 program and adopting a full-matrix least square (full-matrix least-square-refined-on F)2) And (5) performing structure fine trimming. All non-hydrogen atoms are anisotropically refined. The hydrogen atoms on the organic ligands being generated geometrically symmetrically
As shown in FIGS. 1 and 2, the results of the tests showed that a copper metal organic framework material as a gas separation material had the same structure as the template iron metal organic framework material, and thus had the chemical formula [ Cu ]18I18(H2O)9(L)9]nWherein H is2L is 4-amino-3, 5-dibenzoic acid-1, 2, 4-triazole, n is infinity, wherein the two secondary building element metal clusters are respectively [ Cu [ ]2(COO)4]And [ Cu ]2I4(tra)]And tra represents triazole, one ligand is connected with three secondary units to form a three-dimensional integral framework structure, and two pore channel structures are shown. The copper metal organic frame material belongs to a trigonal system, the space group is R-3, and the unit cell parameter is
α ═ β ═ 90 °, γ ═ 120 °, unit cell volume
2) And (3) morphological characterization of the copper frame material:
mercury fits the iron metal organic framework single crystal structure to obtain powder diffraction data, and the powder diffraction data are compared with a powder diffraction pattern actually measured by a copper metal organic framework material single crystal sample to find that the peak positions are basically consistent, so that the purity and the structural correctness of the sample are verified, and the figure is 3.
The porous characteristic of the prepared copper metal organic framework material is proved by a low-temperature nitrogen adsorption test experiment, and the copper metal organic framework shows an I-type adsorption curve under 77K, which indicates that the material has a microporous structure. The Langmuir surface area is 834.2m by calculation2 g-1BET surface area of 503.3m2 g-1。
In addition, the copper metal organic framework material can also show adsorption capacity to ethane, ethylene and acetylene. Calculated by fitting a formula, for C2H2,C2H4And C2H6The adsorption enthalpy change values are respectively 31.2,29.5 and 18.2kJ mol-1. Theoretical calculation results show that the copper metal organic framework can be used as an ethylene/acetylene separation material. The separation behavior was verified by penetration test, as shown in fig. 4, the test result shows that 1/99C was calculated according to the penetration curve with copper metal organic frame material as the gas separation material2H2/C2H4Hybrid system C adsorbed at 0-breakthrough time2H2The amount was 1.08cm each3g-1The method shows a good separation effect, and shows that the related copper frame material can realize the selective separation of the simple substance object.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
(1) the copper frame material provided by the embodiment of the invention has excellent gas separation performance and can realize selective separation of ethylene and acetylene. Different from the traditional copper metal organic framework material with a single two-level construction element, the material has two-level construction elements and forms a three-dimensional framework pore channel structure through ligand connection. The two multi-connection metal cluster elements and the multi-connection mode of the ligand increase the overall chemical stability of the material. Through the connection of the metal cluster elements and the ligand, a one-dimensional pore channel structure is reserved in the three-dimensional structure, and the pore size is about 0.8 nm. The copper metal organic framework material can show obvious separation effect;
(2) the analysis result of the method system provided by the embodiment of the invention fully shows the important role of different copper cluster elements in the aspect of gas separation, and provides another research and development approach for reference for the preparation of the separation material taking the metal organic framework as the substrate. The implementation of the strategy can not only effectively meet the requirements on new structure and new performance, but also effectively improve the gas separation effect of the material;
(3) the method provided by the embodiment of the invention utilizes the prepared novel iron metal organic framework material as a template, and the copper metal organic framework material prepared by the post-modification method can be used as a material for separating acetylene and ethylene gas. In addition, the preparation method of the copper metal organic framework is simple and convenient, novel in structure and high in stability of the porous framework structure, and is suitable for being popularized and prepared as a novel gas separation material.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (7)
1. A copper frame material, characterized in that, the chemical formula of the copper frame material is: [ Cu ]18I18(H2O)9(L)9]nWherein L is a part formed by coordination of 4-amino-3, 5-dibenzoic acid-1, 2, 4-triazole, and n is a positive integer;
the structural formula of the copper frame material is as follows:
wherein n is a positive integer;
the copper frame material belongs to a trigonal system; the space group is R-3; having a cell parameter of
α ═ β ═ 90 °, γ ═ 120 °, β ═ 93.965 °; having a cell volume of
The copper frame material comprises a first construction unit and a second construction unit, wherein the first construction unit is as follows: paddle-wheel [ Cu ]2(COO)4](ii) a The second construction unit is as follows: [ Cu ]2I4(tra)]Wherein tra represents triazole.
2. A method of making the copper frame material of claim 1, comprising:
dissolving CuI and a dicarboxylic acid ligand in a solvent to obtain a mixed solution; the dicarboxylic acid ligand has the formula: h2L, wherein H2L is 4-amino-3, 5-dibenzoic acid-1, 2, 4-triazole;
and reacting the mixed solution at 110-130 ℃ to obtain the copper frame material.
3. The method for preparing a copper frame material according to claim 2, wherein the CuI and the dicarboxylic acid ligand are dissolved in a solvent to obtain a mixed solution, and 25mg to 35mg of the CuI is mixed and dissolved in every 5mL to 7mL of the solvent.
4. The method for preparing a copper frame material according to claim 2, wherein the molar concentration of the dicarboxylic acid ligand in the mixed solution is 0.04mol/L to 0.05 mol/L.
5. The method for preparing a copper frame material according to claim 2, wherein the solvent is N, N' -dimethylformamide.
6. The method for preparing a copper frame material according to claim 2, wherein the method for preparing the dicarboxylic acid ligand comprises:
dissolving methyl cyanobenzoate, hydrazine hydrate and hydrazine monohydrochloride in ethylene glycol, and then reacting to obtain a white solid;
and washing the white solid, and reacting with methanol and NaOH solution to obtain the dicarboxylic acid ligand.
7. Use of a copper frame material according to claim 1, wherein the copper frame material is a copper frame material, the use comprising: the copper frame material is applied to separation of acetylene/ethylene mixed gas.
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