CN117417546A - Adsorption of gaseous CO 2 Porous crystalline material of (2) and preparation method and application thereof - Google Patents
Adsorption of gaseous CO 2 Porous crystalline material of (2) and preparation method and application thereof Download PDFInfo
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- CN117417546A CN117417546A CN202311557052.4A CN202311557052A CN117417546A CN 117417546 A CN117417546 A CN 117417546A CN 202311557052 A CN202311557052 A CN 202311557052A CN 117417546 A CN117417546 A CN 117417546A
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- 239000002178 crystalline material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 title claims description 21
- 239000013078 crystal Substances 0.000 claims abstract description 39
- SAAQRUMAXVBWDL-UHFFFAOYSA-N 4-(10-pyridin-4-ylanthracen-9-yl)pyridine Chemical compound C=12C=CC=CC2=C(C=2C=CN=CC=2)C2=CC=CC=C2C=1C1=CC=NC=C1 SAAQRUMAXVBWDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZSLCDSMUKOZRPQ-UHFFFAOYSA-N 4-[10-(4-carboxyphenyl)anthracen-9-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=C(C(O)=O)C=C1 ZSLCDSMUKOZRPQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003463 adsorbent Substances 0.000 claims abstract 2
- 239000011701 zinc Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011521 glass Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 16
- 239000003446 ligand Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 13
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- -1 Zn (II) ions Chemical class 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- 238000010586 diagram Methods 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical group [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229940045799 anthracyclines and related substance Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28095—Shape or type of pores, voids, channels, ducts
Abstract
The invention discloses a method for adsorbing gas CO 2 Porous crystalline material of (2) and a method for the preparation and use thereof. The crystal belongs to monoclinic system, the space group is P2/n, and the molecular formula is C 52 H 32 N 2 O 4 Zn, molecular weight 814.16, unit cell parameters α＝90°，β＝107.2960(10)°，γ＝90°；Zn 2+ The ion center adopts a four-coordination mode and passes through the ligandThe 9, 10-di (4-carboxyphenyl) anthracene and the 9, 10-di (4-pyridyl) anthracene are alternately connected to form a diamond-like cage structure; the diamond-like cage structure forms a six-fold interpenetration structure through pi-pi action; the unit cell stacking diagram along the b-axis shows its channel structure, which has wide application as a gas selective adsorbent material.
Description
Technical Field
The invention belongs to the field of porous crystal material chemistry, and in particular relates to an adsorption deviceGaseous CO 2 Porous crystalline material of (2) and a method for the preparation and use thereof.
Background
The metal organic complex crystalline material, also commonly referred to as metal-organic framework materials (Metal Organic Frameworks, MOFs for short), is an organic-inorganic hybrid material, a material in which organic ligands and metal ions or clusters form intramolecular pores by self-assembly of coordination bonds. MOFs have their own characteristics such as having a large porosity and specific surface area, structural and functional diversity, and having unsaturated metal sites. MOFs are unique porous materials due to the characteristics, and are widely applied to the fields of catalysis, ion transmission and the like.
Ethylene and acetylene are important petrochemical products and play a vital role in the petrochemical and polymer industries, and since ethylene, acetylene and carbon dioxide gases possess molecules of close size and their physicochemical properties are very similar, the highly selective separation of acetylene from mixtures of ethylene, acetylene and carbon dioxide is very important to meet the petrochemical industry.
Disclosure of Invention
The invention aims at the problems existing in the prior art and provides a method for adsorbing gas CO 2 Porous crystalline material of (2) and a method for the preparation and use thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: adsorption gas CO 2 The porous crystal material is named Zn (anth-py) (anth-ca) and belongs to monoclinic system, the space group is P2/n, and the molecular formula is C 52 H 32 N 2 O 4 Zn, molecular weight 814.16, unit cell parameters α=90°, β= 107.2960 (10) °, γ=90°; the basic unit of crystalline Zn (anth-py) (anth-ca) consists of a 9, 10-bis (4-carboxyphenyl) anthracene, a 9, 10-bis (4-pyridyl) anthracene, from which 2 carboxylic acid protons have been removedOne Zn 2+ Ion composition; each Zn 2+ The ion adopts a four-coordination mode, four coordination points are respectively coordinated with carboxyl oxygen atoms on two 9, 10-di (4-carboxyphenyl) anthracene ligands and pyridine nitrogen atoms on two 9, 10-di (4-pyridyl) anthracene ligands (figure 1), and the distance between Zn and O bonds is->The Zn-N bond distance is +.>Zn (II) ions are alternately connected with 9, 10-bis (4-pyridyl) anthracene through the ligand 9, 10-bis (4-carboxyphenyl) anthracene to form a diamond-like cage structure (figure 2); the diamond-like cage structure forms a six-fold interpenetration structure through pi-pi action (figure 3); the packing diagram of the unit cells along the b-axis shows the channel structure (fig. 4).
The invention also provides a preparation method of the porous crystal material, which comprises the following steps:
weighing a certain amount of 9, 10-di (4-carboxyphenyl) anthracene, 9, 10-di (4-pyridyl) anthracene and zinc salt, putting into a glass bottle, and then adding DMF and ethanol solvent into the glass bottle to form a mixture solution; the mixture solution was stirred for 15 minutes by ultrasonic wave, and a small amount of HNO of 2mol/L was dropped by a pipette 3 The method comprises the steps of carrying out a first treatment on the surface of the Placing the glass bottle in an oven, heating at a constant temperature of 80-100 ℃ for reaction for 3-5 days, cooling to room temperature after the reaction is finished, filtering, washing with ethanol, and drying to obtain blocky yellow crystals; the yellow crystal is an adsorption gas CO 2 Is a porous crystalline material of (a);
the zinc salt can be one or more of zinc nitrate, zinc acetate and zinc sulfate;
the ratio of the amounts of the substances of the ligands 9, 10-bis (4-carboxyphenyl) anthracene, 9, 10-bis (4-pyridyl) anthracene and zinc salt is 1:1:2;
the ligand 9, 10-di (4-carboxyphenyl) anthracene is abbreviated as anth-ca, and the structural formula is shown as formula (I):
the ligand 9, 10-di (4-pyridyl) anthracene is abbreviated as anth-py, and the structural formula is shown as the following formula (II):
the substances or solvents which participate in the reaction are all chemically pure.
The invention also provides the application of the porous crystal material, the porous crystal material is used as a metal organic framework material for selecting adsorptive gas, and the material can selectively adsorb acetylene/CO at 273K and 298K 2 And acetylene/ethylene and other gases, and has wide application prospect as a gas selective adsorption material.
Compared with the prior art, the invention is characterized in that:
(1) The ligand 9, 10-bis (4-carboxyphenyl) anthracene contains a large conjugated pi 28 28 The system, ligand 9, 10-di (4-pyridyl) anthracene contains large conjugated pi 26 28 The system can form specific porous coordination compound crystal materials with zinc ions, and specific pi-pi stacking effect can be formed by a specific conjugated system, so that specific adsorption and desorption forces can be formed on other molecules; (2) The ligands 9, 10-di (4-carboxyphenyl) anthracene, 9, 10-di (4-pyridyl) anthracene and zinc ions form a diamond-like cage structure, a six-fold interpenetration structure is formed by specific pi-pi action on an anthracycline, and a pore channel is arranged along the direction of a b axis, so that the crystal material has good gas selective adsorption performance, and the maximum adsorption values of carbon dioxide, acetylene and ethylene at 273K are respectively 68.6cm 3 g -1 、80.1cm 3 g -1 And 63.5cm 3 g -1 At 298K, 52.7cm each 3 g -1 、67.3cm 3 g -1 、53.1cm 3 g -1 The porous crystalline material has wide application prospect in other adsorption aspects.
Drawings
FIG. 1 is the presentZn in the porous crystal material 2+ A coordination environment diagram of ions;
FIG. 2 is a diagram of a diamond-like cage structure of the porous crystalline material of the present invention;
FIG. 3 is a six-fold cross-over block diagram of a porous crystalline material of the present invention;
FIG. 4 is a graph of pore channels along the b-axis of the porous crystalline material of the present invention;
FIG. 5 is a thermogram of a porous crystalline material of the present invention;
FIG. 6 is an X-ray diffraction pattern of a porous crystalline material of the present invention at various temperatures;
FIG. 7 shows acetylene/ethylene/CO at 273K for the porous crystalline material of the present invention 2 Sucking the attached drawings;
FIG. 8 is an acetylene/ethylene/CO at 298K for a porous crystalline material of the present invention 2 The drawing is sucked.
Detailed Description
The present invention is described in further detail below with reference to examples.
Example 1:
9, 10-bis (4-pyridyl) anthracene (33.2 mg,0.1 mmol), 9, 10-bis (4-carboxyphenyl) anthracene (42.7 mg,0.1 mmol), and Zn (NO 3 ) 2 ·6H 2 O (59.6 mg,0.2 mmol) was placed in a 20mL glass bottle, and then 1.0mL DMF, 5.0mL ethanol solvent was added to the glass bottle to form a mixture solution; the mixture solution was stirred with ultrasonic waves for 15 minutes, and 0.1mL of HNO having a concentration of 2mol/L was dropped into the mixture solution with a pipette 3 . Placing the glass bottle in an oven, setting the temperature to 90 ℃ and heating the glass bottle at constant temperature for reaction for 4 days, cooling the glass bottle to room temperature, filtering the glass bottle, washing the glass bottle with ethanol and drying the glass bottle to obtain blocky yellow crystals (the crystal material is named as Zn (anth-py) (anth-ca)), and the yield is 30.13%; the yellow crystal is an adsorption gas CO 2 Is a porous crystalline material of (a).
Example 2:
9, 10-bis (4-pyridyl) anthracene (66.4 mg,0.2 mmol), 9, 10-bis (4-carboxyphenyl) anthracene (85.4 mg,0.2 mmol) and (CH) were weighed out 3 COO) 2 Zn·2H 2 O (87.8 mg,0.4 mmol) was placed in a 20mL glass bottle, and then 2.0mL DMF, 8.0mL ethanol solvent was added to the glass bottle to form a mixtureA solution of matter; the mixture solution was stirred with ultrasonic waves for 15 minutes, and 0.1mL of HNO having a concentration of 2mol/L was dropped into the mixture solution with a pipette 3 . Placing the glass bottle in an oven, heating at a constant temperature of 80 ℃ for reaction for 5 days, cooling to room temperature, filtering, washing with ethanol, and drying to obtain blocky yellow crystals with a yield of 30.13%; the yellow crystal is an adsorption gas CO 2 Is a porous crystalline material of (a).
Example 3:
9, 10-bis (4-pyridyl) anthracene (33.2 mg,0.1 mmol), 9, 10-bis (4-carboxyphenyl) anthracene (42.7 mg,0.1 mmol), and ZnSO were weighed out 4 ·7H 2 O (57.5 mg,0.2 mmol) was placed in a 20mL glass bottle, and then 1.0mL DMF, 5.0mL ethanol solvent was added to the glass bottle to form a mixture solution; the mixture solution was stirred with ultrasonic waves for 15 minutes, and 0.05mL of HNO having a concentration of 2mol/L was dropped with a pipette 3 . Placing the glass bottle in an oven, heating at a constant temperature of 100 ℃ for reaction for 3 days, cooling to room temperature, filtering, washing with ethanol, and drying to obtain blocky yellow crystals with a yield of 30.13%; the yellow crystal is an adsorption gas CO 2 Is a porous crystalline material of (a).
The yellow bulk crystal obtained in example 1 was subjected to single crystal X-ray diffraction analysis test, crystals of a proper size and a regular shape were selected at room temperature and fixed on a test needle with an epoxy resin gel, and then the test needle was placed above Bruker APEX-IICCD diffraction using graphite monochromatic MoK alpha raysTesting the sample, collecting data by using CrysAlisPro-Agilent software, screening diffraction points, determining the lattice type, and carrying out absorption correction and data reduction; the crystal structure was solved directly by the ShellXS procedure, anisotropically refined with ShellXL, at F 2 The method comprises the steps of carrying out finishing correction by using a full matrix least square method, gradually determining the coordinates of non-hydrogen atoms in the structure through difference Fourier peak synthesis, carrying out anisotropic finishing, obtaining hydrogen atoms through theoretical hydrogenation, carrying out isotropic finishing on all the hydrogen atoms, and obtaining yellow blocky crystals named as Zn #anth-py)(anth-ca)。
The analysis result of the X-ray single crystal diffraction test shows that the yellow blocky crystal belongs to a monoclinic system, the space group is P2/n, and the molecular formula is C 52 H 32 N 2 O 4 Zn, molecular weight 814.16, unit cell parameters α=90°, β= 107.2960 (10) °, γ=90°; the basic unit of crystalline Zn (anth-py) (anth-ca) consists of a 9, 10-bis (4-carboxyphenyl) anthracene, a 9, 10-bis (4-pyridyl) anthracene, from which 2 carboxylic acid protons have been removed, and a Zn 2+ Ion composition; each Zn 2+ The ion adopts a four-coordination mode, four coordination points are respectively coordinated with carboxyl oxygen atoms on two 9, 10-di (4-carboxyphenyl) anthracene ligands and pyridine nitrogen atoms on two 9, 10-di (4-pyridyl) anthracene ligands (figure 1), and the distance between Zn and O bonds is->The Zn-N bond distance is +.>Zn (II) ions are alternately connected with 9, 10-bis (4-pyridyl) anthracene through the ligand 9, 10-bis (4-carboxyphenyl) anthracene to form a diamond-like cage structure (figure 2); the diamond-like cage structure forms a six-fold interpenetration structure through pi-pi action (figure 3); the packing pattern of unit cells along the b-axis shows the channel structure in the crystal (fig. 4).
The crystal prepared by the method is subjected to thermal gravimetric analysis (figure 5), and the result shows that the MOFs framework can be kept stable at about 420 ℃, which shows that the crystal has good thermal stability. The crystal phase, purity and crystal quality of the crystals were analyzed by an X-ray diffractometer, and diffraction peak data of diffraction at different temperatures were compared with Mercury software simulation data, and the results showed that the obtained crystals were high in purity, high in crystallinity and high in thermal stability (fig. 6).
Conditions 273K and 298K were usedCO at the bottom 2 Acetylene and ethylene adsorption isotherms detect adsorption and desorption properties of crystal Zn (anth-py) (anth-ca), and the crystal shows typical I-type adsorption characteristic isotherms; the maximum adsorption values of carbon dioxide, acetylene and ethylene at 273K are 68.6, 80.1 and 63.5cm respectively 3 g -1 (FIG. 7), 52.7, 67.3, 53.1cm at 298K, respectively 3 g -1 (FIG. 8).
Claims (3)
1. Adsorption gas CO 2 The porous crystal material is characterized in that the porous crystal material is named Zn (anth-py) (anth-ca) and belongs to monoclinic system, the space group is P2/n, and the molecular formula is C 52 H 32 N 2 O 4 Zn, molecular weight 814.16, unit cell parametersα=90°, β= 107.2960 (10) °, γ=90°; the basic unit of the crystal consists of 9, 10-di (4-carboxyphenyl) anthracene from which 2 carboxylic acid protons are removed, 9, 10-di (4-pyridyl) anthracene and Zn 2+ Ion composition; zn (zinc) 2+ The ion center adopts a four-coordination mode, four coordination points respectively coordinate oxygen atoms on two 9, 10-di (4-carboxyphenyl) anthracene ligands and nitrogen atoms on two 9, 10-di (4-pyridyl) anthracene ligands, and the distance between Zn and O bonds is->The Zn-N bond distance is +.>Zn (II) ions are alternately connected with 9, 10-di (4-pyridyl) anthracene through the ligand 9, 10-di (4-carboxyphenyl) anthracene to form a diamond-like cage structure; the diamond-like cage structure forms a six-fold interpenetration structure through pi-pi action; the cell packing along the b-axis shows its channel structure.
2. A gas adsorption CO according to claim 1 2 Is prepared from porous crystal materialA method, the preparation method comprising the steps of:
weighing a certain amount of 9, 10-di (4-carboxyphenyl) anthracene, 9, 10-di (4-pyridyl) anthracene and zinc salt, putting into a glass bottle, and then adding DMF and ethanol solvent into the glass bottle to form a mixture solution; the mixture solution was stirred for 15min by ultrasonic wave, and a small amount of HNO of 2mol/L was added dropwise with a pipette 3 The method comprises the steps of carrying out a first treatment on the surface of the Placing the glass bottle in an oven, heating at a constant temperature of 80-100 ℃ for reaction for 3-5 days, cooling to room temperature after the reaction is finished, filtering, washing with ethanol, and drying to obtain blocky yellow crystals; the yellow crystal is an adsorption gas CO 2 Is a porous crystalline material of (a);
the zinc salt comprises one or more of zinc nitrate, zinc acetate and zinc sulfate;
the ratio of the amounts of the substances of the ligands 9, 10-di (4-pyridyl) anthracene, zinc salt is 1:1:2.
3. Use of a porous crystalline material according to claim 1, characterized in that the porous crystalline material is capable of selective adsorption of acetylene/CO at 273K and 298K 2 And acetylene/ethylene gas, as a gas selective adsorbent material.
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|---|---|---|---|
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| CN202311557052.4A CN117417546A (en) | 2023-11-21 | 2023-11-21 | Adsorption of gaseous CO 2 Porous crystalline material of (2) and preparation method and application thereof |
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