CN108654564B - Preparation method and application of coordination polymer porous material - Google Patents
Preparation method and application of coordination polymer porous material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a coordination polymer porous material. The chemical formula of the coordination polymer porous material is (Me)2NH2)[Co3(DCPN)2(μ3‑OH)(H2O)]·11H2And O, DCPN in the formula represents a 5- (3',5' -dicarboxyphenyl) nicotinic acid anion ligand. The preparation process of the porous coordination polymer material is also disclosed, and the porous coordination polymer material is prepared through the reaction of ligand 5- (3',5' -dicarboxyphenyl) nicotinic acid and cobalt salt in solvent. The application of the coordination polymer porous material as an adsorbent is also disclosed. The coordination polymer porous material provided by the invention can be used as an adsorbent, can be used for preparing materials for storage, separation, catalysis, sensing, molecular recognition and the like, and has a good application prospect.
Description
Technical Field
The invention relates to a preparation method and application of a coordination polymer porous material.
Background
Metal-Organic Frameworks (MOFs), also known as porous coordination polymers, are a class of crystalline porous materials. MOFs porous materials contain abundant pores, have good performance in the fields of adsorption separation, fluorescence sensing, catalysis, magnetism and the like, and are widely concerned. The material is a coordination polymer which is formed by connecting an organic ligand containing carboxylic acid, phosphoric acid or nitrogen and metal ions or metal clusters through coordination bonds and has a periodic network structure and regular pore channels, wherein the organic ligand is used as a connector (linker), and the metal ions or the metal clusters are used as nodes (nodes). The organic ligand as the connector can be modified and has controllable length, and the metal elements of the nodes which can participate in coordination are more in variety, so that the MOFs material has rich structure. 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 properties of the material, such as gas adsorption separation, catalysis, photoelectromagnetism and the like, can be effectively improved by modifying or optimizing the connecting body or the node.
Ethylene is an important chemical raw material for polymer production, and the purity of the raw material determines the quality of the product. Acetylene is the main by-product (about 1% by volume) of ethylene production by cracking ethane and poisons and deactivates the catalyst in the ethylene polymerization reaction. In addition, the products of ethane cracking also contain a small excess of ethane, and the separation of ethylene and ethane is one of the most important processes in industry, and its energy consumption is very high (7GJ · t)-1) Accounting for 75-85% of the ethane production cost. Thus, the removal of acetylene and ethane from ethylene using separation processes that are efficient and consume low energy is of great interest to scientists.
At present, some scientists synthesize and utilize MOFs porous materials to separate and remove ethane or acetylene from ethylene at room temperature and normal pressure, so that the energy consumption is reduced, the separation cost is saved, and the method is a separation method with great development prospect. However, the existing materials can be prepared from two components or C2H4/C2H2The ethylene is separated and purified, and multiple purifications are needed to reach the polymerization level>99.95% requirement. Can be prepared from three components C2H2/C2H4/C2H6The MOFs material for separating and purifying ethylene is not reported at present.
Disclosure of Invention
In order to overcome the defects of the prior MOFs porous material technology, the invention aims at providing a coordination polymer porous material, the invention aims at providing a preparation method of the coordination polymer porous material, and the invention aims at providing an application of the coordination polymer porous material, wherein the coordination polymer porous material can solve the problems of high energy consumption and three-component ethylene purification in the separation and purification process in the prior art.
The technical scheme adopted by the invention is as follows:
a coordination polymer porous material with chemical formula of (Me)2NH2)[Co3(DCPN)2(μ3-OH)(H2O)]·11H2And O, DCPN in the formula represents a 5- (3',5' -dicarboxyphenyl) nicotinic acid anion ligand. Such a coordination polymer porous material is hereinafter referred to as TJT-100.
The porous material is a three-dimensional frame structure material with one-dimensional pore channels formed by connecting DCPN with a trinuclear Co cluster, wherein the trinuclear Co cluster unit is formed by two hexacoordinated Co (II) and one pentacoordinated Co (II) through mu3-OH are linked together.
The crystal form of the porous material belongs to an orthorhombic system, the space group is Pbca, and the unit cell parameters are as follows: 23.539
，b＝11.9980
，c＝32.450
。
The preparation method of the coordination polymer porous material is that the ligand 5- (3',5' -dicarboxyphenyl) nicotinic acid and cobalt salt react in N, N-dimethylformamide solvent.
In the preparation method, the molar ratio of the 5- (3',5' -dicarboxyphenyl) nicotinic acid to the cobalt salt is 1: 1.
In the preparation method, the cobalt salt is divalent Co salt.
In the preparation method, the N, N-dimethylformamide solvent is a mixed solution of N, N-dimethylformamide and water.
In the preparation method, the reaction temperature is 120-180 ℃, and the reaction time is 48-96 h.
The coordination polymer porous material is applied as an adsorbent.
Further, the adsorbent used is C2s gas adsorbent.
The invention has the beneficial effects that:
the coordination polymer porous material provided by the invention can be used as an adsorbent, can be used for preparing materials for storage, separation, catalysis, sensing, molecular recognition and the like, and has a good application prospect.
The method comprises the following specific steps:
(1) the coordination polymer porous material provided by the invention has good thermal stability and can be stabilized to 573K; the chemical stability is good, and the framework structure can not be damaged when the composite material is soaked in an aqueous solution with the pH value of more than or equal to 2 and less than or equal to 12 for 24 hours;
(2) under the condition of 298K and normal pressure, the coordination polymer porous material synthesized by the invention has good separation performance of ethylene/acetylene and ethylene/ethane, can adsorb and separate two main impurity components of acetylene and ethane in industrial ethylene, and can obtain high-purity ethylene with the purity of more than 99.997%.
(3) Under the condition of 298K and normal pressure, the coordination polymer porous material synthesized by the invention has good acetylene/ethylene/acetylene three-component gas separation performance, can adsorb and separate two main impurity components of acetylene and ethane in the coordination polymer porous material, and can obtain high-purity ethylene with the purity of more than 99.997%.
Drawings
FIG. 1 is a schematic three-dimensional structure of the porous material TJT-100 of the present invention;
FIG. 2 is a schematic diagram of the crystal synthesis process and activation process of the porous material TJT-100 of the present invention;
FIG. 3 is a crystal structure diagram of the porous material TJT-100 of the present invention: (a) a trinuclear cluster unit of cobalt; (b) the coordination structure diagram of ligand 5- (3',5' -dicarboxyphenyl) nicotinic acid and cobalt salt;
FIG. 4 is a simulated adsorption site diagram of the porous material TJT-100 of the present invention: (a) c2H2An adsorption site map within the pore; (b) c2H4An adsorption site map within the pore; (c) c2H6An adsorption site map within the pore;
FIG. 5 is a graph comparing thermogravimetric curves of a porous material TJT-100 of the present invention before and after activation;
FIG. 6 is a graph showing the X-ray diffraction pattern of the starting powder and the treated porous material TJT-100 of the present invention;
FIG. 7 is an X-ray diffraction pattern of a porous material TJT-100 of the present invention processed at different temperature conditions;
FIG. 8 is an X-ray diffraction pattern of a porous material TJT-100 of the present invention treated at different pH conditions;
FIG. 9 is a isotherm diagram of the adsorption of acetylene, ethylene and ethane at 298K for the porous material TJT-100 of the present invention;
FIG. 10 is a graph of the adsorption isotherm of acetylene in the porous material TJT-100 of the present invention at different temperature conditions;
FIG. 11 is a graph of the adsorption isotherm of ethylene for the porous material TJT-100 of the present invention at different temperature conditions;
FIG. 12 is a graph of the sorption isotherm of ethane for the porous material TJT-100 of the present invention at different temperature conditions;
FIG. 13 is a graph of experimental data of the breakthrough curves of a fixed adsorption bed prepared from the porous material TJT-100 of the present invention at 298K and one atmosphere for a 99:1 gas mixture of ethylene/acetylene in volume ratio;
FIG. 14 is a graph of an experimental ethylene gas separation curve of an adsorption fixed bed prepared from the porous material TJT-100 of the present invention under 298K and one atmosphere for a gas mixture of 99:1 by volume ratio of ethylene/acetylene gas: (a) separation C2H2/C2H4Detecting a gas chromatogram of outlet gas in the process of mixing gas; (b) adsorption of C by TJT-1002H2/C2H4Detecting a gas chromatogram of outlet gas after the mixed gas is saturated;
FIG. 15 is a graph of experimental data of the breakthrough curves of a fixed adsorption bed prepared from the porous material TJT-100 of the present invention at 298K and one atmosphere for a 99:1 gas mixture of ethylene/ethane;
FIG. 16 is a graph showing the experimental results of the fixed adsorption bed prepared from the porous material TJT-100 of the present invention on the separation of ethylene gas from ethylene/ethane gas in a 99:1 gas mixture at 298K and one atmosphere: (a) separation C2H6/C2H4Detecting a gas chromatogram of outlet gas in the process of mixing gas; (b) Adsorption of C by TJT-1002H6/C2H4Detecting a gas chromatogram of outlet gas after the mixed gas is saturated;
FIG. 17 is a graph of experimental data of the breakthrough curves of the fixed adsorption bed prepared from the porous material TJT-100 of the present invention at 298K and one atmosphere for the acetylene/ethane/ethylene gas mixture at a volume ratio of 0.5:0.5: 99;
FIG. 18 is a graph of an experimental ethylene gas separation curve of an adsorption fixed bed prepared from the porous material TJT-100 of the present invention under 298K and one atmosphere for a gas mixture of acetylene/ethane/ethylene at a volume ratio of 0.5:0.5: 99: (a) separation C2H2/C2H4/C2H6Detecting a gas chromatogram of outlet gas in the process of mixing gas; (b) and detecting a gas chromatogram of the outlet gas after the TJT-100 adsorbs the three-component mixed gas to saturate.
Detailed Description
A coordination polymer porous material with chemical formula of (Me)2NH2)[Co3(DCPN)2(μ3-OH)(H2O)]·11H2O, DCPN in the formula represents 5- (3',5' -dicarboxyphenyl) nicotinic acid (H)3DCPN) anionic ligand which is H3Deprotonated DCPN anion; wherein Me represents a methyl group.
Further, the porous material is formed by DCPN (DCPN)3-) Three-dimensional frame structure material with one-dimensional pore canal formed by connecting with a trinuclear Co cluster, wherein the trinuclear Co cluster unit is formed by two hexa-coordinated Co (II) and one penta-coordinated Co (II) passing through mu3-OH are linked together. The three-dimensional structure of the coordination polymer porous material can be seen in figure 1.
Furthermore, the crystal form of the porous material belongs to an orthorhombic system, the space group is Pbca, and the unit cell parameters are as follows: 23.539
，b＝11.9980
，c＝32.450
。
The preparation method of the coordination polymer porous material is that the ligand 5- (3',5' -dicarboxyphenyl) nicotinic acid and cobalt salt react in N, N-dimethylformamide solvent.
Preferably, in the preparation method, the molar ratio of the 5- (3',5' -dicarboxyphenyl) nicotinic acid to the cobalt salt is 1: 1.
Preferably, in the preparation method, the cobalt salt is a divalent Co salt; more preferably, the cobalt salt is CoCl2、Co(NO3)2、Co(CH3COO)2At least one of; still more preferably, the cobalt salt is CoCl2Specifically, CoCl is selected for use2·6H2O。
Preferably, in the preparation method, the N, N-dimethylformamide solvent is a mixed solution of N, N-Dimethylformamide (DMF) and water; further preferably, in the mixed solution, the volume ratio of DMF to water is (4-6): 1.
preferably, in the preparation method, the reaction temperature is 120-180 ℃, and the reaction time is 48-96 hours; more preferably, the reaction temperature is 140-160 ℃, and the reaction time is 70-75 h.
The coordination polymer porous material is applied as an adsorbent.
Further, the adsorbent used is C2s a gas adsorbent; preferably, is C2The s gas is selected from acetylene, ethylene or ethane.
Further, the coordination polymer porous material is used as an adsorbent in separating and purifying ethylene gas, and further, the coordination polymer porous material is used as an adsorbent in separating and purifying ethylene gas in acetylene/ethylene, or the coordination polymer porous material is used as an adsorbent in separating and purifying ethylene gas in ethane/ethylene, or the coordination polymer porous material is used as an adsorbent in separating and purifying ethylene gas in acetylene/ethylene/ethane.
Furthermore, the coordination polymer porous material needs to be activated before being used as an adsorbent.
Preferably, the activation treatment is specifically: firstly, the coordination polymer porous material is soaked in methanol for solvent exchange, then the coordination polymer porous material is dried and then placed in an activation workstation, and the activation workstation is vacuumized for 20 to 30 hours at the temperature of between 140 and 160 ℃ to obtain an activated product.
The present invention will be described in further detail with reference to specific examples.
The raw materials and reagents used in the invention are respectively as follows: ligand 5- (3',5' -dicarboxyphenyl) nicotinic acid (H)3DCPN); n, N-dimethylformamide (AR); cobalt chloride hexahydrate (AR). These starting materials are all available from conventional commercial sources.
Preparation and activation of porous MOFs material TJT-100 single crystal
Ligand H3DCPN is synthesized according to the prior art; ligand H3DCPN(57.0mg，0.2mmol)，CoCl2·6H2O (48.0mg, 0.2mmol), DMF (20mL), and ultrapure water (4mL) were added to a hydrothermal reaction vessel, and the reaction was carried out at 150 ℃ for 72 hours to obtain a bluish purple TJT-100 single crystal with a yield of 78%.
The samples were activated prior to testing the adsorption curve as follows: and (3) soaking a proper amount of crystals in methanol for 24 hours for solvent exchange, sucking out the methanol, adding the methanol again, soaking for 24 hours, repeating the steps for three times, drying the sample in vacuum, placing the sample in an activation workstation, vacuumizing at 150 ℃, and continuing for 24 hours to obtain the activated sample. The crystal synthesis process and the activation process are shown in figure 2.
Structural characterization of TJT-100 before and after activation
Single crystal X-ray Diffraction data were collected on a Rigaku Oxford Diffraction Gemini diffactometer diffractometer using Cu Ka (λ. 0.71073)
) Ray, collecting data by omega scanning, analyzing by direct method, calculating all non-hydrogen atom coordinates by difference Fourier function method and least square method, and calculatingThe structure is corrected using a least squares method. The hydrogen atom of the compound is obtained by a theoretical hydrogenation method. The calculation work is done on a PC using the SHELXTL program. The detailed crystal determination data are shown in table 1. TJT-100a in the table represents the activated TJT-100. The structural diagrams before and after activation are shown in FIG. 2.
TABLE 1 Crystal determination data
Note:aR1＝∑||F0|-|FC||/∑|F0|；bwR2＝∑[w(F0 2-FC 2)2]/∑[w(F0 2)2]1/2。
FIG. 3 is a crystal structure diagram of the porous material TJT-100 of the present invention, and FIG. 3(a) is a three-core cluster unit (SBU) of cobalt; FIG. 3(b) is a coordination diagram of the ligand 5- (3',5' -dicarboxyphenyl) nicotinic acid with a cobalt salt.
FIG. 4 is a TJT-100 simulated adsorption site diagram of the porous material of the present invention, and FIG. 4(a) is C2H2An adsorption site map within the pore; FIG. 4(b) is C2H4An adsorption site map within the pore; FIG. 4(C) is C2H6Dot pattern of adsorption within the pore.
Thermal stability characterization of porous MOFs material TJT-100
The thermal stability of the porous MOFs TJT-100 is obtained by thermogravimetric analysis (TGA) and temperature-variable powder diffraction (PXRD). The TJT-100 provided by the invention has better thermal stability and can be stabilized to 523K. The thermogravimetric plot is shown in FIG. 5. FIG. 6 is a graph showing the X-ray diffraction pattern of the raw powder and the treated porous material TJT-100 according to the present invention; FIG. 7 is an X-ray diffraction pattern of the porous material TJT-100 of the present invention processed at different temperatures.
Meanwhile, the synthesized TJT-100 is directly soaked in an aqueous solution with the pH value of more than or equal to 2 and less than or equal to 12, the framework structure of the TJT-100 is not damaged through powder diffraction (PXRD) determination and characterization, the good chemical stability of the TJT-100 is shown, and the corresponding powder diffraction characterization is shown in an attached figure 8.
Characterization of gas adsorption properties of porous MOFs material TJT-100
Placing the activated porous material TJT-100 into a quartz sample tube, and measuring acetylene (C) in a BELSORP-max adsorption instrument under the conditions of 273K, 298K and 318K2H2) Ethylene (C)2H4) And ethane (C)2H6) Gas adsorption isotherms. FIG. 9 is a isotherm diagram of the adsorption of acetylene, ethylene and ethane at 298K for the porous material TJT-100 of the present invention. FIGS. 10 to 12 are graphs of adsorption isotherms of acetylene, ethylene and ethane, respectively, of the porous material TJT-100 of the present invention under different temperature conditions.
Application example 1 (preparation of adsorption fixed bed with TJT-100 as packing and separation of two-component mixed gas):
the TJT-100 powder sample is filled into the center of a quartz tube with the inner diameter of 8mm and the length of 45cm, and compacted and packed. Heating the column in He atmosphere at 423K for 24 hr, cooling to 298K, introducing into the column at a total flow rate of 2mL min-1C in a volume ratio of 99:12H4/C2H2Mixed gas, absolute concentration of gas (C)o/CiOutlet/inlet molarity) was detected with a quadrupole mass spectrometer (HPR20, Hiden). The data obtained from the penetration curve experiment are shown in figure 13. FIG. 13 shows the absolute time of gas entering the packing as abscissa and the absolute concentration Co/CiOn the ordinate, the purity of the outlet was determined by gas chromatography (GC-9160, Onhua Shanghai). Under the condition of 298K and normal pressure, the synthesized TJT-100 can separate the ethylene/acetylene mixed gas with the volume ratio of 99:1 to obtain the mixed gas with the purity of 99>99.997% ethylene, the experimental data obtained are graphically shown in figure 14. FIG. 14 is a graph showing the experimental results of the separation of ethylene gas from an adsorption fixed bed prepared from the porous material TJT-100 of the present invention at 298K and one atmosphere for a 99:1 gas mixture of ethylene/acetylene gas;FIG. 14(a) isolation C2H2/C2H4C is detected in the outlet gas in the mixed gas process2H2And C2H4Gas chromatogram of content (the peak at 0.6-0.7 min is the O participating in the pipeline2Peak), spectrum showed no C in the exit gas during the course of separation2H2A peak; FIG. 14(b) adsorption of C by TJT-1002H2/C2H4After the mixed gas is saturated, C is detected in the outlet gas2H2And C2H4Gas chromatogram of content (the peak at 0.6-0.7 min is the O participating in the pipeline2Peak).
Application example 2 (preparation of adsorption fixed bed with TJT-100 as packing and C with volume ratio of 99: 1)2H4/C2H6Separation of mixed gas):
the TJT-100 powder sample is filled into the center of a quartz tube with the inner diameter of 8mm and the length of 45cm, and compacted and packed. Heating the column in He atmosphere at 423K for 24 hr, cooling to 298K, introducing into the column at a total flow rate of 2mL min-1C in a volume ratio of 99:12H4/C2H6Mixed gas, absolute concentration of gas (C)o/CiOutlet/inlet molarity) was detected with a quadrupole mass spectrometer (HPR20, Hiden). The data of the penetration curve experiment is shown in figure 15, and the absolute time of the gas entering the packing is used as the abscissa and the absolute concentration C in figure 15o/CiIs the ordinate. The purity of the outlet was checked by gas chromatography (GC-9160, Ohwa Shanghai). Under the condition of 298K and normal pressure, the synthesized TJT-100 can separate the ethylene/ethane mixed gas with the volume ratio of 99:1 to obtain the mixed gas with the purity of 99>99.997% ethylene, the experimental data obtained are graphically represented in figure 16. FIG. 16 is a graph showing the experimental results of the separation of ethylene gas from an adsorption fixed bed prepared from the porous material TJT-100 of the present invention at 298K and one atmosphere for a 99:1 gas mixture of ethylene/ethane; FIG. 16(a) isolation C2H6/C2H4C is detected in the outlet gas in the mixed gas process2H6And C2H4Gas chromatogram of content (the peak at 0.6-0.7 min is the O participating in the pipeline2Peak), spectrum showed no C in the exit gas during the course of separation2H6A peak; FIG. 16(b) adsorption of C by TJT-1002H6/C2H4After the mixed gas is saturated, C is detected in the outlet gas2H6And C2H4Gas chromatogram of content (the peak at 0.6-0.7 min is the O participating in the pipeline2Peak).
Application example 3 (preparation of adsorption fixed bed with TJT-100 as packing and C with volume ratio of 0.5:0.5: 99)2H2/C2H6/C2H4Three-component mixed gas separation):
the TJT-100 powder sample is filled into the center of a quartz tube with the inner diameter of 8mm and the length of 45cm, and compacted and packed. Heating the column in He atmosphere at 423K for 24 hr, cooling to 298K, introducing into the column at one atmosphere with a total flow rate of 2mL min-1C in a volume ratio of 0.5:0.5:992H2/C2H6/C2H4Three component gases, absolute concentration of gas (C)o/CiOutlet/inlet molarity) was detected with a quadrupole mass spectrometer (HPR20, Hiden). The data obtained from the penetration curve experiment are shown in figure 17, and the absolute time of gas entering the packing is used as the abscissa and the absolute concentration C in figure 17o/CiIs the ordinate. The purity of the outlet was checked by gas chromatography (GC-9160, Ohwa Shanghai). Under the condition of 298K and normal pressure, the synthesized TJT-100 of the invention separates C with the volume ratio of 0.5:0.5:992H2/C2H6/C2H4The three-component gas can be obtained with the purity of>99.997% ethylene, the experimental data obtained are graphically represented in figure 18. FIG. 18 is a graph of an experimental ethylene gas separation curve of an adsorption fixed bed prepared from the porous material TJT-100 of the present invention under 298K and one atmosphere for a gas mixture of acetylene/ethane/ethylene at a volume ratio of 0.5:0.5: 99; FIG. 18(a) isolation C2H2/C2H4/C2H6Detection of the gaseous phase of the outlet gas in the course of the mixed gasChromatogram (the peak at 0.6-0.7 min is O participating in the pipeline2Peak), spectrum showed no C in the exit gas during the course of separation2H2And C2H6A peak; FIG. 18(b) is a gas chromatogram in which the gas exiting the column is detected after saturation of the three-component mixed gas adsorbed by TJT-100. As can be seen from fig. 18, TJT-100 has the capability of separating three component gases simultaneously, and can realize the separation of the three component gases, which is not reported in the porous material.
The coordination polymer porous material TJT-100 has good thermal stability and chemical stability, and has very excellent performance in the aspect of practical C2s three-component gas separation application. The material can adsorb acetylene in mixed gas of ethylene and acetylene and ethane in mixed gas of ethylene and ethane, and more importantly, the material has the performance of simultaneously separating ethane/ethylene/acetylene three-component gas, and can realize the separation of the three-component gas. The two-component mixed gas and the three-component mixed gas can obtain the ethylene with the purity of more than 99.997 percent after being separated by the material, and have high industrial application value.
Further summary is as follows:
the TJT-100 is used for adsorbing acetylene in mixed gas of ethylene and acetylene, and the purity of ethylene obtained by single separation under industrial conditions, namely the mixed gas of ethylene/acetylene with the ratio of 99:1, is as high as more than 99.997 percent, so that high-purity ethylene can be obtained.
TJT-100 is used for absorbing ethane in mixed gas of ethylene and ethane, and under industrial conditions, namely the mixed gas of ethylene and ethane with the ratio of 99:1, the purity of ethylene obtained by single separation is as high as > 99.997%, and high-purity ethylene is obtained.
Particularly, the porous material TJT-100 can be used as an adsorption fixed bed packing to be applied to directly separating and purifying high-purity ethylene from acetylene/ethylene/ethane three-component mixed gas, the purity of the ethylene reaches 99.997 percent of the requirement of polymerization purity, and the purity of the ethylene obtained by single separation under industrial conditions, namely the purity of the ethylene obtained by 0.5/0.5/99 of the acetylene/ethylene/ethane mixed gas reaches 99.997 percent.
Claims (9)
1. A coordination polymer porous material with chemical formula of (Me)2NH2)[Co3(DCPN)2(μ3-OH)(H2O)]·11H2And O, DCPN in the formula represents an anion of a 5- (3',5' -dicarboxyphenyl) nicotinic acid ligand.
2. The coordination polymer porous material according to claim 1, characterized in that: the porous material is a three-dimensional frame structure material with one-dimensional pore channels formed by connecting DCPN with a trinuclear Co cluster, wherein the trinuclear Co cluster unit is formed by two hexacoordinated Co (II) and one pentacoordinated Co (II) through mu3-OH are linked together.
3. The coordination polymer porous material according to claim 1 or 2, characterized in that: the crystal form of the porous material belongs to an orthorhombic system, the space group is Pbca, and the unit cell parameters are as follows:
4. the method for preparing a coordination polymer porous material according to claim 1, wherein: is prepared by reacting ligand 5- (3',5' -dicarboxyphenyl) nicotinic acid with cobalt salt in N, N-dimethylformamide solvent.
5. The method for preparing a coordination polymer porous material according to claim 4, wherein: the molar ratio of 5- (3',5' -dicarboxyphenyl) nicotinic acid to cobalt salt was 1: 1.
6. The method for preparing a coordination polymer porous material according to claim 5, wherein: the cobalt salt is a divalent Co salt.
7. The method for preparing a coordination polymer porous material according to claim 4, wherein: the N, N-dimethylformamide solvent is a mixed solution of N, N-dimethylformamide and water.
8. The method for preparing a coordination polymer porous material according to claim 4, wherein: the reaction temperature is 120-180 ℃, and the reaction time is 48-96 h.
9. Use of the coordination polymer porous material of claim 1 as an adsorbent, said adsorbent being C2s gas adsorbent.
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