CN110078751B - Porous crystalline material with sodium chloride type and preparation method thereof - Google Patents

Porous crystalline material with sodium chloride type and preparation method thereof Download PDF

Info

Publication number
CN110078751B
CN110078751B CN201910281240.6A CN201910281240A CN110078751B CN 110078751 B CN110078751 B CN 110078751B CN 201910281240 A CN201910281240 A CN 201910281240A CN 110078751 B CN110078751 B CN 110078751B
Authority
CN
China
Prior art keywords
porous crystalline
crystalline material
zinc
sodium chloride
porous
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.)
Active
Application number
CN201910281240.6A
Other languages
Chinese (zh)
Other versions
CN110078751A (en
Inventor
凌云
周亚明
邓名莉
陈珍霞
刘小锋
杨永泰
贾瑜
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.)
Fudan University
Original Assignee
Fudan University
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 Fudan University filed Critical Fudan University
Priority to CN201910281240.6A priority Critical patent/CN110078751B/en
Publication of CN110078751A publication Critical patent/CN110078751A/en
Application granted granted Critical
Publication of CN110078751B publication Critical patent/CN110078751B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01J20/28014—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
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic System without C-Metal linkages
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

Abstract

The invention relates to a porous crystalline material with a sodium chloride type and a preparation method thereof, wherein the skeleton structure of the porous crystalline material simultaneously contains two secondary structure units of zinc tetraoxide and vehicle-assisted type, and the two secondary structure units are alternately linked to jointly construct a three-dimensional network structure of the sodium chloride type, and the preparation method comprises the steps of enabling zinc salt and an organic ligand H to be connected2L1 and H1L1 is prepared by one-step solution heat reaction. The preparation method of the porous crystalline material provided by the invention is simple and feasible, has high structural stability, can derive a series of isomorphic porous crystalline materials by regulating and controlling the size of the pore channel and the surface functional group of the pore channel, and has wide application prospects in molecular adsorption separation and storage.

Description

Porous crystalline material with sodium chloride type and preparation method thereof
Technical Field
The invention relates to the technical field of porous materials, in particular to a porous crystalline material with a sodium chloride type and a preparation method thereof.
Background
The porous material has wide application in the engineering technical fields of gas separation adsorption and storage, industrial catalysis, molecular recognition, sensing and the like. Therefore, the new porous material is a motive force for promoting technical innovation, and the research on the synthesis, structure and properties of the new porous material is more and more valued by researchers.
Since the last 90 s of the last century, two novel porous crystalline materials, MOF-5 based on Zn4O secondary structural unit and HKUST-1 based on vehicle-assisted secondary structural unit, were reported in the Science journal by professor Omar Yaghi in Nature journal and by professor Ian D.WILLIAMS in Hongkong, respectively, the research enthusiasm of the novel porous crystalline material based on coordination bond assembly was raised. The material has the characteristics obviously different from the traditional molecular sieve and porous carbon material, and comprises the following components: in terms of designability of geometric topology, infinite structural possibilities, ease of functionalization, etc. The porous crystalline material based on the Zn4O secondary structure unit and the porous crystalline material based on the vehicle auxiliary type have been developed in parallel research, and as the application research goes deep, the respective disadvantages are gradually discovered.
Although porous crystalline materials based on Zn4O secondary structural units show high thermal stability, the materials are easily decomposed in an air atmosphere environment, and the performance is seriously influenced. The main reason for the decomposition is that the secondary structural unit of Zn4O is easily attacked by water molecules, resulting in the breakage of coordination bonds. Although the structural unit based on the vehicle auxiliary type has relatively good air atmosphere stability at normal temperature, the low thermal stability and the special structural flexibility cause that the application of the porous crystalline material is greatly limited. Therefore, although these two types of porous crystalline materials exhibit excellent performance in a laboratory environment, they are very challenging to apply in a real-world environment.
Disclosure of Invention
The invention aims to solve the problems and provides a series of porous crystalline materials with a sodium chloride type, which are constructed by zinc tetraoxide and vehicle-auxiliary secondary structure units, and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a framework structure of the porous crystalline state material simultaneously contains two secondary structure units of zinc tetraoxide and vehicle-auxiliary type, and the two secondary structure units are alternately linked to jointly construct a three-dimensional network structure of the sodium chloride type.
Further, the molecular general formula of the skeleton structure of the porous crystalline material is [ Zn ]6(O)(L1)4(L2)2]Wherein: l1 is a fully deprotonated linear diacid ligand, L2 is a fully deprotonated azole ligand with a triangular coordination geometry, O is an oxyanion of the negative divalent state.
The zinc tetraoxide and vehicle-auxiliary two secondary structure units are alternately linked through L2 to form a one-dimensional chain, the one-dimensional chain is further linked with the zinc tetraoxide secondary structure unit through one end of L1, the other end of the one-dimensional chain is linked with the vehicle-auxiliary secondary structure unit, and finally the one-dimensional chain is linked into the three-dimensional porous crystal material with the sodium chloride type structure, wherein the vehicle-auxiliary type is a classical structure type, the zinc tetraoxide secondary structure unit is in a third form (table 1) of the following zinc tetraoxide structure units, namely 4 carboxyl groups occupy an equatorial plane, and two azole nitrogen groups occupy axial positions.
TABLE 1 structural formula of Zinc tetraoxide Secondary building Block
Figure BDA0002021736440000021
Figure BDA0002021736440000031
In the structure L1 is derived from a fully deprotonated linear dicarboxylic acid H2L1, and the structure contains at least one of the compounds listed in Table 2.
TABLE 2H referred to in the present invention2Structural formula of L1
Figure BDA0002021736440000032
L2 in the structure is fromFully deprotonated nitrogen-containing ligand H of triangular coordination geometry1L2, and the structure contains at least one of the following listed in Table 3.
TABLE 3H relating to the invention2Structural formula of L2
Figure BDA0002021736440000041
The regulation of the size of the pore channel of the porous crystalline material is realized by changing the type of L1 and/or L2, and the regulation of the surface functional group of the pore channel of the porous crystalline material is realized by selecting the structure of L1 and/or L2.
The pore size regulation of the porous crystalline material can be realized by three ways. One is as follows: if L1 in the initial porous material is the structural formula with the serial number of 1 in Table 2, L2 is the structural formula with the serial number of 1 in Table 3, any one of the serial numbers of 9-16 in Table 2 can be selected to replace the original L1, and the new material shows the increase of the size of the A pore channel shown in figure 1 relative to the initial material; the second step is as follows: in contrast, any one of serial numbers 9-12 in table 3 was selected to replace the original L2, and the new material showed the B channel size regulation shown in fig. 1 relative to the original material; and thirdly: correspondingly, any one of serial numbers 9-16 in table 2 is selected to replace the original L1, any one of serial numbers 9-12 in table 3 is selected to replace the original L2, and the new material shows the simultaneous regulation and control of the sizes of the A and B pore channels shown in fig. 1 relative to the original material.
The regulation of the channel surface functional groups of the porous crystalline material is realized by selecting any structural formula in table 2 and/or table 3, for example: if the initial porous crystalline material consists of the L1 ligand with the serial number of 1 in the table 2 and the L2 ligand with the serial number of 1 in the table 3, the L1 ligand with the serial number of 1 in the initial structure is replaced by any one of the serial numbers of 2-16 in the table 2, so that the functional modulation of single functional groups such as hydroxylation, fluorination, amination and phenylation and the like on the surface of the pore channel A shown in the figure 1 can be realized; correspondingly, the original single L1 ligand with the serial number of 1 can be replaced by any 2, 3 or 4L 1 combinations with serial numbers 1 to 8 in table 2, so that the composite functional regulation of the combination of multiple functional groups such as hydroxylation, fluorination, amination and phenylation on the surface of the pore channel a shown in fig. 1 can be realized. Similarly, if the initial porous crystalline material is composed of L1 with the serial number of 1 in table 2 and L2 with the serial number of 1 in table 3, then the single functional group can be adjusted and controlled by replacing the L2 ligand with the serial number of 1 in the initial structure with any one of the serial numbers of 2-12 in table 3 to obtain the new material with the B pore channel surface functionalized by the single functional group in fig. 1; or replacing the original single L2 ligand with the serial number 1 by the combination of 2, 3 and 4L 2 with the serial numbers 1-8 in the table 3 to obtain the new material with the composite functionalized surface of the channel B in the figure 1.
The novel porous crystalline material provided by the invention shows high thermal stability and stability of a porous structure under ambient humidity. The high thermal stability means that the temperature of the porous crystalline material which is remarkably heated to weight loss under the condition of nitrogen atmosphere after the pore channel is activated is more than or equal to 350 ℃; the stability of the porous structure at ambient humidity means that the temperature at which significant phase changes occur at ambient conditions is greater than or equal to 200 ℃.
A process for preparing the porous crystalline material with sodium chloride type includes such steps as mixing zinc salt with organic ligand H2L1、H1And carrying out solvothermal reaction on the L1 and an organic solvent at 100-180 ℃ for 8-72 hours, and cooling, filtering, washing and drying to obtain the porous crystalline material.
The zinc salt and organic ligand H2L1、H1The molar ratio of L1 is 2-4.5: 1.5-2: 1, preferably 3:2: 1.
The zinc salt is selected from one of zinc nitrate, zinc sulfate, zinc acetate, zinc chloride or water-containing crystal salt thereof, the organic solvent is selected from one or two of nitrogen dimethyl formamide, nitrogen diethyl formamide, nitrogen dimethyl acetamide, dimethyl sulfoxide or dimethyl pyrrolidone, and the concentration of the zinc salt is 0.02-0.05M optimally.
The zinc salt is one or any two of zinc nitrate, zinc sulfate, zinc acetate, zinc chloride or their water-containing crystal salts, and the zinc nitrate or its water-containing crystal salt is the most preferable.
During the solvent thermal reaction, magnetic force or mechanical stirring is carried out, the rotating speed is 200-600r/min, the time is 5-15 minutes, 500r/min is used, and 10 minutes is optimal. The reaction solution is sealed in a stainless steel outer container reactor with the thickness of not less than 0.5cm, the reaction temperature is 100-180 ℃, the optimal temperature is 140 ℃, the reaction time is 8-72 hours, and the optimal time is 24 hours.
Before the porous crystalline material is applied to gas adsorption, separation, storage and the like, the pore channel activation step comprises the following steps: and heating the porous crystalline material to 200 ℃ in a vacuum degassing environment, and activating for a certain time. The material is firstly degassed to 20 mu mHg in vacuum, then an external heating bag is heated to 200 ℃, and the time of the vacuum degassing activation process is not less than 8 hours.
Compared with the prior art, the invention has the following advantages:
(1) the structure simultaneously contains two 6-linked secondary structure units of zinc tetraoxide and vehicle-assisted type, and the two classic secondary structure units are integrated into a sodium chloride type network structure to construct a novel porous crystalline material, so that the porous crystalline material with high thermal stability, air environment stability and even high humidity environment stability is provided.
(2) The two secondary structure units are orderly assembled into a porous crystalline material with a typical sodium chloride structure;
(3) the size of the pore channel and the functional group on the surface of the pore channel are easily regulated and controlled by ligands L1 and L2;
(4) the preparation method and the activation treatment step before use of the system porous crystalline material are simple and easy to implement.
Drawings
FIG. 1 is a schematic diagram of the framework structure of the porous crystalline material of the present invention;
FIGS. 2-5 are four skeletal structures of the porous crystalline material of the present invention showing the modulation of pore size and functional groups;
FIGS. 6-8 show the results of high thermal stability, environmental thermal stability and porosity of the porous crystalline material of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
Sample preparation: weighing 0.104g of zinc nitrate hexahydrate and 0.033g of terephthalic acid, 0.010g of 3, 5-dimethyl-1H-1, 2, 4-triazole, adding into 10mL of nitrogen-nitrogen diethylformamide, magnetically stirring at room temperature for 10 minutes to prepare a uniform and transparent solution, transferring the solution into a stainless steel reaction kettle, heating at 140 ℃ for 24 hours, cooling, centrifuging, washing, centrifuging again, and drying to obtain the porous crystalline material with the sodium chloride type structure constructed by zinc tetraoxide and a vehicle-assisted secondary structural unit.
Example 2
Sample preparation: weighing 0.086g of zinc chloride tetrahydrate and 0.048g of diphenic acid, 0.012g of 3, 5-diethyl-1H-1, 2, 4-triazole, adding the weighed materials into 10mL of nitrogen-nitrogen dimethylformamide, magnetically stirring the materials at room temperature for 20 minutes to prepare a uniform solution, transferring the solution into a stainless steel reaction kettle, heating the solution at 180 ℃ for reaction for 48 hours, cooling, centrifuging, washing, centrifuging and drying the solution to obtain the porous crystalline material with the sodium chloride type structure constructed by zinc tetraoxide and a vehicle-assisted secondary structural unit, wherein the size of a pore channel of the material prepared in example 2 is increased by about 0.6nm relative to that of the material prepared in example 1, and the functional group on the surface of the pore channel is converted from methyl to ethyl.
Example 3
Sample preparation: weighing 0.154g of zinc nitrate hexahydrate, 0.048g of biphenyldicarboxylic acid and 0.181g of L2 ligand with the number of 10 in Table 3, adding the weighed materials into 10mL of nitrogen-nitrogen dimethylacetamide, magnetically stirring the materials at room temperature for 15 minutes to prepare a uniform solution, transferring the uniform solution into a stainless steel reaction kettle, heating the solution at 100 ℃ for reaction for 72 hours, cooling, centrifuging, washing, centrifuging and drying to obtain the porous crystalline material with the sodium chloride type structure constructed by zinc tetraoxide and vehicle-assisted secondary structural units. The material prepared in example 3 had an increased a channel size of about 0.6nm and an increased B channel size of about 0.6nm relative to example 1.
Example 4
Confirmation of the structure: the obtained porous crystalline material meets the single crystal test requirement, and the single crystal test result can directly confirm that the porous material is a sodium chloride type porous structure constructed by zinc tetraoxide and vehicle-auxiliary secondary structure units. The operation is as follows: selecting a single crystal, and deriving from SMART APEX CCD single crystal of BrukerPerforming measurement on an emission instrument by using Mo/Ka rays
Figure BDA0002021736440000074
And the ω scan mode collects diffraction data. The cell parameters and the orientation matrix are obtained by least square correction, the crystal structure is analyzed by a direct method or a Parteson method to obtain an initial structure, all non-hydrogen atom coordinates are obtained by least square correction and a difference Fourier method, the hydrogen atoms on the organic group are obtained by theoretical hydrogenation, and the hydrogen atoms on the water are determined by the difference Fourier method. And correcting by a full matrix least square method, and refining all non-hydrogen atoms by adopting anisotropic thermal parameters. Taking the structures numbered 1 in table 2 and 1 in table 3 as examples, the crystallographically determined molecular formulae are: C40H28O17N6Zn 6; the molecular weight is: 1257 g/mol; the crystal system is: square; the space group is: i4/m; unit cell size:
Figure BDA0002021736440000071
Figure BDA0002021736440000072
unit cell volume:
Figure BDA0002021736440000073
FIGS. 2-5 are four framework structures of the porous crystalline material of the present invention, showing the modulation of pore size and functional groups.
Example 5
Confirmation of thermal stability: taking the combination of number 1 in table 2 and number 1 in table 3 as an example, the thermal stability of the sodium chloride type porous crystalline material constructed by zinc tetraoxide and the vehicle-assisted secondary structure unit is implemented as follows: 10mg of fresh sample was weighed onto a thermal analyzer under nitrogen flow programmed from room temperature to 800 degrees Celsius and the weight loss during this process was recorded by the instrument. Similarly, 10mg of the activated sample was weighed out to obtain a weight loss map of the activated pore channel sample. The test results are the same as or similar to those of fig. 3, and the temperature deviation does not exceed 5 ℃. Similarly, the thermal stability of all samples can be confirmed by this method, and fig. 6 is a high thermal stability test result of the porous crystalline material.
Example 6
Confirmation of stability of ambient crystalline phase:
taking the combination of number 1 in table 2 and number 1 in table 3 as an example, a sodium chloride type porous crystalline material constructed by zinc tetraoxide and vehicle-assisted secondary structure units is prepared, and the examples of the stability of the environmental crystal phase are as follows: and weighing the activated sample, filling and compacting a sample groove of the powder diffraction instrument, and placing the sample groove on a test platform. Using a Bruker D8X-ray powder diffraction instrument as an example, the test conditions were as follows: copper target
Figure BDA0002021736440000081
The test voltage is 40Kv, the current is 40Ma, the 2 theta angle scanning range is 5-50 degrees, the scanning speed is 0.02 degree/second, and the step length is 0.02 degree. The obtained characteristic diffraction peaks include 2 theta 7.44 (main strong peak), 10.3,10.5, 12.7, 14.9, 16.7 and 18.2 degrees. And then, under the condition of ambient humidity, in-situ heating is carried out to 60 degrees, 90 degrees, 140 degrees and 200 degrees, scanning is carried out at the angle of 2 theta at 5-50 degrees respectively, and data are recorded. The test results are the same as or similar to those of fig. 3, and the 2 θ angle deviation does not exceed 0.2 degrees. Similarly, the environmental crystalline phase stability of all samples can be confirmed by this method, noteworthy: along with the increase and regulation of the pore channels, the 2 theta angle gradually deviates to a small angle, the deviation can be calculated according to a Bragg equation, and fig. 7 is an environmental thermal stability test result of the porous crystalline material.
Example 7
Confirmation of porosity of the sample after activation:
taking a sodium chloride type porous crystalline material constructed by zinc tetraoxide and a vehicle-auxiliary type secondary structure unit prepared by combining a number 1 in a table 2 and a number 1 in a table 3 as an example, the following examples are adopted: weighing 120mg of new sample, placing the new sample in a sample tube of an ASAP2020 adsorption apparatus of Mike company, heating at 200 ℃ in a degassing station, degassing and activating for 8 hours in vacuum, transferring to an analysis station, adopting N2 as a probe molecule, automatically completing the porosity test of the sample according to a default analysis program provided by the apparatus under the condition of 77K, wherein the BET specific surface area is 1213m2G, HK pore size of 0.6nm, different instrumentsThe test data of the device is the same as or similar to that of FIG. 3, and the deviation of the specific surface area is less than 100m2The deviation of the pore size is less than 0.2 nm. Notably: with the combination of tables 2 and 3, a significant difference in BET specific surface area and pore size was measured and was not expected, and fig. 8 is a result of porosity test of the porous crystalline material.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (5)

1. A porous crystalline material with a sodium chloride type is characterized in that a framework structure of the porous crystalline material simultaneously contains two secondary structure units of zinc tetraoxide and a vehicle-auxiliary type, and the two secondary structure units are alternately linked to form a sodium chloride type three-dimensional network structure;
the skeleton structure molecular general formula of the porous crystalline material is [ Zn ]6(O)(L1)4(L2)2]Wherein: l1 is a fully deprotonated linear diacid ligand, L2 is a fully deprotonated azole ligand of triangular coordination geometry, O is an oxyanion of the negative divalent state;
the zinc tetraoxide and the vehicle-auxiliary type two-stage structure units are alternately linked through L2 to form a one-dimensional chain, the one-dimensional chain is further linked with the zinc tetraoxide two-stage structure unit through one end of L1, the other end of the one-dimensional chain is linked with the vehicle-auxiliary type two-stage structure unit, and finally the two-dimensional chain is linked into the three-dimensional porous crystal material with the sodium chloride type structure;
l1 is completely deprotonated linear diacid ligand H2L, its molecular structural formula is
Figure FDA0002814411660000011
L2 is azole ligand H with completely deprotonated triangular coordination configuration1L, its molecular structural formula is
Figure FDA0002814411660000012
2. The porous crystalline material of claim 1, wherein the vehicle-auxiliary secondary structural unit is of a classical structural type, and wherein the zinc tetraoxide secondary structural unit has a structure in which 4 carboxyl groups occupy the equatorial plane and two azole groups occupy the axial positions.
3. The method for preparing a porous crystalline material having the sodium chloride form according to claim 1, wherein the zinc salt is mixed with an organic ligand H2L1、H1And carrying out solvothermal reaction on the L1 and an organic solvent at 100-180 ℃ for 8-72 hours, and cooling, filtering, washing and drying to obtain the porous crystalline material.
4. The method for preparing a porous crystalline material in the form of sodium chloride according to claim 3, wherein said zinc salt is associated with an organic ligand H2L1、H1The molar ratio of L1 is 2-4.5: 1.5-2: 1.
5. the method according to claim 3, wherein the zinc salt is selected from zinc nitrate, zinc sulfate, zinc acetate, zinc chloride or their aqueous crystalline salts, and the organic solvent is selected from one or two of nitrogen-containing dimethylformamide, nitrogen-containing diethylformamide, nitrogen-containing dimethylacetamide, dimethylsulfoxide or dimethylpyrrolidone.
CN201910281240.6A 2019-04-09 2019-04-09 Porous crystalline material with sodium chloride type and preparation method thereof Active CN110078751B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910281240.6A CN110078751B (en) 2019-04-09 2019-04-09 Porous crystalline material with sodium chloride type and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910281240.6A CN110078751B (en) 2019-04-09 2019-04-09 Porous crystalline material with sodium chloride type and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110078751A CN110078751A (en) 2019-08-02
CN110078751B true CN110078751B (en) 2021-04-02

Family

ID=67414693

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910281240.6A Active CN110078751B (en) 2019-04-09 2019-04-09 Porous crystalline material with sodium chloride type and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110078751B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113416316B (en) * 2021-06-28 2022-11-15 福建师范大学 MOFs-zinc material and preparation method and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102886249B (en) * 2012-10-15 2014-10-29 复旦大学 Self-assembled microporous material capable of selectively absorbing and separating methanol molecules and preparation method thereof
GB2514437A (en) * 2013-01-24 2014-11-26 Johnson Matthey Plc Method of manufacture
ES2856694T3 (en) * 2013-03-11 2021-09-28 Uti Lp Organometallic structure, production and use of it
CN103396424B (en) * 2013-07-02 2015-06-17 复旦大学 Micropore self-assembling material with structural deformation memory capability and preparation method thereof

Also Published As

Publication number Publication date
CN110078751A (en) 2019-08-02

Similar Documents

Publication Publication Date Title
Lee et al. Synthesis of metal-organic frameworks: A mini review
US20210260535A1 (en) Uio-66-nh2 doped organosilicon high salinity wastewater treatment membrane and a preparation method thereof
US9302258B2 (en) Complex comprising crystalline hybrid nanoporous material powder
Tari et al. One pot microwave synthesis of MCM-41/Cu based MOF composite with improved CO2 adsorption and selectivity
Kim et al. Pilot-scale synthesis of a zirconium-benzenedicarboxylate UiO-66 for CO2 adsorption and catalysis
US20090263621A1 (en) Porous organic-inorganic hybrid materials and adsorbent comprising the same
KR100982641B1 (en) Adsorbent including crystalline porous organic-inorganic hybrid materials
JP6808172B2 (en) Manufacturing method of adsorbent material
KR20070092592A (en) Adsorbent for water adsorption and desorption
CN108404868B (en) Based on doping of NH by alkali metal cations2-MIL-125(Ti) material and preparation method thereof
CN111100149A (en) Having a structure of C2H2And CH4Metal organic framework material with adsorption separation function and preparation method thereof
CN107286185A (en) A kind of cadmium metal organic framework material and preparation method thereof
EP3529252B1 (en) A crystalline metal organic framework
CN113087918B (en) Zirconium-based metal organic framework material and preparation method and application thereof
CN110078751B (en) Porous crystalline material with sodium chloride type and preparation method thereof
Nandigama et al. Rapid synthesis of mono/bimetallic (Zn/Co/Zn–Co) zeolitic imidazolate frameworks at room temperature and evolution of their CO 2 uptake capacity
CN111825849B (en) Metal-organic framework compound containing carbamido and preparation method thereof
CN112795023B (en) Ultra-stable metal organic framework material and preparation method and application thereof
CN109942833B (en) Three-dimensional porous metal zinc coordination polymer and preparation method and application thereof
CN109180956B (en) Preparation method of composite material of hydrophilic oligomer @ hydrophobic metal organic framework
CN110862549A (en) Three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine and preparation method thereof
KR101094075B1 (en) Novel organic­inorganic hybrid nano porous material and method for preparing thereof
CN114456337A (en) Preparation method of ionic porous organic cage material applied to radioactive iodine adsorption under high-temperature and low-concentration conditions
Yang et al. Vapor-assisted preparation of Mn/Fe/Co/Zn–Cu bimetallic metal–organic frameworks based on octahedron micron crystals (PCN-6′)
KR101082832B1 (en) Method for preparing organic-inorganic hybrid nano porous material, organic-inorganic hybrid nano porous materials obtained by said method and use as an absorbent

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