CN113201144A - Rigid tetracarboxyl hydrogen bond organic framework material and preparation and application thereof - Google Patents
Rigid tetracarboxyl hydrogen bond organic framework material and preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a rigid tetracarboxyl hydrogen bond organic framework material, and preparation and application thereof. The rigid tetracarboxyl hydrogen bond organic framework material monomer molecule H4TPA is: n, N' -tetrakis (4-carboxyphenyl) -1, 4-phenylenediamine, which belongs to the orthorhombic system, the space groups are Ibca, α ═ β ═ γ ═ 90 °, Z ═ 8, and each tetrahedron H4TPA molecules pass through four pairs of intermolecular-COOH … HOOC-hydrogenBond with four adjacent H4TPA molecules are connected, and the distance of O … O and the angle of O-H … O are respectively
And 171. The invention has the beneficial effects that: the rigid tetracarboxyl hydrogen bond organic framework material has the advantages of simple preparation process and low cost, and is applied to C3H4/C3H6The mixed gas is selectively separated and adsorbed with propylene and propyne, is easy to recover and regenerate, and has good separation stability.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a rigid tetracarboxyl hydrogen bond organic framework material, and preparation and application thereof.
Background
At present, propylene is one of the most important chemical raw materials in the world (the global capacity exceeds 1.16 million tons in 2020), propyne impurities are inevitably generated in the production process, and the production of downstream polypropylene is obviously influenced by the existence of propyne with extremely low concentration (more than or equal to 1 ppm). Therefore, the realization of the high-efficiency purification of the low-concentration propyne in the propylene has important industrial and scientific significance. In the traditional petrochemical industry, the propyne is separated mainly by adopting a low-temperature refining or catalytic hydrogenation process, and the defects of high energy consumption, low selectivity and the like exist. Thus, efficient removal of C was developed3H6Middle trace amount of C3H4The new technology and the new material have important practical significance. Therefore, the development of energy-saving and environment-friendly C is urgently needed3H4/C3H6A separation method. In recent years, porous materials have been used as physical adsorbents for selective adsorption of C3H4And not C3H6Has become a simple and effective method.
The hydrogen bond organic framework is a novel porous crystal material and is formed by the interaction of organic groups through non-covalent bonds such as hydrogen bonds, pi-pi, static electricity and the like. As early as 90 s in the 20 th century, chemists gained inspiration from hydrogen bonds that are widely present in biological systems, and utilized hydrogen bonds to construct porous frameworks. The material has the unique advantages of high crystallinity, large specific surface area, mild synthesis conditions, solvent processability and the like. Thus, HOFs have become an excellent platform in the fields of gas storage, catalysis, molecular conformation determination, fluorescence sensing, enzyme encapsulation, and the like. Furthermore, in recent years, HOFs have been in the field of engineering and regulation of pore size, shape and surface functionThere is a great deal of interest in gas separation/purification. These characteristics enable us to design target materials with desired pore size and function for various gas separation and purification including CO separation2/N2、CO2/CH4Light hydrocarbon, C2H2/CO2、O2/N2And the like. However, due to C3H4/C3H6The kinetic diameter and the molecular size of (A) are similar, and the separation is difficult. For C3H4/C3H6Isolated HOFs materials are still in the blank of research.
Disclosure of Invention
The invention discloses a rigid tetracarboxyl hydrogen bond organic framework material, and preparation and application thereof.
In order to solve the problems, the technical scheme of the invention is as follows: a rigid tetracarboxyl hydrogen bond organic frame material is HOF-30 series (HOF-30-C)1，HOF-30-C2And HOF-30-C3) The series of HOFs materials are activated by a gas adsorption instrument and then converted into the same compound: HOF-30 a. HOF-30a has Excellent C3H4/C3H6Separation performance.
The organic framework material belongs to an orthorhombic system and has a space group ofIbcaα ═ β ═ γ ═ 90 °, Z ═ 8, and in the crystal structure of HOF-30a, each tetrahedron H4The TPA molecule is connected to four adjacent H4TPA molecules through four pairs of intermolecular-COOH · HOOC-hydrogen bonds. The distance and angle of O-H.O are 2.6A and 171oAll belong to the range of strong hydrogen bonds, and a robust three-dimensional hydrogen bond skeleton can be formed in this way. On the topology, if H is to be4The TPA molecule is regarded as one with four connected nodes, and HOF-30a has 10 weight interpenetrationdiaTopology structure. HOF-30a has irregular two-dimensional pores, and the solvent can reach 20.3% of the pores. The above-mentioned monomer molecule H4TPA is:N，N，N'，N'-tetrakis (4-carboxyphenyl) -1, 4-phenylenediamine, of the formula:
the invention also aims to provide a method for preparing the rigid tetracarboxyl hydrogen bond organic framework material, which is characterized by comprising the following steps:
S1）N，N，N'，N'mixing the tetra (4-carboxyphenyl) -1, 4-phenylenediamine ligand and a solvent according to a certain proportion, heating to a certain temperature, carrying out suction filtration,
s2), cooling to room temperature after suction filtration, standing until the solvent is volatilized to obtain a yellow octahedral crystal product A,
s3) degassing the obtained yellow octahedral crystal product A at room temperature by using a gas adsorption instrument to obtain the rigid tetracarboxyl hydrogen bond organic framework material.
Further, in the S1)N，N，N'，N'The solid-to-liquid ratio of the tetra (4-carboxyphenyl) -1, 4-phenylenediamine ligand to the solvent is as follows: 1-5:1-1.1.
Further, the heating temperature in the step S1) is 25-80 ℃.
Further, the solvent in S1) is one or more of methanol, ethanol and n-propanol.
The rigid tetracarboxyl hydrogen bond organic framework material is prepared at the step C3H4/C3H6The method is applied to selectively separating and adsorbing propylene and propyne in mixed gas.
The invention has the beneficial effects that: the rigid tetracarboxyl hydrogen bond organic framework material has the advantages of simple preparation process and low cost, and is applied to C3H4/C3H6The mixed gas is selectively separated and adsorbed with propylene and propyne, is easy to recover and regenerate, and has good separation stability.
Description of the drawings:
FIG. 1 is HOF-30-C1The picture appearance of (1);
FIG. 2 is HOF-30-C2The picture appearance of (1);
FIG. 3 is HOF-30-C3The picture appearance of (1);
FIG. 4 is HOF-30-C1The crystal structure of (1);
FIG. 5 is HOF-30-C2The crystal structure of (1);
FIG. 6 is HOF-30-C3The crystal structure of (1);
FIG. 7 is the crystal structure of HOF-30 a;
FIG. 8 is a schematic diagram of the crystal channel of HOF-30a
FIG. 9 is HOF-30-C1XRD pattern of
FIG. 10 is HOF-30-C2XRD pattern of
FIG. 11 is HOF-30-C3XRD pattern of
FIG. 12 is an XRD pattern of HOF-30a
FIG. 13 is a thermogravimetric plot of HOF-30a at 25-800 deg.C
FIG. 14 is a nitrogen adsorption/desorption curve of HOF-30a at 77K;
FIG. 15 is a plot of propylene, propyne desorption from HOF-30a at 298K;
FIG. 16 shows HOF-30a vs. C3H4/C3H6(1/99 v/v) penetration test;
FIG. 17 is C3H4/C3H6(1/99 v/v) cycle chart of breakthrough experiment.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific embodiments.
The invention relates to a rigid tetracarboxyl hydrogen bond organic framework material, and a monomer molecule H of the rigid tetracarboxyl hydrogen bond organic framework material4TPA is:N，N，N'，N'-tetrakis (4-carboxyphenyl) -1, 4-phenylenediamine, of the formula:
each tetrahedron H of said rigid tetracarboxyl hydrogen bonding organic framework material4The TPA molecule is connected with four adjacent H4TPA molecules through four pairs of intermolecular-COOH-HOOC-hydrogen bonds, and the distance and the angle of O-H-O are 2.6A and 171A respectivelyo。
The four of the rigidityThe carboxyl hydrogen bond organic frame material belongs to an orthorhombic system and has a space group ofIbca，α＝β＝γ＝90°，Z＝8。
The hydrogen rigid tetracarboxyl hydrogen bond organic framework material has 10 weight interpenetrationdiaTopological structure, and has irregular two-dimensional pore canal, and the clearance reaches 20.3%.
The invention also aims to provide a method for preparing the rigid tetracarboxyl hydrogen bond organic framework material, which specifically comprises the following steps:
s1) mixing the ligand of N, N, N ', N' -tetra (4-carboxyphenyl) -1, 4-phenylenediamine with solvent according to a certain proportion, heating to a certain temperature, carrying out suction filtration,
s2), cooling to room temperature after suction filtration, standing until the solvent is volatilized to obtain a yellow octahedral crystal product A,
s3) degassing the obtained yellow octahedral crystal product A at room temperature by using a gas adsorption instrument to obtain the rigid tetracarboxyl hydrogen bond organic framework material.
Said S1)N，N，N'，N'The solid-to-liquid ratio of the tetra (4-carboxyphenyl) -1, 4-phenylenediamine ligand to the solvent is as follows: 1-5:1-1.1.
The heating temperature in the S1) is 25-80 ℃.
The solvent in S1) is one or more of methanol, ethanol and n-propanol.
A rigid tetracarboxyl hydrogen bonding organic framework material as defined in any of claims 1 to 8 at C3H4/C3H6The method is applied to selectively separating and adsorbing propylene and propyne in mixed gas.
Example (b):
HOF-30-C1，HOF-30-C2，HOF-30-C3and synthesis of HOF-30a
HOF-30-C in the above1The specific synthesis method comprises the following steps: under the condition of heating, 50.0mgN，N，N'，N'The tetrakis (4-carboxyphenyl) -1, 4-phenylenediamine ligand was dissolved in methanol (100.0 mL). The solution was filtered while hot (25-80 ℃) and allowed to cool to room temperature. By standing at room temperature for several weeks to obtainYellow octahedral crystal (HOF-30-C)1) 35.0mg, yield: 70 percent. As shown in figure 1 of the drawings, in which,
HOF-30-C in the above2The specific synthesis method comprises the following steps: 50.0mg of N, N, N ', N' -tetrakis (4-carboxyphenyl) -1, 4-phenylenediamine ligand was dissolved in ethanol (50.0 mL) with heating. The solution was filtered while hot (25-80 ℃) and allowed to cool. By slow evaporation at room temperature for several weeks, yellow octahedral crystals (HOF-30-C) are obtained2) 37.5mg, yield: 75 percent. As shown in figure 2 of the drawings, in which,
under the condition of heating, 250.0 mg of the above-mentioned raw materialsN，N，N'，N'The tetrakis (4-carboxyphenyl) -1, 4-phenylenediamine ligand was dissolved in n-propanol (60.0 mL). The solution was filtered while hot (25-80 ℃) and allowed to cool. By slow evaporation at room temperature for several weeks, yellow octahedral crystals (HOF-30-C) are obtained3) 150.0mg, yield: 60.0 percent. As shown in figure 3 of the drawings,
the specific synthesis method of the HOF-30a comprises the following steps: use of gas adsorption apparatus for the synthesis of HOF-30-C1，HOF-30-C2Or HOF-30-C3The porous adsorbing material of the invention can be obtained by degassing treatment at room temperature: HOF-30a
HOF-30-C1，HOF-30-C2，HOF-30-C3And structural information of HOF-30a
HOF-30-C1The molecular formula of (A) is: c36H32N2O10Belonging to the orthorhombic system, the space group beingIbca，α＝β＝γ＝90°，Z＝8。
HOF-30-C2The molecular formula of (A) is: c38H36N2O10Belonging to the orthorhombic system, the space group beingIbca，α＝β＝γ＝90°，Z＝8。
HOF-30-C3The molecular formula of (A) is: c40H38N2O10Belonging to the orthorhombic system, the space group beingIbca，α＝β＝γ＝90°，Z＝8。
The molecular formula of HOF-30a is: c34H24N2O8Belonging to the orthorhombic system, the space group beingIbca，α＝β＝γ＝90°，Z＝8。
HOF-30-C1，HOF-30-C2And HOF-30-C3Each H in (1)4TPA molecules are all adjacent to four H4TPA connected to two adjacent H4TPA connects molecules directly through two pairs of O-H.O hydrogen bonds (H-bonds). The other two adjacent connecting molecules are connected by two pairs of intermolecular hydrogen bond dimers-COOH-O-H-HOOC-, the hydroxyl of the alcohol molecule is taken as a bridge,
HOF-30-C1，HOF-30-C2and HOF-30-C3The structure of HOF-30a can be obtained after removing the corresponding alcohol molecules,
structural characterization and application of adsorption separation of propylene and propyne based on HOF-30 and HOF-30 a.
1，HOF-30-C2，HOF-30-C3And structural determination of HOF-30 a:
(1) selecting high-quality single crystals for structural analysis, and collecting diffraction data of the crystals on a Supernova diffractometer at 150K. Cu Ka radiation monochromatized with graphite (λ = 1.54184 a) was performed in a ω -2 θ scan mode, all intensity data were corrected by Lp factor, and the crystal structure was solved by direct method. The hydrogen atoms on the carbon and nitrogen atoms were theoretically hydrogenated and refined using a riding (riding) model. Anisotropy correction is performed on non-hydrogen atoms. The weighted R-factor, wR and GOOF values (S) are all based on F2All calculations were done in the SHELXTL-2014 Structure parser Package, see FIG. 4 for the structure (HOF-30-C)1) FIG. 5 (HOF-30-C)2) FIG. 6 (HOF-30-C)3) And FIG. 7 (HOF-30 a), the crystallographic data are shown in Table 1 below.
(3) Powder X-ray diffraction (PXRD) data were collected at room temperature using a PANalytical Empyrean series 3 diffractometer with instrument parameters: monochromatization with graphiteThe Cu target is an X-ray light source, and the test voltage is as follows: 45KV, test current: 40mA, the test step size is: 0.01313 deg. 2 theta. The powder X-ray diffraction (XRD) pattern of the hydrogen bonding organic framework crystal substantially coincided with the XRD pattern of the hydrogen bonding organic framework crystal simulated by the single crystal structure data through Mercury software, indicating that the synthesized material is pure phase and free of impurities: FIG. 9 (HOF-30-C)1) FIG. 10 (HOF-30-C)2) FIG. 11 (HOF-30-C)3) And FIG. 12 (HOF-30 a).
(4) Thermogravimetric analysis (TGA) was performed on a Perkin-Elmer instrument at a temperature range of 25-800 ℃ and a temperature ramp rate of 10 ℃/min under a nitrogen atmosphere. Thermogravimetric analysis shows that HOF-30a has good thermal stability, and the decomposition temperature is higher than 400 ℃: FIG. 13.
(5) The nitrogen adsorption and desorption isotherms of HOF-30a at 77K were measured using a Micromeritics ASAP 2020 PLUS HD 88. The BET areas are respectively: 361 m2(ii) in terms of/g. Fig. 14.
(6) The adsorption and desorption isotherms of propylene, propyne for HOF-30a at 273K and 298K were measured using a Micromeritics ASAP 2020 PLUS HD 88. Fig. 15, fig. 16.
Application of HOF-30a in adsorption separation of propylene and propyne (breakthrough experiment):
to C3H4/C3H6(1/99 v/v) mixture at 1 mL min-1The breakthrough experiment was carried out at a flow rate of (298K, 1.01 bar). HOF-30a (about 1.0g per run) was powdered and loaded onto a d.p. 4X 100 mm stainless steel column under pure He atmospheric pressure. The samples in the column were compressed under the same conditions and the column void ratios of the different samples were similar to compare the separation performance. The experimental apparatus consisted of two fixed bed stainless steel reactors. One reactor was loaded with adsorbent and the other reactor was used as a blank to stabilize gas flow. The horizontal reactor was placed in a temperature controlled environment of 298K. The flow rate of all gas mixtures was adjusted using a mass flow controller and the gas flow out of the column was monitored using gas chromatography (fid-flame ionization detector, detection limit 100 ppb). Prior to breakthrough experiments, we pushed the adsorbent bed for 30 minutes at 323K heliumThe sample is activated. Before each separation test, He flow (40 mL min) was used-1) Regeneration was carried out at 363K for 12.0 h to ensure complete removal of adsorbed gas. Fig. 17.
Experimental study
In order to verify the beneficial effects of the invention, the inventor carries out a great deal of experimental research, and part of the experimental processes and results are as follows:
single crystal testing: determination of HOF-30-C1，HOF-30-C2，HOF-30-C3And the molecular structure of HOF-30a, FIG. 4 (HOF-30-C)1) FIG. 5 (HOF-30-C)2) FIG. 6 (HOF-30-C)3) And FIG. 7 (HOF-30 a), the crystallographic data are as follows:
HOF-30-C1the molecular formula of (A) is: c36H32N2O10Belonging to the orthorhombic system, the space group beingIbcaA =14.7692 a, =18.0457 a, c =27.2329 a, α β ═ γ ═ 90 °, Z ═ 8, the unit cell volume: 7258.1A3The crystal density is: 1.194g/cm3。
HOF-30-C2The molecular formula of (A) is: c38H36N2O10Belonging to the orthorhombic system, the space group beingIbcaA =14.5011 a, =18.2020 a, c =27.9085 a, α β ═ γ ═ 90 °, Z ═ 8, the unit cell volume: 7366.4A3The crystal density is: 1.228g/cm3。
HOF-30-C3The molecular formula of (A) is: c40H38N2O10Belonging to the orthorhombic system, the space group beingIbcaA =14.5011 a, =18.6402 a, c =27.9536 a, α β ═ γ ═ 90 °, Z ═ 8, the unit cell volume: 7457.6A3The crystal density is: 1.259g/cm3。
The molecular formula of HOF-30a is: c34H24N2O8Belonging to the orthorhombic system, the space group beingIbcaA =14.3282 a, =15.9253 a, c =28.603 a, α β ═ γ ═ 90 °, Z ═ 8, the unit cell volume: 6526.6A3The crystal density is: 1.198g/cm3。
Powder X-ray diffraction study: using PANalPowder X-ray diffraction (PXRD) data were collected at room temperature with a clinical Empyrean series 3 diffractometer, instrument parameters: the method adopts a graphite monochromized Cu target as an X-ray light source, and the test voltage is as follows: 45KV, test current: 40mA, the test step size is: 0.01313 deg. 2 theta. The powder X-ray diffraction (XRD) pattern of the hydrogen bonding organic framework crystal substantially coincided with the XRD pattern of the hydrogen bonding organic framework crystal simulated by the single crystal structure data through Mercury software, indicating that the synthesized material is pure phase and free of impurities: FIG. 9 (HOF-30-C)1) FIG. 10 (HOF-30-C)2) FIG. 11 (HOF-30-C)3) And FIG. 12 (HOF-30 a).
Thermogravimetric analysis: thermogravimetric analysis (TGA) was performed on a Perkin-Elmer instrument at a temperature range of 25-800 ℃ and a temperature ramp rate of 10 ℃/min under a nitrogen atmosphere. Thermogravimetric analysis shows that HOF-30a has good thermal stability, and the decomposition temperature is higher than 400 ℃: FIG. 13 (HOF-30 a).
Gas adsorption and specific surface area testing: the HOF-30a is subjected to gas adsorption and specific surface area tests, and shows that the HOF-30a has a permanent pore structure, and the specific surface area is as follows: 361 m2 g−1The results are shown in FIG. 14; the adsorption isotherm of propylene and propyne of HOF-30a under 298K and 0-1atm was measured, and the maximum adsorption amounts were respectively: 36.8cm3 g-1And 54.9cm3 g-1Fig. 15.
Penetration test: to C3H4/C3H6(1/99 v/v) mixture at 1 mL min-1The breakthrough experiment is carried out at the flow rate of (298K, 1.01 bar), the capability of HOF-30a for dynamically separating propylene/propyne is proved, and the adsorption separation C of HOF-30a is determined3H4/C3H6See fig. 16 for results; furthermore, the breakthrough experiment was repeated, and after 5 cycles, the separation performance of HOF-30a was not decreased, demonstrating the stability of HOF-30a, FIG. 17.
Table 1: crystallography data sheet
[a] R 1 = Σ|F o-|F c||/Σ|F o|; [b] wR 2 = [Σw(F o 2-F c 2)2/Σw(F o 2)2]1/2。
The rigid tetracarboxyl hydrogen bond organic framework material provided by the embodiment of the application, and the preparation and application thereof are described in detail above. The above description of the embodiments is only for the purpose of helping to understand the method of the present application and its core ideas; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
As used in the specification and claims, certain terms are used to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, and a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect. The description which follows is a preferred embodiment of the present application, but is made for the purpose of illustrating the general principles of the application and not for the purpose of limiting the scope of the application. The protection scope of the present application shall be subject to the definitions of the appended claims.
It is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a good or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such good or system. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a commodity or system that includes the element.
It should be understood that the term "and/or" as used herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the application as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.
Claims (9)
1. A rigid tetracarboxyl hydrogen bond organic framework material is characterized in that monomer molecules H of the rigid tetracarboxyl hydrogen bond organic framework material4TPA is: n, N' -tetrakis (4-carboxyphenyl) -1, 4-phenylenediamine, the structural formula of which is:
2. a rigid tetracarboxyl hydrogen bonding organic framework material according to claim 1, characterized in that each tetrahedron H of said rigid tetracarboxyl hydrogen bonding organic framework material4The TPA molecule is bonded to four adjacent H via four pairs of intermolecular-COOH. HOOC-hydrogen bonds4TPA molecules are connected, and the distance and the angle of O-H.O are respectively
And 171.
3. A rigid tetracarboxyl hydrogen bonding organic framework material according to claim 1, wherein the rigid tetracarboxyl hydrogen bonding organic framework material belongs to the orthorhombic system, and the space group is Ibca, α ═ β ═ γ ═ 90 °, Z ═ 8.
4. The rigid tetracarboxylic hydrogen bonding organic framework material of claim 1, wherein the rigid tetracarboxylic hydrogen bonding organic framework material has 10-fold interpenetrating dia topology with irregular one-dimensional pores with up to 20.3% voids.
5. A method for preparing the rigid tetracarboxyl hydrogen bonding organic framework material according to any one of claims 1 to 4, characterized by comprising the following steps:
s1) mixing the ligand of N, N, N ', N' -tetra (4-carboxyphenyl) -1, 4-phenylenediamine with solvent according to a certain proportion, heating to a certain temperature, carrying out suction filtration,
s2), cooling to room temperature after suction filtration, standing until the solvent is volatilized to obtain a yellow octahedral crystal product A,
s3) degassing the obtained yellow octahedral crystal product A at room temperature by using a gas adsorption instrument to obtain the rigid tetracarboxyl hydrogen bond organic framework material.
6. The method as claimed in claim 5, wherein the solid-to-liquid ratio of the N, N, N ', N' -tetrakis (4-carboxyphenyl) -1, 4-phenylenediamine ligand to the solvent in S1) is: 1-5:1-1.1.
7. The method as claimed in claim 5, wherein the heating temperature in S1) is 25-80 ℃.
8. The method as claimed in claim 3, wherein the solvent in S1) is one or more of methanol, ethanol, and n-propanol.
9. A rigid tetracarboxyl hydrogen bonding organic framework material prepared by the method of any one of claims 5 to 8 at C3H4/C3H6The method is applied to selectively separating and adsorbing propylene and propyne in mixed gas.
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