CN115678024A - Fluorosilicate MOF material and preparation method and application thereof - Google Patents
Fluorosilicate MOF material and preparation method and application thereof Download PDFInfo
- Publication number
- CN115678024A CN115678024A CN202211280111.3A CN202211280111A CN115678024A CN 115678024 A CN115678024 A CN 115678024A CN 202211280111 A CN202211280111 A CN 202211280111A CN 115678024 A CN115678024 A CN 115678024A
- Authority
- CN
- China
- Prior art keywords
- fluorosilicate
- sif
- tpyp
- hybrid material
- porous hybrid
- 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
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention relates to the technical field of industrial gas adsorption separation, and discloses a novel fluosilicate metal-organic framework material for separating acetylene carbon dioxide and a preparation method thereof 2+ Inorganic anion SiF 6 2‑ And organic ligand m-tetra (4-pyridyl) porphine under the condition of heating to obtain the compound with unit structure of Cu (TPyP) (SiF) 6 ) The microporous metal-organic framework material has relatively large specific surface area; the novel fluorosilicate MOF material has proper pore size and fluorinated functional sites, can enhance the recognition of acetylene through the action of hydrogen bonds, and can be used for C 2 H 2 /CO 2 The mixed gas is subjected to adsorption separation, and the separation selectivity is high, the adsorption capacity is large, and the separation performance is excellent.
Description
Technical Field
The invention relates to the technical field of industrial gas separation, in particular to a fluorosilicate porous hybrid material, a preparation method thereof and application thereof in gas adsorption separation.
Background
Acetylene is an important chemical raw material, which is a basic raw material for acetaldehyde, acetic acid, benzene, synthetic rubber and synthetic fiber, and generally needs to meet the requirement of high purity to achieve high yield and high safety. In industry, acetylene production is mainly derived from methane combustion and thermal hydrocarbon cracking, wherein carbon dioxide is a notable impurity, the presence of which reduces acetylene purity and negatively impacts subsequent utilization. Thus, in order to obtain acetylene of industrially required purity, it is necessary to remove the carbon dioxide impurities mixed therein. Most of the existing separation processes adopt energy-intensive solvent extraction and low-temperature distillation methods to separate acetylene and carbon dioxide mixtures, but because the boiling points of the acetylene and the carbon dioxide are very close (acetylene is 189.3K; carbon dioxide is 194.7K), the separation difficulty is high, and the methods are low in energy efficiency and environment-friendly. Therefore, it is necessary to develop a novel separation technique at normal temperature and pressure to efficiently separate acetylene and carbon dioxide.
In recent years, adsorbent-based separation technologies for gas separation and purification have attracted extensive attention in academia and industry, which has made it possible to shift future separation technologies from traditional energy-intensive cryogenic distillation to energy-efficient adsorbent separation processes. The adsorption separation is an energy-saving and high-efficiency separation technology, has the characteristics of low energy consumption, simple operation and the like, and can obtain higher separation selectivity. With the development of adsorption separation materials such as carbon materials, molecular sieves, porous polymers and the like, adsorption separation technology has made great progress in the field of gas separation.
Metal-organic framework materials are of widespread interest with their easily adjustable pore size/shape and internal surface modification. In the field of gas separation, metalsCompared with the traditional gas adsorbent, the organic framework has larger specific surface area, and can obtain separation performance meeting specific functions by adjusting the actions of the size, the configuration, the central metal cation and the like of the framework pore channel, thereby showing great potential in the fields of low-carbon hydrocarbon gas separation and purification. For example, SIFSIX-21-Cu prepared by Zaworkko et al [1] They layered the ligand 3,5-dimethyl-1H-pyrazol-4-yl methanol solution in the ethylene glycol solution of copper hexafluorosilicate, sealed and stood to obtain small blue/purple crystals, prepared with a material separation selectivity of 10, equivalent to the present invention, and having adsorption amounts of acetylene and carbon dioxide of 87.36cm, respectively 3 /g，33.6cm 3 /g(Kumar Naveen,Mukherjee Soumya,Harvey-Reid Nathan C.,Bezrukov Andrey A.,Tan Kui,Martins Vinicius,Vandichel Matthias,Pham Tony,van Wyk Lisa M.,Oyekan Kolade,Kumar Amrit,Forrest Katherine A.,Patil Komal M.,Barbour Leonard J.,Space Brian,Huang Yining,Kruger Paul E.,Zaworotko Michael J..Breaking the trade-off between selectivity and adsorption capacity for gas separation[J]Chem,2021,7 (11)). Hong Maochun et al, SIFSIX-tpa-Cu [2] The crystal culture method comprises dispersing methanol solution of tris (pyridin-4 yl) amine in copper hexafluorosilicate aqueous solution, standing at room temperature for 1 week, and separating to obtain dark purple block crystal, which is used for preparing material with high adsorption amount of two gases and acetylene content of 185cm 3 Per g, carbon dioxide 107cm 3 (ii)/g, but the IAST selectivity is only 5.3 (Li Hao, liu clipping, chen Cheng, di Zhengyi, yuan Daqiang, pang Jiandong, wei Wei, wu Mingyan, hong Maochun.an UndrenchedcedPillar-Cage fluorated Hybrid pores with high efficiency acetic acid Storage and Separation [ J Hao, liu clipping, chen Cheng, di Zhengyi, yuan Cheng, di Zhuangyi, yuan Daqiang, and Wei Wei, wu Mingyan, hong Maochun.an Undrected Pillar-Cage fluorated Hybrid pores with high efficiency acetic acid styrene Storage and Separation [ J].Angewandte Chemie International Edition,2021,60(14))。
Disclosure of Invention
The invention aims to overcome the traditional separation C 2 H 2 /CO 2 The method has the problems of high energy consumption and high cost, and provides a novel fluorosilicate MOF material which has large adsorption capacity and high separation selectivity at normal temperature and normal pressure.
In order to realize the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) 6 )]。
TPyP is meta-tetra (4-pyridyl) porphine.
In a second aspect, the present invention provides the above-mentioned fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) 6 )]The preparation method comprises the following steps:
uniformly dispersing m-tetra (4-pyridyl) porphine in an organic solvent to obtain a m-tetra (4-pyridyl) porphine solution; dissolving copper hexafluorosilicate in a solvent to obtain a copper hexafluorosilicate solution; dropwise adding the copper hexafluorosilicate solution into the m-tetra (4-pyridyl) porphine solution at 60-70 ℃ (preferably 70 ℃), reacting for 8-10h (preferably 10 h) after dropwise adding, and performing post-treatment on the obtained reaction solution to obtain the fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) 6 )]；
The mass ratio of the meta-tetrakis (4-pyridyl) porphine to copper hexafluorosilicate is 1.75-2.15 (preferably 1:2); the organic solvent is acetic acid or methanol (preferably acetic acid); the solvent is ethanol or water (preferably ethanol).
In the solvent and the organic solvent selected by the invention, the prepared fluorosilicate porous hybrid material has higher purity.
Further, the volume of the organic solvent is 30 to 50mL/mol (preferably 40 mL/mol) based on the amount of substance of m-tetrakis (4-pyridyl) porphine.
Further, the volume of the solvent is 10 to 20mL/mol (preferably 13 mL/mol) based on the amount of the substance of copper hexafluorosilicate.
Preferably, the dropping rate of the copper hexafluorosilicate solution is 0.05 to 0.2mL/s.
Specifically, the present invention recommends that both solutions be preheated at 60-70 deg.C (preferably 70 deg.C) before dropping the copper hexafluorosilicate solution into the meta-tetrakis (4-pyridyl) porphine solution. Generally, 50-60min is enough, and in the embodiment of the invention, the preheating time is 50min. The invention also recommends that the copper hexafluorosilicate solution is continuously shaken during the dropping process to prevent it from settling before dropping.
Further, the post-treatment is: standing the reaction solution at room temperature for one day, filtering, washing the obtained filter cake with absolute ethyl alcohol and absolute methyl alcohol in sequence (preferably washing for three times), and drying to obtain the fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) 6 )]。
In a third aspect, the invention also provides the above fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) 6 )]In separation C 2 H 2 /CO 2 Application in mixed gas.
The fluorosilicate MOF material is characterized in that the metal salt is copper hexafluorosilicate, the organic ligand is m-tetra (4-pyridyl) porphine, and the metal salt and the organic ligand are connected with C through an anion column and a porphyrin ligand due to proper pore size and fluorinated functional sites 2 H 2 Hydrogen bond and strong interaction are formed between the two components, so that the material enhances the recognition of acetylene and can be used for separating C 2 H 2 /CO 2 The mixed gas has high separation selectivity and high adsorption capacity, and is an excellent solid adsorbent with two characteristics.
Adsorption-based gas separation is an environmentally friendly and efficient separation technique, in which metal organic framework materials show a surprising prospect in the separation of industrial gases due to adjustable pore size, high specific surface area, easy functionalization, and the like. Because the novel fluorosilicate MOF material has proper pore size and fluorinated functional sites, the recognition of acetylene can be enhanced through the action of hydrogen bonds, and C is realized 2 H 2 /CO 2 Separating the mixed gas at normal temperature and normal pressure. The novel fluorosilicate MOF material is a material with excellent separation selectivity and acetylene adsorption capacity.
Compared with the prior art, the invention has the following beneficial effects:
(1) The metal salt used by the fluorosilicate porous hybrid material is copper hexafluorosilicate, the organic ligand is m-tetra (4-pyridyl) porphine, and the material is an anionic pillared metal organic framework material with a proper pore diameter and fluorinated functional sites;
(2) The fluorosilicate porous hybrid material of the invention has the advantages ofThe proper pore size and the fluorinated functional sites enhance the recognition of the material to acetylene through the hydrogen bond and strong interaction between the anion column and the porphyrin and the acetylene, so that the adsorption capacity of the acetylene is higher than that of carbon dioxide, and the material has the function of separating C 2 H 2 /CO 2 Mixed gas capacity, high separation selectivity, high adsorption capacity and high separation performance.
Drawings
FIG. 1 is an XRD pattern of the novel fluorosilicate MOF material prepared in example 1.
Figure 2 is a nitrogen adsorption desorption isotherm at 77K for the novel fluorosilicate MOF material prepared in example 1.
FIG. 3 is C of the novel fluorosilicate MOF material prepared in example 1 2 H 2 /CO 2 Adsorption profile.
FIG. 4 is fluorosilicate hybrid material prepared in example 1 at 296K for C 2 H 2/ CO 2 IAST selectivity profile of mixed gas.
FIG. 5 shows example 1 at 296K C 2 H 2 Gas adsorption isotherm data fitting graph
FIG. 6 is a 296K CO of example 1 2 Gas adsorption isotherm data fitting graph
Detailed Description
The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
0.075mmol,48mg of m-tetrakis (4-pyridyl) porphine was dispersed in 3mL of acetic acid with shaking, and was designated as solution A; 0.15mmol,32mg of copper hexafluorosilicate were dissolved in 2mL of ethanol and designated as solution B, and the solution A, B was simultaneously preheated in an oven at 70 ℃ for 50min. Slowly dropping the solution B into the solution A while shaking at 70 ℃, wherein the dropping rate is kept between 0.05 and 0.2mL/s. The mixed solution was kept in an oven at 70 ℃ for 10 hours, taken out and left at room temperature for one day. Filtering to obtain dark red powder after the reaction is finished, washing the powder with absolute ethyl alcohol and absolute methyl alcohol respectively for three times, and performing vacuum drying at 70 ℃ to obtain the novel fluorosilicate MOF material.
The purity was first verified by powder X-ray diffraction and, as shown in FIG. 1, [ Cu (TPyP) (SiF) is demonstrated by the XRD pattern of the novel fluorosilicate MOF material 6 )]The material is successfully prepared, the permanent porosity of the material is determined by measuring a nitrogen adsorption and desorption isotherm at 77K, and the specific surface area is 534.8m as shown in figure 2 2 The/g, 77K temperature was maintained by liquid nitrogen.
The gas separation capability of the fluorosilicate porous hybrid material prepared in this example was examined, and before the gas adsorption separation capability was examined, the guest solvent in the framework was removed by activation treatment: firstly, a newly synthesized novel fluorosilicate multi-MOF material product powder sample is subjected to solvent exchange with dry methanol for at least 8 times within two days, and then on a Micromeritics ASAP 2020 instrument, the temperature is raised to 65 ℃ at the temperature rise rate of 5 ℃ and vacuum pumping is carried out for 24 hours until the exhaust rate is 4mmHg/min before measurement.
The detected gas is C 2 H 2 And CO 2 The temperature is 296K, can carry out the stability through the low temperature constant temperature groove, and the pressure of test is 0 ~ 1bar, and gas and its purity that use includes: n is a radical of 2 (>99.999％)、He(99.999％)、C 2 H 2 (99.99％)、CO 2 (99.99％)。
The dry methanol used for the exchange was HPLC grade methanol produced by Alfa Aesar.
The gas adsorption test results are shown in fig. 3 and 4:
as shown in FIG. 3, the gas adsorption test was carried out using a Micromeritics ASAP 2020 full automatic adsorption apparatus, and the results showed that the adsorption amount of acetylene was as high as 92.1cm at 296K and 1bar 3 G, carbon dioxide adsorption capacity 77.9cm 3 /g。
As shown in FIG. 4, C was calculated at 296K, 1bar by IAST 2 H 2 /CO 2 The (50/50, v/v) IAST selectivity was 7. It follows that the novel fluorosilicate MOF materials have both gas adsorption capacity and gas adsorption capacityThe separation selectivity is excellent.
The gas adsorption selectivity IAST is calculated as follows:
the pure component isotherm data of acetylene and carbon dioxide were calculated by fitting using a two-site langmuir-frendeck isotherm model:
a saturation capacity of the gas component, C 1 And C 2 Is the Freund's constant, b 1 And b 2 Is Langmuir constant, dependent on temperature, C 1 、C 2 And b 1 、b 2 Obtained by Origin software fitting, p is pressure.
Pure gas adsorption equation parameters obtained based on the fitting define C 2 H 2 /CO 2 Ideal gas adsorption separation theory of separation (iatt) model:
x 1 and x 2 At a partial pressure of p 1 And p 2 Molar loading of lower adsorption phase in equilibrium with gas phase, S ads I.e. the IAST value, is obtained by Origin software calculation.
Example 2 (reaction temperature different from example 1)
0.0778mmol,48mg of meta-tetrakis (4-pyridyl) porphine was dispersed in 3mL of acetic acid, 0.1556mmol,32mg of copper hexafluorosilicate was dissolved in 2mL of ethanol at a ligand to salt molar ratio of 1:2, preheating for 50 minutes at 60 ℃ in an oven. And dropwise adding the salt solution into the ligand solution at 60 ℃, keeping the solution at 60 ℃ overnight, filtering and drying to obtain a dark red product. The desired material was successfully prepared at this temperature, but characterization showed that the material was not pure.
Example 3 (reaction ligand to salt ratio different from example 1)
0.0778mmol,48mg of meta-tetrakis (4-pyridyl) porphine was dispersed in 3mL of acetic acid, 0.0778mmol, 1695g of copper hexafluorosilicate was dissolved in 2mL of ethanol, the ligand to salt molar ratio was 1:1, preheating for 50 minutes in an oven at 70 ℃. And dropwise adding the salt solution into the ligand solution at 70 ℃, keeping the solution at 70 ℃ overnight, filtering and drying to obtain a dark red product. The product obtained in this ratio is not pure and there is incomplete reaction of the ligand.
Comparative example 1
0.25mmol,150mg of m-tetrakis (4-pyridyl) porphine and 2.5mmol,515mg of copper hexafluorosilicate were dissolved in 10mlN, N-dimethylformamide, and the mixed solution was placed in an oven at 120 ℃ to be heated and reacted for 2 days. Filtering to obtain mauve powder after the reaction is finished, washing with water and absolute methanol for three times respectively, drying in vacuum to obtain mauve product, and testing by XRD to not synthesize the required material.
Comparative example 2
0.25mmol and 150mg of m-tetrakis (4-pyridyl) porphine were dispersed and dissolved in 5mL of methanol, 0.5mmol and 103mg of copper hexafluorosilicate were dissolved in 5mL of water, and the two were mixed, heated under reflux at 65 ℃ for 12 hours, filtered, washed and dried to obtain the desired product.
Comparative example 3
0.25mmol and 150mg of m-tetrakis (4-pyridyl) porphine were dispersed in 8mL of chloroform, 0.25mmol and 51.5mg of copper hexafluorosilicate were dissolved in 2mL of methanol, and the two were mixed, and the mixed solution was heated under reflux at 65 ℃ for 12 hours, filtered, washed and dried to obtain the desired product.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. Fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) 6 )]。
2. The fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) of claim 1 6 )]The preparation method is characterized by comprising the following steps:
subjecting meta-tetra (4-pyridyl) porphineUniformly dispersing in an organic solvent to obtain a m-tetra (4-pyridyl) porphin solution; dissolving copper hexafluorosilicate in a solvent to obtain a copper hexafluorosilicate solution; dropwise adding the copper hexafluorosilicate solution into the m-tetra (4-pyridyl) porphine solution at 60-70 ℃, reacting for 8-10h after dropwise adding, and performing post-treatment on the obtained reaction liquid to obtain the fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) 6 )]；
The mass ratio of the meta-tetrakis (4-pyridyl) porphine to copper hexafluorosilicate is 1.75-2.15; the organic solvent is acetic acid or methanol; the solvent is ethanol or water.
3. The fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) of claim 2 6 )]The preparation method is characterized in that: the volume of the organic solvent is 30-50mL/mol based on the amount of substance of m-tetra (4-pyridyl) porphine.
4. The fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) of claim 2 6 )]The preparation method is characterized by comprising the following steps: the volume of the solvent is 10-20mL/mol based on the amount of the substance of the copper hexafluorosilicate.
5. The fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) of claim 2 6 )]The preparation method is characterized by comprising the following steps: the dropping speed of the copper hexafluorosilicate solution is 0.05-0.2mL/s.
6. The fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) of claim 2 6 )]The preparation method is characterized by comprising the following steps: the temperature of the reaction was 70 ℃.
7. The fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) of claim 2 6 )]The preparation method is characterized by comprising the following steps: the organic solvent is acetic acid.
8. The fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) of claim 2 6 )]Preparation ofThe method is characterized in that: the solvent is ethanol.
9. The post-treatment comprises the following steps: standing the reaction solution at room temperature for one day, filtering, washing the obtained filter cake with absolute ethyl alcohol and absolute methyl alcohol in sequence, and drying to obtain the fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) 6 )]。
10. The fluorosilicate porous hybrid material [ Cu (TPyP) (SiF) of claim 1 6 )]In separation C 2 H 2 /CO 2 Application in mixed gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211280111.3A CN115678024B (en) | 2022-10-19 | 2022-10-19 | Fluorosilicate MOF material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211280111.3A CN115678024B (en) | 2022-10-19 | 2022-10-19 | Fluorosilicate MOF material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115678024A true CN115678024A (en) | 2023-02-03 |
| CN115678024B CN115678024B (en) | 2023-07-25 |
Family
ID=85065593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211280111.3A Active CN115678024B (en) | 2022-10-19 | 2022-10-19 | Fluorosilicate MOF material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115678024B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116554492A (en) * | 2023-05-17 | 2023-08-08 | 浙江师范大学 | Ion hybridization hierarchical pore metal organic framework material with wly topological structure and preparation and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8324342B1 (en) * | 2007-06-13 | 2012-12-04 | Sandia Corporation | Porphyrin coordination polymer nanospheres and nanorods |
| US20170137450A1 (en) * | 2014-06-17 | 2017-05-18 | King Abdullah University Of Science And Technology | Green methods for preparing highly co2 selective and h2s tolerant metal organic frameworks |
| CN109678905A (en) * | 2018-12-22 | 2019-04-26 | 吉林大学 | It is a kind of to be coordinated the self-assembled supermolecular cage driven, preparation method and applications |
| CN111298771A (en) * | 2020-02-27 | 2020-06-19 | 浙江大学 | Layered fluorine-containing metal-organic framework material for adsorbing and separating acetylene and ethylene and preparation method and application thereof |
| CN112295550A (en) * | 2020-09-24 | 2021-02-02 | 浙江工业大学 | Fluorosilicate porous hybrid material, and preparation method and application thereof |
| CN112473625A (en) * | 2019-09-11 | 2021-03-12 | 杭州市富阳区浙工大银湖创新创业研究院 | Preparation method of ultra-microporous metal organic framework material for separating acetylene and ethylene |
| CN114230803A (en) * | 2020-09-09 | 2022-03-25 | 中国科学院宁波材料技术与工程研究所慈溪生物医学工程研究所 | Metal organic framework composite nano material and preparation method and application thereof |
-
2022
- 2022-10-19 CN CN202211280111.3A patent/CN115678024B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8324342B1 (en) * | 2007-06-13 | 2012-12-04 | Sandia Corporation | Porphyrin coordination polymer nanospheres and nanorods |
| US20170137450A1 (en) * | 2014-06-17 | 2017-05-18 | King Abdullah University Of Science And Technology | Green methods for preparing highly co2 selective and h2s tolerant metal organic frameworks |
| CN109678905A (en) * | 2018-12-22 | 2019-04-26 | 吉林大学 | It is a kind of to be coordinated the self-assembled supermolecular cage driven, preparation method and applications |
| CN112473625A (en) * | 2019-09-11 | 2021-03-12 | 杭州市富阳区浙工大银湖创新创业研究院 | Preparation method of ultra-microporous metal organic framework material for separating acetylene and ethylene |
| CN111298771A (en) * | 2020-02-27 | 2020-06-19 | 浙江大学 | Layered fluorine-containing metal-organic framework material for adsorbing and separating acetylene and ethylene and preparation method and application thereof |
| CN114230803A (en) * | 2020-09-09 | 2022-03-25 | 中国科学院宁波材料技术与工程研究所慈溪生物医学工程研究所 | Metal organic framework composite nano material and preparation method and application thereof |
| CN112295550A (en) * | 2020-09-24 | 2021-02-02 | 浙江工业大学 | Fluorosilicate porous hybrid material, and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116554492A (en) * | 2023-05-17 | 2023-08-08 | 浙江师范大学 | Ion hybridization hierarchical pore metal organic framework material with wly topological structure and preparation and application thereof |
| CN116554492B (en) * | 2023-05-17 | 2024-02-20 | 浙江师范大学 | Ion hybridization hierarchical pore metal organic framework material with wly topological structure and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115678024B (en) | 2023-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Guest-molecule-induced self-adaptive pore engineering facilitates purification of ethylene from ternary mixture | |
| CN110938213B (en) | Preparation method of copper-based microporous metal organic framework material and gas separation application thereof | |
| CN111362774B (en) | Application of ethoxy column [6] arene crystal material in selective adsorption of heterocyclic compound | |
| CN109776252B (en) | Propylene propane separation method | |
| CN107805260B (en) | Metal complex, adsorbing material, separating material, and method for separating 1, 3-butadiene | |
| CN112473625B (en) | Preparation method of ultra-microporous metal organic framework material for separating acetylene and ethylene | |
| CN113603897B (en) | Preparation of zinc-based metal organic framework material and selective adsorption application thereof | |
| CN113198423A (en) | Covalent organic framework material and preparation method and application thereof | |
| CN113019330A (en) | Preparation of copper-based metal-organic framework material and acetylene/carbon dioxide separation application thereof | |
| CN115678024A (en) | Fluorosilicate MOF material and preparation method and application thereof | |
| CN113087918A (en) | Zirconium-based metal organic framework material and preparation method and application thereof | |
| CN113817116A (en) | Preparation of covalent organic framework material and application of covalent organic framework material in rare earth separation | |
| CN112295550A (en) | Fluorosilicate porous hybrid material, and preparation method and application thereof | |
| CN114522668B (en) | Application of ethoxy column [6] arene crystal material in selective adsorption of tetrahydropyrrole | |
| CN115651203B (en) | Supramolecular crystal framework material based on BN coordination bond and preparation method and application thereof | |
| CN115505084B (en) | Covalent organic framework material, ligand and application | |
| US20060278077A1 (en) | Gas separation method using adsorbent | |
| CN114805187B (en) | Bipyridyl porous organic cage, covalent organic framework derived from cage and application | |
| CN114031788B (en) | Microporous zinc coordination polymer for propyne propylene separation and preparation method thereof | |
| CN106866985B (en) | A kind of metal-organic framework materials and preparation method thereof separated for acetylene and methane adsorption | |
| CN112898583A (en) | Preparation method and application of metal organic framework material | |
| CN113372525A (en) | Covalent organic framework material with molecular imprinting type and preparation method and application thereof | |
| CN115282941B (en) | Metal organic framework material and preparation method and application thereof | |
| JP4777153B2 (en) | Gas separation method and gas collection method | |
| CN112851593B (en) | Amino-bridged hexacarboxylic acid ligand, metal organic framework material, and preparation methods and applications thereof |
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 |