CN114163651A - Cu-MOFs material with 3D structure, and preparation method and application thereof - Google Patents

Cu-MOFs material with 3D structure, and preparation method and application thereof Download PDF

Info

Publication number
CN114163651A
CN114163651A CN202111415927.8A CN202111415927A CN114163651A CN 114163651 A CN114163651 A CN 114163651A CN 202111415927 A CN202111415927 A CN 202111415927A CN 114163651 A CN114163651 A CN 114163651A
Authority
CN
China
Prior art keywords
copper
mofs
organic framework
paddle wheel
och
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111415927.8A
Other languages
Chinese (zh)
Other versions
CN114163651B (en
Inventor
刘大欢
郭彭涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CN202111415927.8A priority Critical patent/CN114163651B/en
Publication of CN114163651A publication Critical patent/CN114163651A/en
Application granted granted Critical
Publication of CN114163651B publication Critical patent/CN114163651B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • B01D—SEPARATION
    • B01D53/00—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
    • 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
    • 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
    • B01J20/28054—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
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • 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
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/105—Removal of contaminants of nitrogen

Abstract

The invention relates to the technical field of nano porous materials, in particular to a Cu-MOFs material with a 3D structure, a preparation method and an application thereof. The Cu-MOFs material with the 3D structure comprises a copper-organic framework material Cu-MOFs-OCH with methoxyl3Wherein the mass ratio of the organic framework is 68.2-82.4 wt%, and the mass ratio of the copper is 17.6-31.8 wt%. The material pair CH4The adsorption capacity can reach 18cm3·g‑1Above, toCH4/N2Has selectivity as high as 12.5 and is very suitable for enriching CH from coal bed gas4And has good regeneration performance and thermal stability. The preparation method provided by the invention is simple, and the Cu-MOFs material with the 3D structure can be prepared only by removing water molecules on the framework at high temperature in vacuum.

Description

Cu-MOFs material with 3D structure, and preparation method and application thereof
Technical Field
The invention relates to the technical field of nano porous materials, in particular to a Cu-MOFs material with a 3D structure, a preparation method and an application thereof.
Background
Natural gas as oneA clean energy source, mainly composed of methane (CH)4) And (4) forming. Natural gas resources can be divided into two broad categories: conventional natural gas and unconventional natural gas, such as shale gas, landfill gas, low grade natural gas, agricultural waste gas and coal bed gas, store large amounts of CH4But also often contain a large amount of N2Impurities, especially Coal Bed Methane (CBM), cannot be used directly, so at present, CH4The main treatment of unconventional natural gas at low levels is direct venting to the atmosphere. And CH4Is one of six major greenhouse gases, and the potential for global warming is CO2More than 20 times higher, thus recovering and capturing CH from unconventional natural gas4Has important significance for effectively utilizing energy and protecting environment.
The adsorption separation technology has the advantages of simple operation, low energy consumption and the like. The key to adsorptive separation is the selection of a suitable adsorbent. Traditional adsorbents such as molecular sieves, zeolites, etc., often have low adsorption capacity or low selectivity and cannot meet practical requirements. Therefore, the development of adsorbents with good selectivity and high adsorption amount is still the focus of research. The metal-organic framework has the advantages of high porosity, ordered structure, adjustable pore diameter and the like, and has important application in the aspect of gas adsorption separation.
Disclosure of Invention
The invention aims to provide a Cu-MOFs material with a 3D structure, for CH4Has good adsorption capacity and selectivity, and can be applied to separating CH in coal bed gas4And N2And enriching methane gas.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a Cu-MOFs material with a 3D structure comprises a Cu-organic framework material Cu-MOFs-OCH with methoxyl3Wherein the mass ratio of the organic framework is 68.2-82.4 wt%, and the mass ratio of the copper is 17.6-31.8 wt%;
cu in the material and a ligand in an organic framework form a paddle wheel unit, and paddle wheel units of adjacent layers are connected through the ligand to form a one-dimensional infinite channel stacked along a c axis; wherein adjacent layers are spaced apart
Figure BDA0003375298560000021
In the meantime.
The carboxylic acid oxygen atoms in the organic framework are connected with the positions of water molecules lost on the paddle wheel units of the adjacent layers, and a paddle wheel chain with a 3D structure is formed along a Cu-Cu shaft;
the aromatic plane in the organic framework inclines towards the pore channel direction of the material;
the material has a nonpolar ultramicropore structure and an average pore diameter of
Figure BDA0003375298560000022
Average specific surface area 265-293m2·g-1。
The invention also provides a preparation method of the Cu-MOFs material with the 3D structure, which comprises the following steps:
s1: dissolving a copper salt and an organic ligand in a solvent, adding a modifier, stirring at room temperature for 10-18h, soaking a suction filtration product in the solvent for 48-96h, and drying at 50-80 ℃ to obtain a precursor material;
wherein the copper salt comprises one or more of copper nitrate, copper sulfate, copper chloride, copper acetate, copper sulfite, copper oxalate, copper carbonate, copper phosphate, copper hypohalite and copper sulfite,
preferably, the copper salt is copper nitrate;
wherein the organic ligand comprises one or more of 5-methoxy isophthalic acid, 2-methoxy benzoic acid and p-methoxyphenol,
preferably, the organic ligand is 5-methoxy isophthalic acid;
wherein the modifying agent comprises pyridine;
preferably, the molar mass ratio of the copper salt, the organic ligand and the modifier is 1: 0.9-1.1: 0.95-1.05;
more preferably, the molar mass ratio of the copper salt, the organic ligand and the modifier is 1:1: 1.
Wherein the solvent comprises methanol, ethanol, acetone, methyl acetate, ethyl acetate, propylene oxide, N-dimethylformamide and/or diethyl ether,
preferably, the solvent is methanol.
S2: and degassing the precursor material in a vacuum environment at the temperature of 100-150 ℃ for 10-18h to obtain the Cu-MOFs material with the 3D structure.
Wherein the vacuum degree of the vacuum environment is (0.7-1.2) x 10-3Pa。
In the step, the degassing treatment can remove coordinated water molecules in the organic framework, so that the structure of the precursor material is converted from 2D to the 3D structure of the material provided by the invention. Cu in the structure of precursor material2+And ligand to form Cu2+Paddle wheel units, the axial positions of which are occupied by water molecules, forming an infinite kagomie type two-dimensional (2D) lamellar structure by the connection of ligands between the paddle wheel units, the two-dimensional layers being arranged in layers of
Figure BDA0003375298560000023
Are stacked at intervals, and two one-dimensional infinite channels with different cross section sizes are respectively formed along the C axis. And removing water molecules from the paddle wheel unit through vacuum degassing treatment, so that one carboxylic acid oxygen atom on the organic framework of the adjacent layer is coordinated with the position of the removed water molecule to form a 3D paddle wheel chain structure along the Cu-Cu axis.
After water molecules are removed, the shape of the pore channel of the material is obviously changed, and the material Cu-MOF-OCH provided by the invention3In the structure (2), the carboxylate is twisted on the Cu-Cu axis, and the aromatic plane is further inclined toward the pore channel, so that the pore diameter becomes narrower than that of the precursor material, and ultra-micropores having a nonpolar pore environment are formed due to CH4Has a polarizability higher than N2The non-polar pore environment may be associated with CH4The molecules form stronger van der Waals interactions favoring the exchange from CH4/N2Trapping CH in mixtures4。
The invention also provides a method for adsorbing CH by the Cu-MOFs material with the 3D structure4Application in the aspect of adsorption separation of CH in coal bed gas4And N2Application of the aspect.
Compared with the prior art, the invention has the following advantages:
(1) Cu-MOFs material pair CH with 3D structure4The adsorption capacity can reach 18cm3·g-1Above, to CH4/N2Has selectivity of more than 12.5 and is very suitable for enriching CH from coal bed gas4。
(2) The preparation method is simple, and the water molecule on the framework can be removed at high temperature in vacuum to prepare the water-soluble organic silicon material.
(3) The Cu-MOFs material with the 3D structure has good regeneration performance and thermal stability, and is suitable for industrial application.
Drawings
FIG. 1(a) is Cu-MOFs-OCH3PXRD pattern of the material, (b) is Cu-MOFs-OCH3Material N at 77K2Adsorption isotherms;
FIG. 2 is a Cu-MOFs-OCH3SEM images of the material;
FIG. 3 is a Cu-MOFs-OCH3An infrared spectrum of the material;
FIG. 4 is a Cu-MOFs-OCH3PXRD comparison of the material and the precursor material;
FIG. 5(a) is a diagram of a precursor material along the C-axis, (b) is a Cu paddlewheel coordination diagram of the precursor material, (C) is a two-dimensional stacking diagram of the precursor material kagomie-type, (d) is a diagram of Cu-MOFs-OCH3The structure of the material along the C axis, (e) is Cu-MOFs-OCH3Cu-paddle coordination diagram of the material, (f) is Cu-MOFs-OCH3A Kagomei-type two-dimensional stacking graph of materials;
FIG. 6(a) is a diagram showing Cu-MOFs-OCH samples of examples 1-23Material pair CH4And N2Adsorption isotherm of (a), (b) is the CH of the material at 298K predicted by ideal solution adsorption theory4/N2Selectivity;
FIG. 7(a) is CH for material4/N2(50/50) penetration test Curve, (b) is CH of the Material penetration cycle4Comparing the penetration adsorption quantity with the penetration time;
FIG. 8 shows STAM-1 vs. CH for the prior art materials4And N2Adsorption isotherm of (1).
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
The technical solutions of the present invention will be described in detail with reference to specific examples, but those skilled in the art will understand that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Example 1
Cu-MOFs material Cu-MOFs-OCH with 3D structure3The material is a copper-organic framework material with methoxyl, wherein the mass proportion of the organic framework is 74.5 wt%, and the mass proportion of copper is 25.5 wt%.
As shown in FIG. 1-FIG. 5, Cu-MOFs-OCH3Cu in the material and a ligand in an organic framework form a paddle wheel unit, and paddle wheel units of adjacent layers are connected through the ligand to form a one-dimensional infinite channel stacked along a c axis; wherein the adjacent layers have a spacing of
Figure BDA0003375298560000041
And carboxylic acid oxygen atoms on adjacent layers of the material are connected with the positions of the paddle wheel units, which are used for removing water molecules, a paddle wheel chain is formed along a Cu-Cu shaft, and an aromatic plane in the organic framework inclines towards the pore channel direction of the material.
Cu-MOFs-OCH3The material has nonpolar ultramicropore structure and pore diameter
Figure BDA0003375298560000042
Specific surface area 281m2·g-1。
Preparation of Cu-MOFs-OCH3The preparation method of the material comprises the following steps:
s1: 2.4 g of Cu (NO)3)·3H2Dissolving O (10mmol) and 2.12 g of 5-methoxy isophthalic acid (10mmol) in 200mL of methanol, performing ultrasonic treatment until the O and the 5-methoxy isophthalic acid are completely dissolved, adding 0.8g of pyridine (10mmol), stirring at room temperature for 12h, soaking a suction filtration product in methanol for 72h, replacing the methanol every 8h, and drying in a vacuum oven at 60 ℃ after the soaking is finished to obtain a precursor material;
s2: placing the precursor material at 120 deg.C under vacuum degree of 1 × 10-3Degassing for 12h in a Pa vacuum environment to obtain the Cu-MOFs material Cu-MOFs-OCH with the 3D structure3。
Test example 1
The resulting material was subjected to an adsorption test in which 1.3g of dried Cu-MOFs-OCH3The sample powder of the material was placed in the sample tube of the adsorption apparatus. To completely remove the solvent molecules from the organic framework, the sample powder was degassed in vacuo at 393K for 12 hours. During the adsorption isotherm measurements, the adsorption measurement pressure was varied from 0.0 to 1.0bar and the water and ice water baths were used to maintain the temperature of the entire system (298 and 273K), respectively.
As shown in FIG. 6, CH was collected using Quantachrome Autosorb-IQ analyzer4And N2Single component adsorption isotherms at 273 and 298K. The adsorption-desorption isotherms were measured at different temperatures, and the adsorption equilibrium time was maintained at 30 minutes at each pressure point of the adsorption isotherm. For CH4The desorption process of each cycle measurement is performed immediately after the adsorption measurement, and is completed by gradually reducing the measurement pressure to a vacuum state. Then, the same procedure is started in the next adsorption-desorption cycle.
As shown in FIG. 7, the dynamic separation performance of the material was tested by a breakthrough experiment, and 1.0 g of Cu-MOFs-OCH3A sample of the powder of the material was loaded into a cylindrical stainless steel penetrating column of 200mm in length and 6mm in internal diameter, and the length of the loaded sample was approximately 47 mm. Before carrying out breakthrough measurements, the fixed bed with sample was flushed with a helium gas flow (30 mL. min) at 373K-1) Purge in situ for 6 hours to ensure that the bed is saturated with helium. Then equimolar CH was introduced at 298K and 1.0bar4/N2Mixture (4 mL. min)-1). The component concentrations of the effluent gas were continuously monitored by a multicomponent mass spectrometer (BSD-MAB, incicon).
As can be seen from FIG. 1(b), 77K N2The adsorption isotherm belongs to the type I curve, which shows that the material has ultramicropore property.
From FIGS. 1(a) and 2, it can be seen that Cu-MOFs-OCH3Has good crystallization, regular structure and obvious layered structure.
From FIG. 3, it can be seen that at 923 and 2847cm-1There is a band belonging to the group-OCH 3, indicating the presence of a methoxy group.
From fig. 4 and 5, it can be seen that after water molecules coordinated in the precursor material are removed at high temperature, PXDR diffraction peak shifts to the left, the structure of the material changes, coordination occurs between adjacent layers, the structure is changed from 2D to 3D, the pore diameter is narrowed, a large number of nonpolar ultramicropore structures are formed, and CH is favorably coordinated4Adsorption of (3). .
As can be seen from FIG. 6, Cu-MOFs-OCH3Material pair CH4The adsorption capacity of (A) is far greater than that of (N)2Shows excellent adsorption to CH4Selectivity of (2).
Example 2
Cu-MOFs material Cu-MOFs-OCH with 3D structure3Is a copper-organic framework material with methoxyl,wherein the mass ratio of the organic framework is 82.4 wt%, and the mass ratio of the copper is 17.6 wt%.
Cu-MOFs-OCH3Cu in the material and a ligand in an organic framework form a paddle wheel unit, and paddle wheel units of adjacent layers are connected through the ligand to form a one-dimensional infinite channel stacked along a c axis; wherein the adjacent layers have a spacing of
Figure BDA0003375298560000061
And carboxylic acid oxygen atoms on adjacent layers of the material are connected with the positions of the paddle wheel units, which are used for removing water molecules, a paddle wheel chain is formed along a Cu-Cu shaft, and an aromatic plane in the organic framework inclines towards the pore channel direction of the material.
Cu-MOFs-OCH3The material has nonpolar ultramicropore structure and pore diameter
Figure BDA0003375298560000062
Specific surface area 265m2·g-1。
Preparation of Cu-MOFs-OCH3The preparation method of the material comprises the following steps:
s1: 2.4 g of Cu (NO)3)·3H2Dissolving O (10mmol) and 1.91 g of 5-methoxy isophthalic acid (9mmol) in 200mL of methanol, performing ultrasonic treatment until the O and the 5-methoxy isophthalic acid are completely dissolved, adding 0.76g of pyridine (9.5mmol), stirring at room temperature for 10h, soaking a suction filtration product in methanol for 48h, replacing the methanol every 8h, and drying in a vacuum oven at 50 ℃ after soaking is completed to obtain a precursor material;
s2: placing the precursor material at 100 deg.C and vacuum degree of 1 × 10-3Degassing for 10 hours in a Pa vacuum environment to obtain the Cu-MOFs material Cu-MOFs-OCH with the 3D structure3。。
Example 3
Cu-MOFs material Cu-MOFs-OCH with 3D structure3The material is a copper-organic framework material with methoxyl, wherein the mass proportion of the organic framework is 68.2 wt%, and the mass proportion of copper is 31.8 wt%.
Cu-MOFs-OCH3Cu in the material and a ligand in an organic framework form a paddle wheel unit, and the paddle wheel units of adjacent layers are connected through the ligand to form a stack along a c axisThe one-dimensional infinite channel of (a); wherein the adjacent layers have a spacing of
Figure BDA0003375298560000063
And carboxylic acid oxygen atoms on adjacent layers of the material are connected with the positions of the paddle wheel units, which are used for removing water molecules, a paddle wheel chain is formed along a Cu-Cu shaft, and an aromatic plane in the organic framework inclines towards the pore channel direction of the material.
Cu-MOFs-OCH3The material has nonpolar ultramicropore structure and pore diameter
Figure BDA0003375298560000064
Specific surface area 293m2·g-1。
Preparation of Cu-MOFs-OCH3The preparation method of the material comprises the following steps:
s1: 2.4 g of Cu (NO)3)·3H2Dissolving O (10mmol) and 2.33 g of 5-methoxy isophthalic acid (11mmol) in 200mL of methanol, performing ultrasonic treatment until the O and the 5-methoxy isophthalic acid are completely dissolved, adding 0.84g of pyridine (10.5mmol), stirring at room temperature for 18h, soaking a suction filtration product in methanol for 96h, replacing the methanol every 8h, and drying in a vacuum oven at 80 ℃ after soaking is completed to obtain a precursor material;
s2: placing the precursor material at 150 deg.C under vacuum degree of 1 × 10-3Degassing for 18h in a Pa vacuum environment to obtain the Cu-MOFs material Cu-MOFs-OCH with the 3D structure3。
Test comparative example 1
Performing an adsorption test on the existing material STAM-1, wherein the specific surface area of the material is 110m2·g-1Pore diameter of
Figure BDA0003375298560000065
A sample powder of 1.3g of dried STAM-1 material was placed in a sample tube of an adsorption apparatus. During the adsorption isotherm measurements, the adsorption measurement pressure was varied from 0.0 to 1.0bar and the water and ice water baths were used to maintain the temperature of the entire system (298 and 273K), respectively.
The adsorption curve of the STAM-1 material is shown in FIG. 8.
Pass test example 1 and test comparative example1, the Cu-MOFs-OCH provided by the invention3To CH4/N2The selectivity far exceeds that of the existing material STAM-1.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (10)

1. The Cu-MOFs material with the 3D structure is characterized by comprising a Cu-organic framework material Cu-MOFs-OCH with methoxyl3Wherein the mass ratio of the organic framework is 68.2-82.4 wt%, and the mass ratio of the copper is 17.6-31.8 wt%.
2. The material of claim 1, wherein the Cu in the material forms paddle wheel units with ligands in the organic framework, and the paddle wheel units of adjacent layers are connected to each other by the ligands to form a one-dimensional infinite channel stacked along the c-axis, wherein the adjacent layers are spaced at intervals
Figure FDA0003375298550000011
In the meantime.
3. The material of claim 2, wherein the carboxylic acid oxygen atoms in the organic backbone are attached to the positions of missing water molecules on the paddle wheel units of adjacent layers, forming a paddle wheel chain of 3D structure along the Cu-Cu axis.
4. The material of claim 1, wherein the aromatic plane in the organic framework is inclined toward the pore channel direction of the material.
5. The material according to claim 1, wherein the material has a nonpolar ultramicropore structure with an average pore diameter of
Figure FDA0003375298550000012
Average specific surface area 265-293m2·g-1。
6. A preparation method of a Cu-MOFs material with a 3D structure is characterized by comprising the following steps:
s1: dissolving a copper salt and an organic ligand in a solvent, adding a modifier, stirring, soaking a suction filtration product in the solvent for t1 time, and drying to obtain a precursor material;
s2: and placing the precursor material in a vacuum environment at the temperature of T1 for degassing for T2 time to obtain the Cu-MOFs material with the 3D structure.
7. The method according to claim 6, wherein step S1 satisfies one or more of the following conditions:
a. the copper salt comprises one or more of copper nitrate, copper sulfate, copper chloride, copper acetate, copper sulfite, copper oxalate, copper carbonate, copper phosphate, copper hypohalite and copper sulfite;
b. the organic ligand comprises one or more of 5-methoxy isophthalic acid, 2-methoxy benzoic acid and p-methoxyphenol;
c. the solvent comprises methanol, ethanol, acetone, methyl acetate, ethyl acetate, propylene oxide, N-dimethylformamide and/or diethyl ether;
d. the modifier comprises pyridine;
e. the stirring temperature is room temperature, and the stirring time is 10-18 h;
f. the t1 time is 48-96 h;
g. the drying temperature is 50-80 ℃;
preferably, the copper salt is copper nitrate;
preferably, the organic ligand is 5-methoxy isophthalic acid;
preferably, the molar mass ratio of the copper salt, the organic ligand and the modifier is 1: 0.9-1.1: 0.95-1.05;
preferably, the molar mass ratio of the copper salt, the organic ligand and the modifier is 1:1: 1.
8. The method according to claim 6, wherein step S2 satisfies one or more of the following conditions:
h. the temperature T1 is 100-150 ℃;
i. the vacuum degree of the vacuum environment is (0.7-1.2) multiplied by 10-3Pa；
j. The t2 time is 10-18 h.
9. Adsorption of CH by the material according to any of claims 1 to 54Application of the aspect.
10. Use of the material of any one of claims 1-5 for adsorptive separation of CH from coal bed methane4And N2Application of the aspect.
CN202111415927.8A 2021-11-25 2021-11-25 Cu-MOFs material with 3D structure, and preparation method and application thereof Active CN114163651B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111415927.8A CN114163651B (en) 2021-11-25 2021-11-25 Cu-MOFs material with 3D structure, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111415927.8A CN114163651B (en) 2021-11-25 2021-11-25 Cu-MOFs material with 3D structure, and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114163651A true CN114163651A (en) 2022-03-11
CN114163651B CN114163651B (en) 2022-11-15

Family

ID=80480788

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111415927.8A Active CN114163651B (en) 2021-11-25 2021-11-25 Cu-MOFs material with 3D structure, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114163651B (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102762536A (en) * 2010-02-24 2012-10-31 可乐丽股份有限公司 Metal complex, and adsorbent, occlusion material and separator material made from same
CN102962036A (en) * 2012-10-30 2013-03-13 中国科学院大连化学物理研究所 Porous metal organic framework material based on transition metal cobalt and preparation method thereof
CN103100372A (en) * 2013-01-25 2013-05-15 浙江大学 Metal-organic framework material for methane adsorption and storage and preparation method thereof
CN103748064A (en) * 2011-08-17 2014-04-23 株式会社可乐丽 Metal complex and adsorbent material, storage material, and separating material comprising same
CN104549185A (en) * 2014-12-04 2015-04-29 同济大学 Surface modification method of metal-organic framework adsorbing materials
CN104755453A (en) * 2012-11-02 2015-07-01 新日铁住金株式会社 Porous polymer-metal complex, gas adsorbent, and gas separation device and gas storage device using same
CN113019330A (en) * 2021-03-11 2021-06-25 北京工业大学 Preparation of copper-based metal-organic framework material and acetylene/carbon dioxide separation application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102762536A (en) * 2010-02-24 2012-10-31 可乐丽股份有限公司 Metal complex, and adsorbent, occlusion material and separator material made from same
CN103748064A (en) * 2011-08-17 2014-04-23 株式会社可乐丽 Metal complex and adsorbent material, storage material, and separating material comprising same
CN102962036A (en) * 2012-10-30 2013-03-13 中国科学院大连化学物理研究所 Porous metal organic framework material based on transition metal cobalt and preparation method thereof
CN104755453A (en) * 2012-11-02 2015-07-01 新日铁住金株式会社 Porous polymer-metal complex, gas adsorbent, and gas separation device and gas storage device using same
CN103100372A (en) * 2013-01-25 2013-05-15 浙江大学 Metal-organic framework material for methane adsorption and storage and preparation method thereof
CN104549185A (en) * 2014-12-04 2015-04-29 同济大学 Surface modification method of metal-organic framework adsorbing materials
CN113019330A (en) * 2021-03-11 2021-06-25 北京工业大学 Preparation of copper-based metal-organic framework material and acetylene/carbon dioxide separation application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DU L , LU Z , LI X , ET AL: "A new mfj-type metal-organic framework constructed from a methoxyl derived V-shaped ligand and its H2, CO2 and CH4 adsorption properties", 《RSC ADVANCES》 *
FENGLI CHEN, DONGJIE BAI, YAO WANG, DONGHAO JIANG AND YABING HE: "A family of ssa-type copper-based MOFs", 《MATERIALS CHEMISTRY》 *
MA L F , ZHAO J W , HAN M L: "Two novel 3-D coordination polymers with 5-methoxyisophthalate and flexible N-donor co-ligands showing pentanuclear or alternate mono/binuclear Cu(II) units", 《DALTON TRANSACTIONS》 *
WANG, YAO, HE, ET AL: "Exploring the Effect of Ligand-Originated MOF Isomerism and Methoxy Group Functionalization on Selective Acetylene/Methane and Carbon Dioxide/Methane Adsorption Properties in Two NbO-Type MOFs", 《ACS APPLIED MATERIALS & INTERFACES》 *

Also Published As

Publication number Publication date
CN114163651B (en) 2022-11-15

Similar Documents

Publication Publication Date Title
Wang et al. Highly efficient CO2 adsorption by nitrogen-doped porous carbons synthesized with low-temperature sodium amide activation
Rao et al. N-doped porous carbons from low-temperature and single-step sodium amide activation of carbonized water chestnut shell with excellent CO2 capture performance
Ye et al. Post-combustion CO2 capture with the HKUST-1 and MIL-101 (Cr) metal–organic frameworks: Adsorption, separation and regeneration investigations
Chuah et al. Potential of adsorbents and membranes for SF6 capture and recovery: A review
JP5732451B2 (en) Use of zeolitic microporous crystalline materials with RHO structure in natural gas processing
Xiong et al. A microporous metal–organic framework with commensurate adsorption and highly selective separation of xenon
US6491740B1 (en) Metallo-organic polymers for gas separation and purification
Sevilla et al. High-performance CO 2 sorbents from algae
CN108380189B (en) Adsorbent material
Kim et al. High SF6 selectivities and capacities in isostructural metal-organic frameworks with proper pore sizes and highly dense unsaturated metal sites
US20180214849A1 (en) Mof-derived porous carbon materials for carbon dioxide capture
Wang et al. A versatile synthesis of metal–organic framework-derived porous carbons for CO 2 capture and gas separation
CA2688687A1 (en) Process for removing a target gas from a mixture of gases by swing adsorption
CA2788961A1 (en) Metal complex, and adsorbent, occlusion material and separator material made from same
Dong et al. Gas storage and separation in a water-stable [Cu I 5 BTT 3] 4− anion framework comprising a giant multi-prismatic nanoscale cage
Asghar et al. Efficient electrochemical synthesis of a manganese-based metal–organic framework for H 2 and CO 2 uptake
Wang et al. General strategies for effective capture and separation of noble gases by metal–organic frameworks
Tian et al. Identification of solid-state forms of cucurbit [6] uril for carbon dioxide capture
Cheng et al. Enhanced CO2 selectivity of mixed matrix membranes with carbonized Zn/Co zeolitic imidazolate frameworks
Ge et al. CO2 capture and separation of metal–organic frameworks
Li et al. The effect of pore sizes on D 2/H 2 separation conducted by MOF-74 analogues
Zhu et al. A dense 3d–4f metal–organic framework with “gas pockets” for highly efficient CH 4/N 2 separation
CN114042436A (en) Molded MOFs material and preparation method and application thereof
CN114163651B (en) Cu-MOFs material with 3D structure, and preparation method and application thereof
Choi et al. CO 2-selective zeolitic imidazolate framework membrane on graphene oxide nanoribbons: experimental and theoretical studies

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant