CN114870819A - Aerobic atmosphere synthesis method of Fe (II) -MOF-74 material with NO adsorption performance - Google Patents
Aerobic atmosphere synthesis method of Fe (II) -MOF-74 material with NO adsorption performance Download PDFInfo
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 40
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- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 25
- 235000019441 ethanol Nutrition 0.000 claims description 19
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 15
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- 238000006243 chemical reaction Methods 0.000 claims description 12
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- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
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- 239000000126 substance Substances 0.000 claims description 4
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- 239000000523 sample Substances 0.000 description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
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- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- 125000002524 organometallic group Chemical group 0.000 description 1
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- 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]
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
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- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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Abstract
The invention discloses a method for synthesizing an Fe (II) -MOF-74 organic metal framework material with NO adsorption performance under an aerobic condition, which is applied to the field of NO adsorption. By changing the conditions for synthesizing Fe (II) -MOF-74 by a solvothermal method in an aerobic environment and the types and the proportions of raw materials, the Fe (II) -MOF-74 material with improved adsorption capacity can be finally obtained, and is suitable for adsorption, separation, purification and resource utilization of atmospheric pollutants NO.
Description
Technical Field
The invention discloses an improved method for synthesizing Fe (II) -MOF-74 material under aerobic condition, and is applied to the field of NO adsorption, and the improvement is mainly reflected in the increase of NO adsorption capacity of the material. By changing the conditions for synthesizing Fe (II) -MOF-74 by a solvothermal method in an aerobic environment and the types and the proportions of raw materials, the Fe (II) -MOF-74 material with improved adsorption capacity can be finally obtained, and is suitable for adsorption, separation, purification and resource utilization of atmospheric pollutants NO in mixed gas.
Background
With the growth of the world population and the advance of science and technology, the atmospheric layer is more and more seriously damaged, and the nitrogen oxides (NO and NO) generated by automobile exhaust and industrial emission 2 ) Becoming a major pollutant in the atmosphere. NOx can react with water vapor in the atmosphere to produce nitric acid or nitrous acid, and further produce acid rain, which causes various hazards to water ecological systems, forest systems, agricultural systems, human health and the like (DOI:10.1021/ie9507179), and ground ozone is also generated by chemical reaction of NOx and volatile organic compounds under the irradiation of sunlight. It is clear that nitrogen oxides not only have a direct and significant impact on human health and the environment, but also have more negative effects by forming other air pollutants, causing acid rain, photochemical smog and greenhouse effects. Therefore, the removal of nitrogen oxides has become one of the important environmental issues in the world today. At present, catalytic decomposition is the simplest and most effective method for removing the catalyst, but the catalytic decomposition method has the defects of high consumption cost of a reducing agent, easy poisoning of the catalyst, low efficiency of removing low-concentration NOx, secondary pollution caused by leakage of the reducing agent, high required reaction temperature and the like, so that the adsorption method has a greater development prospect in the aspect of gas adsorption and separation in flue gas. NOx can be directly adsorbed at a high concentration by trapping NOx by an adsorption method, and NOx is released and utilized by a method such as temperature rise or pressure reduction. It also has a number of advantages: such as less energy required for adsorbent regeneration, relatively simple adsorber design, less waste disposal problems, etc., and thus can be a promising alternative to the catalytic decomposition process for removing NO. Compared with other adsorbing materials, MOFs have high porosity (50-90% of free volume), large specific surface area (100-10400 m2/g) (DOI:10.1021/ja2118255) and highly adjustable and controllable hole size
(DOI:10.1039/c2cc34047j) and exposed active sites (DOI:10.1021/ja3055639) make it a more potential gas adsorbing material.
In many kindsOf the MOFs, MOF-74 materials have significant structural features such as high density of open metal sites, hexagonal channels along the carbon axis, and high porosity, and are considered as one of the most promising metal-organic frameworks, and many studies have also demonstrated that MOF-74 has strong adsorption capacity for NO. For example, Dietzel et al (DOI:10.1021/cr300014x) successfully synthesized M-CPO-27 series MOFs material (Zn-CPO-27 is also called MOF-74) with Co, Ni, Mg, Mn, Zn, Fe, etc. as central atoms. Wherein the BET specific surface area of Mg-CPO-27 can reach 1540m 2 The porosity is up to 63% (10.1002/adma.201704303), and the Co-CPO-27 and Ni-CPO-27 materials activated at 383K contain about 6.4mmol/g unsaturated metal sites (DOI:10.1021/ja903726 m).
For metal species in the MOFs, Fe has low application toxicity in the fields of biology, environment and the like, so that Fe can be used as a metal with high potential for material synthesis. In addition, considering that the metal sites have great influence on the NO adsorption capacity of the material, Fe (II) has been proved to have stronger binding effect on NO than Fe (III) sites (DOI:10.1063/1.4904069), so that the Fe (II) is selected as the metal sites of the MOF-74 material to further ensure the NO adsorption capacity of the material. However, currently, Fe (II) -MOF-74 materials are only reported and characterized in NO adsorption performance under anaerobic conditions (DOI:10.1021/ja5132243), while the few reports of synthesis under aerobic conditions are poor in NO adsorption performance (DOI: 10.1166/jnn.2010.1493). Wherein, the synthesis difficulty is increased by the synthesis condition of the anaerobic environment, and the valence state change under the aerobic environment is unstable, thereby limiting the application of the oxygen-free environment.
In view of the above, the invention discloses an improved synthesis method of Fe (II) -MOF-74 material with easily controllable chemical components and good repeatability and improved NO adsorption capacity in an aerobic environment.
Disclosure of Invention
The present invention is directed to the synthesis of fe (ii) -MOF-74 materials with improved adsorption capacity by an improved method in an oxygen environment with easily controllable chemical composition and good reproducibility.
The invention provides a method for synthesizing Fe (II) -MOF-74 organic metal framework material with NO adsorption property under aerobic condition, which comprises the following steps:
(1) ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O), 2, 5-dihydroxy terephthalic acid (DOBDC), ascorbic acid, N-Dimethylformamide (DMF), absolute ethyl alcohol and deionized water are mixed and put into a polytetrafluoroethylene inner container of a reaction kettle, and the mixture is stirred until the mixture is completely dissolved. Among them, DOBDC and FeCl 2 ·4H 2 The molar ratio of O to FeCl is 0.75-0.80: 1 2 ·4H 2 The feeding molar ratio of O is 0.48-0.67: 1, and DMF and FeCl 2 ·4H 2 The feeding molar ratio of O is 361.13-404.47: 1, and the volume ratio of DMF, ethanol and deionized water is 15:1: 1.
(2) Placing the liner filled with the synthetic raw material mixed solution in the step (1) in a reaction kettle for sealing, then placing the liner in a drying oven, raising the temperature to 150-170 ℃ at a heating rate of 2 ℃/min, reacting for 72 hours in an air atmosphere, and then reacting at 5 ℃ h -1 Is cooled to room temperature. The obtained solid is taken out and ultrasonically washed three times by DMF, and after the DMF is removed by centrifugation, absolute ethyl alcohol is added for soaking for 3 days (the ethyl alcohol is replaced every 12 hours) to remove residual unreacted materials. Wherein the amount of DMF used in each washing is: solid/DMF (volume ratio) 1: 10; the ethanol amount for each soaking is as follows: solids/ethanol (volume) 1: 10.
(3) And (3) centrifuging the product obtained in the step (2) to remove ethanol, and drying the product in an air drying oven at 100-120 ℃ for 6-8 hours in an air atmosphere to obtain a dark brown Fe (II) -MOF-74 product.
(4) And (4) heating the product obtained in the step (3) in a vacuum drying oven at 200 ℃ to obtain an activated material with open metal sites, wherein the color of the sample is dark brown, and the sample is applied to NO adsorption test.
The invention principle is as follows: the synthesis of the organometallic complex is influenced by the feeding proportion of the metal and the ligand, the concentration of metal ions (namely the dosage of the solvent), the synthesis temperature and crystallization time, the heating and cooling rates and the like. The invention optimizes and adjusts ferrous chloride tetrahydrate (FeCl) in the synthetic fluid 2 ·4H 2 O) to 2, 5-dihydroxyterephthalic acid (DOBDC), i.e., increasing the amount of DOBDC ligand, increasing the solvent DMF and ethanol aqueous solutionThe using amount of the Fe- (II) -MOF-74 complex is reduced, the concentration of ferrous ions in the synthetic liquid is reduced, the crystallization synthesis temperature is increased, the crystallization time is prolonged, the more appropriate synthesis conditions of the Fe- (II) -MOF-74 complex rich in ferrous ions under the aerobic condition are found, and the synthetic product is applied to NO adsorption and has excellent adsorption performance.
Drawings
FIG. 1 is a PXRD (powder X-ray diffraction pattern) of Fe-MOF-74 obtained in example.
FIG. 2 is a TG thermostability graph of Fe-MOF-74 obtained in example.
FIG. 3 is a comparison graph of the NO isothermal adsorption curves of Fe-MOF-74 obtained in the examples.
FIG. 4 is the N at 77K of the Fe-MOF-74 obtained in the example 2 Isothermal adsorption profile.
FIG. 5 is an XPS analysis of the content of Fe ions of different valences in Fe-MOF-74 obtained in the examples.
Detailed Description
The present invention will be described in detail below with reference to specific examples.
Example 1
(1) Raw materials
Ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) and 2, 5-dihydroxyterephthalic acid (DOBDC), absolute ethanol, ascorbic acid, N-Dimethylformamide (DMF), methanol, isopropanol are all analytically pure. The addition of ascorbic acid serves to reduce the oxidation degree of divalent Fe.
(2) 0.3569g (1.79mmol) of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O), 0.272g (1.37mmol)2, 5-dihydroxyterephthalic acid (DOBDC), 0.1922g ascorbic acid (1mmol), 35mL N, N-Dimethylformamide (DMF), 3.5mL ethanol, and 3.5mL deionized water were mixed into a 100mL polytetrafluoroethylene liner and stirred until the solids were completely dissolved. The liner is placed in a reaction kettle, a sealing cover is screwed, then the liner is placed in an oven to be heated to 160 ℃ at the heating rate of 2 ℃/min for reaction for 72 hours, and then the temperature is increased to 5 ℃ h -1 Is cooled to room temperature. The obtained product is taken out and added with DMF for ultrasonic washing three times, and the dosage is 16mL each time. After removing DMF by centrifugation, the mixture was soaked in ethanol for 3 days (ethanol was replaced every 12 hours) to remove the residual unreacted materials, and the amount of each time was 16 mL. Separation deviceAfter the ethanol was removed, the product was dried in a forced air oven at 200 ℃ for 6 hours to give a dark brown fe (ii) -MOF-74 product.
(3) Putting the Fe-MOF-74 powder obtained in the step (2) into a vacuum drying oven, and activating at 200 ℃ for 8 hours to obtain an Fe (II) -MOF-74 material with open metal sites, wherein the color of the sample is cyan-brown, and the sample is marked as follows: fe (II) -MOF-74-invention.
(4) Synthesis of control samples: the synthesis of the control samples was performed according to the study published by Bhattacharjee et al (DOI: 10.1166/jnn.2010.1493). 0.4g (2mmol) of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O), 0.2g (1mmol) of 2, 5-dihydroxyterephthalic acid (DOBDC), 0.217g of ascorbic acid (1.13mmol), 18.5mL of N, N-Dimethylformamide (DMF), 1mL of isopropanol, and 1mL of deionized water were mixed and added to a 100mL polytetrafluoroethylene liner and stirred until the solid was completely dissolved. The liner is placed in a reaction kettle, a sealing cover is screwed, then the liner is placed in a drying box, the temperature is raised to 105 ℃ at the heating rate of 2 ℃/min, the reaction is carried out for 24 hours, and then the temperature is raised to 5 ℃ h -1 Is cooled to room temperature. The obtained product is taken out and added with DMF for ultrasonic washing three times, and the dosage is 16mL each time. After removing DMF from the sample by centrifugation, the sample was soaked in ethanol for 3 days (ethanol was replaced every 12 hours) to remove the residual unreacted materials, and the amount of each time was 16 mL. After removing the ethanol by centrifugation, the product was dried in a forced air drying oven at 200 ℃ for 6 hours to obtain a dark brown fe (ii) -MOF-74 product. And (3) putting the obtained powder into a vacuum drying oven, activating for 8 hours at 200 ℃, wherein the color of the activated sample is dark brown, and the sample marks are as follows: fe (II) -MOF-74-control.
(5) Material characterization
Mixing the Fe (II) -MOF-74 material obtained in the steps (3) and (4) with X' Pert 3 A Powder type multifunctional X-ray diffractometer (Dutch Pasnake company) tests a crystalline phase structure (PXRD), an American SDT-Q600 type synchronous TGA/DSC analyzer characterizes thermal stability, a Peard electronic technology limited SSA-7000 physical adsorption instrument characterizes an isothermal adsorption curve, and an ESCALB 250XiX ray photoelectron spectrometer (XPS) measures the content, specific surface area and aperture size of Fe ions with different valence states in a product, and the results are respectively shown in the attached figure 1, the attached figure 2, the attached figure 3, the attached figure 4, the attached figure 5 and the table 1 of the specification.
(6) EXAMPLES analysis of results
The crystalline phase structure (PXRD) of the MOF-74 material synthesized from the examples FIG. 1 shows that the diffraction characteristic peaks of the Fe (II) -MOF-74-invention sample and the Fe (II) -MOF-74-control sample are consistent and are consistent with the characteristic peak of the MOF-74 material, and the material still has the MOF-74 framework structure characteristics.
FIG. 2 shows that the TG thermostable weight loss curves of the Fe (II) -MOF-74-invention sample and the Fe (II) -MOF-74-control sample have basically consistent trends, most weight loss below 200 ℃ is attributed to the removal of solvent molecules, and the sample is completely decomposed when the temperature is raised to 457 ℃.
FIG. 3 shows that the NO adsorption capacity of the Fe (II) -MOF-74-invention at 100KPa is 118cc/g, which is about 87.3% higher than that of the reference synthetic Fe (II) -MOF-74-control, and at the same time, the Fe (II) -MOF-74-control exhibits stronger adsorption performance under low pressure, which is about 400%.
FIG. 4 shows the N at 77K of the Fe-MOF-74 obtained in the example 2 Isothermal adsorption profile. N at 77K 2 The adsorption curve measurements were used to characterize the BET specific surface area versus pore volume data of the material. Table 1 shows the comparative data of specific surface area and pore size of Fe-MOF-74 obtained in the examples, which shows that the two have similar BET specific surface area and pore volume.
FIG. 5 shows the XPS valence state analysis of the sample obtained in the example. Divalent Fe of the samples obtained according to the invention 2+ The ion content was 82.95% compared to the divalent Fe in the control 2+ The ion content (56.1%) is higher than 26.85%. This should be the reason for the significant improvement in NO adsorption performance.
In conclusion, the results of the examples show that the invention synthesizes bivalent Fe in the product by improving the synthesis method of Fe (II) -MOF-74 metal organic framework material in aerobic environment 2+ The ion content is obviously improved, and the NO adsorption performance is obviously improved, which shows that the method has substantial obvious progress, and the obtained material with improved adsorption capacity has better purification and resource application potential of the atmospheric pollutant NO.
TABLE 1 specific surface area and pore size of Fe (II) -MOF-74-invention and Fe (II) -MOF-74-control
Claims (5)
1. A method for synthesizing Fe (II) -MOF-74 organic metal framework material with NO adsorption performance under aerobic condition is characterized in that divalent Fe in a synthetic product is improved remarkably by changing the conditions, raw material types and mixture ratio for synthesizing Fe (II) -MOF-74 by a solvothermal method under the aerobic environment 2+ The content of ions is improved, the stability is improved, the adsorption performance is improved when the ion is applied to NO gas adsorption, and the method mainly comprises the following steps:
(1) ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 Mixing O), 2, 5-dihydroxy terephthalic acid (DOBDC), ascorbic acid, N-Dimethylformamide (DMF), absolute ethyl alcohol and deionized water, putting the mixture into a polytetrafluoroethylene inner container of a reaction kettle, and stirring until the mixture is completely dissolved; among them, DOBDC and FeCl 2 ·4H 2 The molar ratio of O to FeCl is 0.75-0.80: 1 2 ·4H 2 The feeding molar ratio of O is 0.48-0.67: 1, and DMF and FeCl 2 ·4H 2 The feeding molar ratio of O is 361.13-404.47: 1, and the volume ratio of DMF to ethanol to deionized water is 15:1: 1;
(2) placing the liner filled with the synthetic raw material mixed solution in the step (1) in a reaction kettle for sealing, then placing the liner in a drying oven, raising the temperature to 150-170 ℃ at a heating rate of 2 ℃/min, reacting for 72 hours in an air atmosphere, and then reacting at 5 ℃ h -1 Cooling to room temperature; taking out the obtained solid, ultrasonically washing the solid for three times by using DMF (dimethyl formamide), centrifugally removing the DMF, adding absolute ethyl alcohol, soaking for 3 days to remove residual unreacted substances, and replacing the ethyl alcohol once every 12 hours; wherein the amount of DMF used in each washing is: the volume ratio of solid to DMF is 1: 10; the ethanol amount for each soaking is as follows: the volume ratio of the solid substance to the ethanol is 1: 10;
(3) centrifuging the product obtained in the step (2) to remove ethanol, and drying the product in an air drying oven at 100-120 ℃ for 6-8 hours in an air atmosphere to obtain a dark brown Fe (II) -MOF-74 product;
(4) and (4) heating the product obtained in the step (3) in a vacuum drying oven at 200 ℃ to obtain an activated material with open metal sites, wherein the color of the sample is dark brown, and the sample is applied to NO adsorption test.
2. The method of synthesis according to claim 1, characterized in that: with ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O), 2, 5-dihydroxyterephthalic acid (DOBDC), ascorbic acid, N-Dimethylformamide (DMF), absolute ethyl alcohol and deionized water.
3. The method of synthesis according to claim 1, characterized in that: DOBDC and FeCl 2 ·4H 2 The molar ratio of O to FeCl is 0.75-0.80: 1 2 ·4H 2 The feeding molar ratio of O is 0.48-0.67: 1, and DMF and FeCl 2 ·4H 2 The feeding molar ratio of O is 361.13-404.47: 1, and the volume ratio of DMF, ethanol and deionized water is 15:1: 1.
4. The method of synthesis according to claim 1, characterized in that: the crystallization reaction condition is that the reaction is carried out for 72 hours under the air atmosphere at the temperature of 150-170 ℃.
5. The method of synthesis according to claim 1, characterized in that: the synthesized product is applied to NO gas adsorption separation.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103402918A (en) * | 2011-01-18 | 2013-11-20 | 日本化学工业株式会社 | Fe(II) substituted beta type zeolite, gas adsorbent containing same and method for producing same, and method for removing nitric monoxide and hydrocarbon |
| CN104548904A (en) * | 2013-10-16 | 2015-04-29 | 北京化工大学 | Technology for liquid-phase complexing absorption of NO with iron-based chelate |
| JP2019193928A (en) * | 2018-04-13 | 2019-11-07 | 三菱ケミカル株式会社 | Nitrogen oxide adsorbent, and manufacturing method therefor |
| CN111187417A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Modification method and application of metal organic framework material |
| CN113797896A (en) * | 2021-10-09 | 2021-12-17 | 湖北中烟工业有限责任公司 | Preparation method of metal organic framework adsorbing material and adsorbing material obtained by same |
| CN114225910A (en) * | 2021-12-06 | 2022-03-25 | 桂林理工大学 | Aminated modified Co-MOFs material with NO adsorption separation performance |
-
2022
- 2022-05-17 CN CN202210531730.9A patent/CN114870819B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103402918A (en) * | 2011-01-18 | 2013-11-20 | 日本化学工业株式会社 | Fe(II) substituted beta type zeolite, gas adsorbent containing same and method for producing same, and method for removing nitric monoxide and hydrocarbon |
| CN104548904A (en) * | 2013-10-16 | 2015-04-29 | 北京化工大学 | Technology for liquid-phase complexing absorption of NO with iron-based chelate |
| JP2019193928A (en) * | 2018-04-13 | 2019-11-07 | 三菱ケミカル株式会社 | Nitrogen oxide adsorbent, and manufacturing method therefor |
| CN111187417A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Modification method and application of metal organic framework material |
| CN113797896A (en) * | 2021-10-09 | 2021-12-17 | 湖北中烟工业有限责任公司 | Preparation method of metal organic framework adsorbing material and adsorbing material obtained by same |
| CN114225910A (en) * | 2021-12-06 | 2022-03-25 | 桂林理工大学 | Aminated modified Co-MOFs material with NO adsorption separation performance |
Non-Patent Citations (1)
| Title |
|---|
| JARROD F. EUBANK ET AL.: "Porous, rigid metal(III)-carboxylate metal-organic frameworks for the delivery of nitric oxide", 《APL MATER》 * |
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Application publication date: 20220809 Assignee: Guilin Juge Project Management Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980044244 Denomination of invention: An aerobic atmosphere synthesis method for Fe (II) - MOF-74 material with NO adsorption performance Granted publication date: 20230811 License type: Common License Record date: 20231027 |
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Application publication date: 20220809 Assignee: GUANGXI GUOBO TECHNOLOGY Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980045084 Denomination of invention: An aerobic atmosphere synthesis method for Fe (II) - MOF-74 material with NO adsorption performance Granted publication date: 20230811 License type: Common License Record date: 20231030 Application publication date: 20220809 Assignee: Guangxi Jikuan Energy Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980045082 Denomination of invention: An aerobic atmosphere synthesis method for Fe (II) - MOF-74 material with NO adsorption performance Granted publication date: 20230811 License type: Common License Record date: 20231030 |