CN110776522B - Copper metal organic framework material and preparation method thereof, gas capture method and gas separation method - Google Patents
Copper metal organic framework material and preparation method thereof, gas capture method and gas separation method Download PDFInfo
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- 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
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- 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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- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
- B01D2256/245—Methane
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Abstract
The invention provides a copper metal organic framework material, the molecular formula of which is { [ Cu ] 2 (P)·(H 2 O) 2 ]·2H 2 O·3DMF·(CH 3 ) 2 NH 2 ]} n Wherein P is a negative pentavalent anion ligand, the metal organic framework material belongs to a trigonal system, the space group is R-3m, the metal organic framework material has a (4, 4) -connected NbO configuration topological structure, and the unit cell parameter is
α/deg＝90.0，β/deg＝90.0，γ/deg＝120.0，
The invention takes the copper metal organic framework material as the adsorbent, the metal organic framework material has good stability, the carbon dioxide is captured, and the mixed gas of the carbon dioxide and the methane is selectively adsorbed, so the adsorption selectivity is high.
Description
Technical Field
The invention relates to the field of materials, in particular to a copper metal organic framework material, a preparation method of the copper metal organic framework material, and CO 2 A gas capture method and also relates to CO 2 Gas and CH 4 A gas separation method.
Background
With the development of global economy and technology, the demand for fossil fuels, petroleum, coal, etc. is continuously increasing in human beings, and at present, and Fossil fuels are still dominant for some time in the future. Combustion resulting in CO 2 And thus cause serious environmental pollution. CO 2 2 As an important component of greenhouse gases, the global ecology is greatly destroyed due to environmental problems caused by the emission of large amounts of greenhouse gases. Therefore, how to effectively remove CO from industrial mixed gas 2 Is the focus of common attention in the scientific and industrial fields in recent years.
On the one hand, low-consumption and high-efficiency method is adopted for CO 2 Will be the key to alleviating the environmental and economic contradiction. On the other hand, natural gas has the advantages of high calorific value, abundant resources, environmental friendliness and the like, and is considered as a good alternative energy. The main component of natural gas is methane, but during the exploitation and transportation of natural gas, CO is often mixed with the main component 2 If the impurity gas cannot effectively remove CO 2 The quality of natural gas can be influenced, the heat value is reduced, and meanwhile, the pipeline corrosion is caused, and the potential safety hazard is generated. Efficient adsorptive separation of CO 2 And CH 4 The gas can relieve the environmental pollution and can also improve the quality of the natural gas. Thus, CO 2 The adsorption separation of (b) has important environmental and industrial significance. The traditional porous adsorption materials such as zeolite, molecular sieve and carbon material are used for adsorbing CO 2 The adsorption amount of (A) is low and the selectivity is poor.
In recent years, metal organic framework Materials (MOFs) have become a novel porous material which is developed most rapidly in the field of materials due to their high specific surface area, adjustable pore structure, and surface chemical properties of pores. Compared with the traditional material, the MOFs material shows excellent performances such as good selectivity, large adsorption capacity, strong stability and the like, and shows great potential in the field of gas adsorption separation. For example, the metal organic framework material can be used for constructing a material with a large specific surface area by adjusting the size of a ligand so as to enhance the adsorption capacity; the MOF material with proper pore size is constructed, and the separation between molecules can be realized differently by utilizing the kinetic radii of different gas molecules. The surface chemical environment of the pore channel is changed and unsaturated sites are generated through functional modification, so that the acting force of the pore channel surface on gas molecules is different, and the gas recognition capability of the framework is improved.
At present, the technical proposal of utilizing metal organic framework materials to adsorb and separate gas molecules has less and simultaneously high CO 2 Adsorption amount and CO 2 /CH 4 And (4) separability.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a copper metal organic framework material and a preparation method, a gas capture method and a gas separation method thereof, and the prepared metal organic framework material can be effectively applied to CO 2 High efficiency of adsorption and CO 2 /CH 4 Selective adsorption of (2).
The technical scheme of the invention is realized as follows:
according to a first aspect of the present invention, a copper metal organic framework material is presented.
In some alternative embodiments, the copper metal organic framework material has a chemical formula { [ Cu ] 2 (P)·(H 2 O) 2 ]·2H 2 O·3DMF·(CH 3 ) 2 NH 2 ]} n In which P is a 1-minus pentavalent anionic ligand, H 5 The structural formula of P is:
optionally, the metal-organic framework material belongs to a trigonal system, has a space group of R-3m, has a topological structure of (4, 4) -connected NbO configuration, and has a unit cell parameter of
α/deg＝90.0，β/deg＝90.0，γ/deg＝120.0，
Optionally, each Cu 2+ The ions adopt penta-coordinationThe mode is coordinated with the oxygen of four carboxylic acids and the oxygen of one water molecule, and the four-pyramid shape is presented, and two adjacent Cu 2+ The center is bridged by four carboxylic acid groups to form a paddle-wheel-shaped secondary construction unit Cu 2 (COO) 4 (H 2 O) 2 Constructing a 3D periodic network structure through ligand bridging; along the c-axis direction, there is 1:1, two types of pore cage: the small spherical cage is composed of six inorganic SBUs and six organic ligands, and the diameter of the pore channel is
The larger shuttle cage is composed of twelve inorganic SBUs and six organic ligands, and the diameter of the pore channel is
The two are connected with each other through a triangular window; the spherical cages and the shuttle-shaped cages are alternately connected in a ratio of 1:1 to form a 3D periodic reticular structure.
According to a second aspect of the present invention, a method for preparing a copper metal organic framework material is provided.
In some optional embodiments, the method for preparing the copper metal organic framework material comprises the following steps:
1.8-2.1 weight parts of solid Cu (NO) 3 ) 2 ·3H 2 O and 2.7-3.0 parts by weight of white powder H 5 P is added to a glass bottle H 5 P＝4-((3,5-dicarboxyphenyl)ethynyl)-[1,1’-biphenyl]-2,3’,5’-tricarboxylic acid；
290-310 parts by weight of DMF/H is added into a glass bottle 2 Mixed solution of O, DMF/H 2 The volume ratio of O is 6: 1, dropwise adding 2.8-3.1 parts by weight of concentrated hydrochloric acid solution (37.5%) into the mixed solution, sealing the mixed solution, putting the sealed mixed solution into a forced air drying oven, and heating the mixed solution to 85-90 ℃ from room temperature;
keeping the temperature for 2500-3500 min at 85-90 ℃;
then, cooling the mixture to 25-35 ℃ at the rate of 5-8 ℃ per hour to obtain a blue blocky crystal;
filtering the blue crystal to obtain copper metal organic frame material with molecular formula { [ Cu { [ 2 (P)·(H 2 O) 2 ]·2H 2 O·3DMF·(CH 3 ) 2 NH 2 ]} n Wherein P is a negative pentavalent anionic ligand, H 5 The structural formula of P is:
alternatively, the mixed solution was sealed and placed in an air-blown dry box and heated from room temperature to 87 ℃.
Optionally, sealing the mixed solution, placing the sealed solution into a forced air drying oven, heating the sealed solution from room temperature to 85-90 ℃, and keeping the heated solution at 85-90 ℃ for 3000 min.
Optionally, cooling the mixture to 25-35 ℃ at a rate of 7 ℃ per hour to obtain blue bulk crystals.
Alternatively, the mixture was cooled to 30 ℃ at a rate of 7 ℃ per hour to give blue bulk crystals.
According to a third aspect of the present invention, there is provided a CO 2 A gas capture process.
In some alternative embodiments, the CO is 2 Gas capture method using copper metal organic framework material as described in any of the alternative embodiments above for CO 2 The gas is adsorbed.
According to a fourth aspect of the present invention, there is provided a CO 2 Gas and CH 4 A gas separation method.
In some alternative embodiments, the CO is 2 Gas and CH 4 Gas separation method adopts the copper metal organic framework material pair CO described in any one of the alternative embodiments 2 The gas is adsorbed.
The invention has the beneficial effects that:
(1) the copper metal organic framework material is used as an adsorbent, the metal organic framework material is good in stability, carbon dioxide is captured, and the mixed gas of carbon dioxide and methane is selectively adsorbed, so that the adsorption selectivity is high;
(2) a pentacarboxylic acid ligand is used, and the ligand on the middle benzene ring does not participate in coordination and deprotonation to form an anionic framework; the carboxylic acid which is not coordinated in the pore channel is a strong polar functional group and can enhance CO 2 Thereby increasing the polarizability of the skeleton and CO 2 Is favorable for CO 2 The adsorption separation of (3);
(3) the functional modification of the acetylenic bond and unsaturated copper site on the pore channel surface of the copper metal organic framework material enhances the functional modification of the copper metal organic framework material and CO 2 Electrostatic interaction of (2);
(4) the synthesis method is simple and easy to operate, has strong operability, low reaction temperature and high process safety, and has wide application in solving greenhouse effect, purifying industrial natural gas and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows a ligand and Cu used in a blue bulk crystal 2+ And (3) a coordination environment diagram of ions.
FIG. 2 is a schematic diagram of a spherical cage and a shuttle cage structure of a blue bulk crystal along the a-axis direction.
FIG. 3 is a three-dimensional frame stacking schematic of blue bulk crystals along the c-axis direction.
Fig. 4 is a graph of the thermal weight loss of an initial synthetic sample of copper metal organic framework material.
FIG. 5 is a powder X-ray diffraction pattern of an initial as-synthesized sample of copper metal organic framework material and the sample after activation.
FIG. 6 shows N of Cu metal organic framework material at 77K temperature 2 Schematic diagram of adsorption isotherms.
FIG. 7a is a graph of CO at 273K and 295K for copper metal organic framework material 2 Schematic diagram of adsorption isotherms.
FIG. 7b shows CH for Cu organometallic framework materials at temperatures of 273K and 295K 4 Schematic diagram of adsorption isotherms.
FIG. 8 shows CO of copper metal organic framework material 2 To CH 4 Selective adsorption curve of (2).
Detailed Description
To make the features and effects of the present invention comprehensible to those having ordinary knowledge in the art, general description and definitions are made with respect to terms and phrases mentioned in the specification and claims. 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.
In this document, the terms "comprising," "including," "having," "containing," or any other similar term, are intended to be open-ended franslational phrase (open-ended franslational phrase) and are intended to cover non-exclusive inclusions. For example, a composition or article comprising a plurality of elements is not limited to only those elements recited herein, but may include other elements not expressly listed but generally inherent to such composition or article. In addition, unless expressly stated to the contrary, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". For example, the condition "a or B" is satisfied in any of the following cases: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), both a and B are true (or present). Furthermore, in this document, the terms "comprising," including, "" having, "" containing, "and" containing "are to be construed as specifically disclosed and to cover both closed and semi-closed conjunctions, such as" consisting of … "and" consisting essentially of ….
All features or conditions defined in numerical ranges or percentage ranges herein are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have covered and specifically disclosed all possible subranges and individual numerical values within the ranges, particularly integer numerical values. For example, a description of a range of "1 to 8" should be considered to have specifically disclosed all subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, and so on, particularly subranges bounded by all integer values, and should be considered to have specifically disclosed individual values such as 1, 2, 3, 4, 5, 6, 7, 8, and so on, within the range. Unless otherwise indicated, the foregoing explanatory methods apply to all matters contained in the entire disclosure, whether broad or not.
If an amount or other value or parameter is expressed as a range, preferred range, or a list of upper and lower limits, it is to be understood that all ranges subsumed therein for any pair of that range's upper or preferred value and that range's lower or preferred value, whether or not such ranges are separately disclosed, are specifically disclosed herein. Further, when a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
Numerical values are herein understood to have the precision of the number of significant digits in the value, provided that the object of the invention is achieved. For example, the number 40.0 should be understood to encompass a range from 39.50 to 40.49.
In this document, where Markush group (Markush group) or Option language is used to describe features or examples of the invention, those skilled in the art will recognize that a sub-group of all elements or any individual element within a Markush group or list of options may also be used to describe the invention. For example, if X is described as "selected from the group consisting of 1 、X 2 And X 3 The group "also indicates that X has been fully described as X 1 Is claimed with X 1 And/or X 2 Claim (5). Furthermore, where Markush group or option terms are used to describe features or examples of the invention, those skilled in the art will recognize that any combination of sub-groups of all elements or individual elements within the Markush group or option list can also be used to describe the invention. Accordingly, for example, if X is described as "selected from the group consisting of 1 、X 2 And X 3 Group consisting of "and Y is described as" selected from Y 1 、Y 2 And Y 3 The group "formed indicates that X has been fully described as X 1 Or X 2 Or X 3 And Y is Y 1 Or Y 2 Or Y 3 Claim (5).
The following detailed description is merely exemplary in nature and is not intended to limit the invention or the application thereof. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or the summary of the invention or the following detailed description or examples.
Results of elemental analysis
The material obtained by the preparation method of the copper metal organic framework material is subjected to elemental analysis.
Results of elemental analysis
Determining C, N, O content based on elemental analysis and single crystal diffraction data, and determining the chemical formula of the metal-organic framework material as C 36 Cu 2 O 17 H 46 N 4 。
Structure description of copper metal organic framework material
As shown in FIG. 1, FIG. 2 and FIG. 3, the molecular formula of the copper metal organic framework material obtained based on elemental analysis, TGA, single crystal X-ray diffraction and the like is { [ Cu ] 2 (P)·(H 2 O) 2 ]·2H 2 O·3DMF·(CH 3 ) 2 NH 2 ]} n . The copper metal organic framework material belongs to a trigonal system, the space group is R-3m, and the copper metal organic framework material has a (4, 4) -connected NbO configuration topological structure which has the same space structure with NOTT-101, ZJU-24 and the like, and only all connecting chains are replaced by P. Each of Cu 2+ The ion adopts a penta-coordination mode to coordinate with oxygen of four carboxylic acids and oxygen of one water molecule, and presents a quadrangular pyramid shape, and two adjacent Cu 2+ The center is bridged by four carboxylic acid groups to form a paddle-wheel-shaped secondary construction unit Cu 2 (COO) 4 (H 2 O) 2 Further bridged by ligandsA 3D periodic network is constructed. Along the c-axis direction, 1:1, two "cage" type pore channel structures: the small spherical cages are composed of six inorganic SBUs (secondary building blocks) and six organic ligands, with pore diameters of approximately
Larger shuttle cages are constructed with twelve inorganic SBUs and six organic ligands, with pore diameters of about
The two are connected with each other through a triangular window. The two hole cages are alternately connected in a ratio of 1:1 to form a 3D periodic mesh structure.
Thermal stability analysis of copper metal organic framework materials
FIG. 4 is a thermogravimetric curve of a copper metal organic framework material, which shows that the thermogravimetric curve shows three distinct drops in the temperature variation range of 0-800 ℃; before the first stage is 100 ℃, corresponding free water molecules in the pore channel of the copper metal organic framework material are lost; in the second stage 100 to 285 ℃, the solvent molecules DMF (N, N-dimethylformamide) and the coordinating water molecules are mainly lost. Above 310 ℃, the crystal framework begins to collapse.
Powder diffraction testing of copper metal organic framework materials
Powder diffraction testing (PXRD) was used to examine the phase purity of copper metal organic framework material samples at room temperature. As shown in FIG. 5, the diffraction pattern (As-synthesized) of the crystal sample obtained by experimental synthesis is matched with the diffraction pattern (diffused) derived from the single crystal data cif document, which indicates that the copper metal organic framework material of the crystal sample is successfully prepared and has higher phase purity. The peak positions of the diffraction peak (Activatecd) of the activated copper metal organic framework material and the diffraction peak (As-synthesized) of the experimental synthetic sample are basically consistent, which shows that the framework of the activated copper metal organic framework material is stable.
Study on gas adsorption separation Performance
To prove thatThe gold-copper metal organic frame material has permanent pore channels, and N is tested when the gold-copper metal organic frame material is 77K 2 The amount of adsorption of (3). The test process specifically comprises the following steps: firstly, a sample is activated by a solvent exchange method, dichloromethane is firstly used for soaking for 1 day, then chromatographic methanol is used for soaking for 3 days, a fresh methanol solution is replaced every 12 hours to replace DMF (dimethyl formamide) and water molecules which do not participate in coordination, and then the sample is activated for 10 hours under the vacuum condition at the temperature of 95 ℃. A desolvated copper metal organic framework material was obtained, at which point the sample color changed from blue to dark blue, indicating that the coordinating water of the copper metal organic framework material had been removed after activation.
Test N under 77K conditions 2 The adsorption isotherm of (2), as shown in FIG. 6, the activated copper metal organic framework material N 2 The adsorption curve is a typical type-I adsorption isotherm. This indicates that the copper metal organic framework material has a continuous microporous structure, and retains the original pore structure after the solvent molecules are removed. Adsorption curve in the low pressure region (P/P) 0 <0.01), indicating the existence and ordered filling of micropores of the copper metal organic framework material. Then, the adsorption amount of nitrogen is saturated at about 0.1bar, and N of the copper metal organic framework material 2 The adsorption capacity reaches 656cm under the conditions of 77K and 1bar 3 (STP)·g -1 . The BET surface area of the copper metal organic framework material is 2560m 2 ·g -1 Ratio ZJU-24-0.5(1700 m) 2 ·g -1 ) Has a large surface area, but is larger than that of the structure NOT-101 (2800 m) 2 ·g -1 ) Has a small surface area. The reason for this is that the uncoordinated carboxyl groups extend into the pores and the counter ion dimethylamine (dimethylamine is a decomposition product of DMF at high temperature, is a counterion of the framework, and is a cationic compound) is also in the pores, so that the pore volume of the copper metal organic framework material is reduced. The copper metal organic framework material has large specific surface area, pore channel surfaces functionalized by carboxyl and acetylene bonds and a stable pore channel structure. In FIGS. 7a and 7b, the CO of the copper metal organic framework material was further determined 2 And CH 4 The adsorption performance of (3). As can be seen from FIG. 7a, at 1bar, 273K, CO 2 The adsorption capacity reaches 161cm 3 (STP)·g -1 The adsorption amount is higher than that of CPF-1(83.5cm 3 (STP)·g -1 ) And NTU-101-Cu (101 cm) 3 (STP)·g -1 ) But less than some with strong CO 2 MOFs materials with adsorptive properties, e.g. NOT-101 (164 cm) 3 (STP)·g -1 ). As can be seen from FIG. 7b, CH is present at 1bar at 273K 4 Has an adsorption capacity of only 28.5cm 3 (STP)·g -1 Under the conditions of 295K and 1bar, CH 4 Has an adsorption capacity of 17.2cm 3 (STP)·g -1 。
As shown in FIG. 8, it can be seen that the copper metal organic framework material is in CO under 273K condition 2 /CH 4 (50:50) the adsorption selectivity in the mixed gas is 12.6, and the high selectivity shows that the modification of the pore channels by carboxylic acid groups can enhance the CO-pair skeleton 2 The affinity of (2) and the formation of hydrogen bond interaction significantly improve the separation performance. On the other hand, CO 2 Has four dipole moments and strong electrostatic interaction with the framework. With CO 2 Increase in adsorption, CO 2 The molecule occupies more of the adsorption site, resulting in CH 4 The amount of adsorption of (a) is relatively reduced. Selective adsorption of CO by copper metal organic framework material 2 Indicating that copper metal organic framework materials have the potential to purify natural gas.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A copper metal organic frame material is characterized in that the molecular formula is { [ Cu ] 2 (P)·(H 2 O) 2 ]·2H 2 O·3DMF·(CH 3 ) 2 NH 2 ]} n Wherein P is a negative pentavalent anionic ligand, H 5 The structural formula of P is:
2. the copper metal-organic framework material according to claim 1, wherein the metal-organic framework material belongs to the trigonal system, has a space group of R-3m, has a (4, 4) -connected NbO topology, and has a unit cell parameter of
α/deg＝90.0，β/deg＝90.0，γ/deg＝120.0，
3. The copper metal-organic framework material according to claim 1,
each of Cu 2+ The ion adopts a penta-coordination mode to coordinate with oxygen of four carboxylic acids and oxygen of one water molecule, and presents a quadrangular pyramid shape, and two adjacent Cu 2+ The center is bridged by four carboxylic acid groups to form a paddle-wheel-shaped secondary construction unit Cu 2 (COO) 4 (H 2 O) 2 Constructing a 3D periodic network structure through ligand bridging; along the c-axis direction, there is 1:1, two types of pore cage: the small spherical cage is composed of six inorganic SBUs and six organic ligands, and the diameter of the pore channel is
The larger shuttle cage is composed of twelve inorganic SBUs and six organic ligands, and the diameter of the pore channel is
The two are connected with each other through a triangular window; the spherical cages and the shuttle-shaped cages are alternately connected in a ratio of 1:1 to form a 3D periodic reticular structure.
4. A preparation method of a copper metal organic framework material is characterized by comprising the following steps:
1.8 to 2.1 parts by weight of solid Cu(NO 3 ) 2 ·3H 2 O and 2.7-3.0 parts by weight of white powder H 5 Adding P into a glass bottle;
290-310 parts by weight of DMF/H is added into a glass bottle 2 Mixed solution of O, DMF/H 2 The volume ratio of O is 6: 1, dropwise adding 2.8-3.1 parts by weight of concentrated hydrochloric acid solution into the mixed solution, sealing the mixed solution, putting the sealed mixed solution into a forced air drying oven, and heating the mixed solution to 85-90 ℃ from room temperature;
keeping the temperature for 2500-3500 min at 85-90 ℃;
then, cooling the mixture to 25-35 ℃ at the rate of 5-8 ℃ per hour to obtain a blue blocky crystal;
filtering the blue crystal to obtain copper metal organic frame material with molecular formula { [ Cu { [ 2 (P)·(H 2 O) 2 ]·2H 2 O·3DMF·(CH 3 ) 2 NH 2 ]} n Wherein P is a negative pentavalent anionic ligand, H 5 The structural formula of P is:
5. the method according to claim 4, wherein the organic framework material of copper is selected from the group consisting of,
the mixed solution was sealed and placed in an air-blown dry box and heated from room temperature to 87 ℃.
6. The method according to claim 4, wherein the organic framework material of copper is selected from the group consisting of,
and sealing the mixed solution, putting the sealed solution into a blast drying oven, heating the solution to 85-90 ℃ from room temperature, and keeping the temperature at 85-90 ℃ for 3000 min.
7. The method according to claim 4, wherein the organic framework material of copper is selected from the group consisting of,
and cooling the mixture to 25-35 ℃ at the rate of 7 ℃ per hour to obtain blue blocky crystals.
8. The method according to claim 7, wherein the organic framework material of copper is selected from the group consisting of,
the mixture was cooled to 30 ℃ at a rate of 7 ℃ per hour to give blue blocky crystals.
9. CO (carbon monoxide) 2 A gas capture process, characterized in that the copper metal organic framework material according to any of claims 1 to 3 is used for CO 2 The gas is adsorbed.
10. CO (carbon monoxide) 2 Gas and CH 4 Gas separation process, characterized in that the copper metal organic framework material according to any of claims 1 to 3 is used for CO 2 The gas is adsorbed.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107602592A (en) * | 2017-10-25 | 2018-01-19 | 青岛大学 | One kind separation CO2Metal-organic framework material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| A NbO-type metal–organic framework exhibiting high deliverable capacity for methane storage;Chengling Song等;《Chem. Commun.》;20150413;第51卷;8508-8511 * |
| A porous metal–organic framework with an elongated anthracene derivative exhibiting a high working capacity for the storage of methane;Hui-Min Wen等;《J. Mater. Chem. A,》;20140528;第2卷;11516-11522 * |
| High methane storage and working capacities in a NbO-type metal–organic framework;Chengling Song等;《Dalton Trans.》;20160330;第45卷;7559–7562 * |
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