CN114870819B - 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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- 239000013118 MOF-74-type framework Substances 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 37
- 238000001308 synthesis method Methods 0.000 title description 5
- 239000002994 raw material Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- 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 21
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 229960002089 ferrous chloride Drugs 0.000 claims description 9
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012621 metal-organic framework Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 10
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 description 8
- 239000011148 porous material Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000013068 control sample Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000003421 catalytic decomposition reaction Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
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- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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]
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- 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
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- 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
- B01J20/02—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- 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
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for synthesizing Fe (II) -MOF-74 organic metal framework material with NO adsorption performance under the aerobic condition, which is applied to the NO adsorption field, and the improvement is mainly reflected in the increase of the NO adsorption capacity of the material. The Fe (II) -MOF-74 material with improved adsorption capacity can be finally obtained by changing the conditions and the raw material types and the proportion of synthesizing the Fe (II) -MOF-74 by a solvothermal method in an aerobic environment, and is suitable for adsorbing, separating, purifying and recycling the atmospheric pollutants NO.
Description
Technical Field
The invention discloses an improved method for synthesizing Fe (II) -MOF-74 material under the aerobic condition, which is applied to the field of NO adsorption, and the improvement is mainly reflected in the increase of the NO adsorption capacity of the material. The Fe (II) -MOF-74 material with improved adsorption capacity can be finally obtained by changing the conditions and the raw material types and the proportion of synthesizing the Fe (II) -MOF-74 by a solvothermal method in an aerobic environment, and the method is suitable for adsorbing, separating, purifying and recycling the atmospheric pollutants NO in the mixed gas.
Background
With the world population growth and technological progress, the atmosphere is more and more severely damaged, and nitrogen oxides (NO and NO) generated by automobile exhaust and industrial emissions 2 ) Becomes the main pollutant in the atmosphere. NOx can react with atmospheric water vapor to produce nitric acid or nitrous acid, so that acid rain is produced, various hazards (DOI: 10.1021/ie 9507179) are caused to water ecosystems, forest systems, agricultural systems, human health and the like, and ground ozone is produced by chemical reaction of NOx and volatile organic compounds under sunlight irradiation. Clearly, nitrogen oxides not only have a direct and significant impact on human health and the environment, but also create more by forming other air pollutantsIs responsible for acid rain, photochemical smog and greenhouse effect. Therefore, 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 higher consumption cost of the reducing agent, easy poisoning of the catalyst, low removal efficiency of low-concentration NOx, secondary pollution caused by leakage of the reducing agent, high required reaction temperature and the like, and the adsorption method has a larger development prospect in the aspect of gas adsorption separation in the flue gas. The NOx trapped by the adsorption method can directly adsorb high-concentration NOx, and then the NOx is released and utilized by a method such as temperature rising or pressure reducing. It also has many 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 catalytic decomposition process for NO removal. Compared with other adsorption materials, MOFs have high porosity (50-90% of free volume), large specific surface area (100-10400 m 2/g) (DOI: 10.1021/ja 2118255), and highly adjustable pore sizeThe advantages of (DOI: 10.1039/c2cc34047 j) and exposed active sites (DOI: 10.1021/ja 3055639) make it a more potential gas adsorbing material.
Among the many types of MOFs, MOF-74 materials have remarkable structural features of high density of open metal sites, hexagonal channels along the carbon axis, high porosity, and the like, are considered to be one of the most promising metal-organic frameworks, and many studies have also demonstrated that MOF-74 has a strong adsorption capacity for NO. For example Dietzel et al (DOI: 10.1021/cr 300014X) successfully synthesized MOFs materials of the M-CPO-27 series (Zn-CPO-27 is also known as MOF-74) centered at Co, ni, mg, mn, zn, fe and the like. Wherein the BET specific surface area of the Mg-CPO-27 can reach 1540m 2 Per g, porosity is as high as 63% (10.1002/adma. 201704303), and Co-CPO-27 and Ni-CPO-27 materials activated at 383K contain approximately 6.4mmol/g unsaturated metal sites (DOI: 10.1021/ja903726 m).
And for metal types in MOFs materials, fe has low application toxicity in the aspects of biological field, environmental field and the like, so that the metal can be used as a metal which has very potential and can be used for material synthesis. In addition, in view of the great influence of the metal sites on the NO adsorption capacity of the material, fe (II) has been shown to have a stronger binding effect on NO than the Fe (III) sites (DOI: 10.1063/1.4904069), so that the selection of Fe (II) as the metal site of the MOF-74 material further ensures the NO adsorption capacity of the material. However, the Fe (II) -MOF-74 material has only been reported to be synthesized under the anaerobic condition and has been characterized for the adsorption performance of NO (DOI: 10.1021/ja 5132243), while the rare synthesis under the aerobic condition has been reported to have poor adsorption performance of NO (DOI: 10.1166/jnn.2010.1493). Wherein, the synthesis conditions of the anaerobic environment increase the synthesis difficulty, and the valence state change in the aerobic environment is unstable, thereby limiting the application.
In view of this, the invention discloses an improved synthesis method of Fe (II) -MOF-74 materials with improved NO adsorption capacity in an aerobic environment, wherein the chemical components of the Fe (II) -MOF-74 materials are easy to control and the repeatability of the Fe (II) -MOF-74 materials is good.
Disclosure of Invention
The present invention aims to synthesize Fe (II) -MOF-74 material with improved adsorption capacity by an improved method in oxygen environment with easily controlled chemical composition and good repeatability.
The invention provides a synthesis method of Fe (II) -MOF-74 organic metal framework material with NO adsorption performance under the aerobic condition, which comprises the following steps:
(1) Ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O), 2, 5-dihydroxyterephthalic acid (DOBDC), ascorbic acid, N-Dimethylformamide (DMF), absolute ethyl alcohol and deionized water are mixed and put into a polytetrafluoroethylene liner of a reaction kettle, and stirred until the mixture is completely dissolved. Wherein DOBDC and FeCl 2 ·4H 2 The feeding mole ratio of O is 0.75-0.80:1, and the ascorbic acid and FeCl 2 ·4H 2 The molar ratio of O to DMF to FeCl is 0.48-0.67:1 2 ·4H 2 The molar ratio of O is 361.13-404.47:1, DMF/ethanol/deionized water (volume ratio) =15:1:1.
(2) Placing the liner filled with the mixed solution of the synthetic raw materials in the step (1) in a reverse directionSealing the kettle, then placing the kettle in an 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 ℃ for h -1 Is cooled to room temperature. The resulting solid was taken out, washed three times with DMF by ultrasonic wave, centrifuged to remove DMF, and then soaked in absolute ethanol for 3 days (ethanol was replaced every 12 hours) to remove residual unreacted material. Wherein the DMF usage per washing is: solid/DMF (volume ratio) =1:10; the ethanol amount for each soaking is as follows: solids/ethanol (vol) =1:10.
(3) And (3) centrifugally removing ethanol from the product obtained in the step (2), and then placing the product into a forced air drying box and drying the product at 100-120 ℃ for 6-8 hours in an air atmosphere to obtain a dark brown Fe (II) -MOF-74 product.
(4) And (3) 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 sample is green brown in color and is applied to an NO adsorption test.
The principle of the invention: the synthesis of the organometallic complex is affected by the metal to ligand feed ratio, metal ion concentration (i.e., solvent usage), synthesis temperature and crystallization time, and heating and cooling rates. The invention adjusts ferrous chloride tetrahydrate (FeCl) in the synthetic liquid by optimizing 2 ·4H 2 The ratio of O) to 2, 5-dihydroxyterephthalic acid (DOBDC) is increased, namely the dosage of DOBDC ligand is increased, the dosage of solvent DMF and ethanol aqueous solution is increased, namely the concentration of ferrous ions in the synthetic solution is reduced, the crystallization synthesis temperature is increased, the crystallization time is increased, more proper synthesis conditions of Fe (II) -MOF-74 complex rich in ferrous ions under aerobic conditions are found, and the synthetic product is applied to NO adsorption and has excellent adsorption performance.
Drawings
FIG. 1 shows a PXRD (powder X-ray diffraction pattern) of Fe-MOF-74 obtained in the example.
FIG. 2 is a graph showing the TG heat stability of Fe-MOF-74 obtained in the examples.
FIG. 3 is a graph comparing the isothermal adsorption curves of NO of Fe-MOF-74 obtained in the examples.
FIG. 4 shows N at 77K of Fe-MOF-74 obtained in the example 2 Isothermal adsorption profile.
FIG. 5 is an XPS analysis of the content of Fe ions in different valence states in Fe-MOF-74 obtained in the example.
Detailed Description
The present invention will be described in detail with reference to the following 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 level of divalent Fe.
(2) 0.3569g (1.79 mmol) of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O), 0.272g (1.37 mmol) of 2, 5-dihydroxyterephthalic acid (DOBDC), 0.1922g of ascorbic acid (1 mmol), 35mLN, N-Dimethylformamide (DMF), 3.5mL of ethanol and 3.5mL of deionized water were mixed into a 100mL polytetrafluoroethylene liner and stirred until the solids were completely dissolved. The inner container is placed in a reaction kettle to screw up a sealing cover, then is placed in an oven to react for 72 hours at a temperature rising rate of 2 ℃/min to 160 ℃, and then is reacted for 5 ℃ h -1 Is cooled to room temperature. The resulting material was removed and washed three times with 16mL of DMF under ultrasound. After centrifugation to remove DMF, ethanol was added for 3 days (ethanol was replaced every 12 hours) to remove residual unreacted material, each in an amount of 16mL. After centrifugation to remove ethanol, the product was dried in an air-atmosphere forced air drying oven at 200℃for 6 hours to give a dark brown Fe (II) -MOF-74 product.
(3) Placing the Fe-MOF-74 powder obtained in the step (2) into a vacuum drying oven, and activating for 8 hours at 200 ℃ to obtain the Fe (II) -MOF-74 material with open metal sites, wherein the color of a sample is green brown, and the identification of the sample is as follows: fe (II) -MOF-74-invention.
(4) Synthesis of control samples: the synthesis of the control sample was as described in Bhattacharjee et al (DOI: 10.1166/jnn.2010.1493). 0.4g (2 mmol) of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O), 0.2g (1 mmol) of 2, 5-dihydroxyterephthalic acid (DOBDC), 0.217g of ascorbic acid (1.13 mmol), 18.5mLN, N-Dimethylformamide (DMF), 1mL of isopropyl alcoholAlcohol and 1mL deionized water were mixed and added to a 100mL polytetrafluoroethylene liner and stirred until the solids were completely dissolved. The inner container is placed in a reaction kettle to be screwed with a sealing cover, then is placed in a drying oven to be heated to 105 ℃ at a heating rate of 2 ℃/min for reaction for 24 hours, and then is heated to 5 ℃ for h -1 Is cooled to room temperature. The resulting material was removed and washed three times with 16mL of DMF under ultrasound. The samples were centrifuged to remove DMF and then soaked with ethanol for 3 days (ethanol replacement every 12 hours) to remove residual unreacted material, 16mL each. After centrifugation to remove ethanol, the product was dried in an air-atmosphere forced air drying oven at 200℃for 6 hours to give a dark brown Fe (II) -MOF-74 product. The obtained powder was placed in a vacuum oven and activated at 200 ℃ for 8 hours, the activated sample was dark brown in color, and the sample mark was: fe (II) -MOF-74-control.
(5) Characterization of materials
The Fe (II) -MOF-74 material obtained in the steps (3) and (4) is prepared by X' Pert 3 The Powder type multifunctional X-ray diffractometer (Panake, netherlands) tests the crystal phase structure (PXRD), the American SDT-Q600 type synchronous TGA/DSC analyzer to characterize the heat stability, the physical adsorption instrument characterization isothermal adsorption curve of the SSA-7000 of Piaode electronic technology Co., ltd., the ESCALAB250XiX ray photoelectron spectrometer (XPS) to determine the content, the specific surface area and the pore size of Fe ions in different valence states in the product, and the results are respectively shown in the specification of figure 1, figure 2, figure 3, figure 4, figure 5 and table 1.
(6) Example results analysis
The crystalline phase structure (PXRD) of the MOF-74 material obtained by the synthesis of the examples, shown in 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 all the diffraction characteristic peaks are consistent with the characteristic peaks of the MOF-74 material, so that the material still has the MOF-74 framework structure characteristics.
FIG. 2 shows that the trend of the TG thermal stability weight loss curve of the Fe (II) -MOF-74-invention sample is basically consistent with that of the Fe (II) -MOF-74-control sample, and most of the weight loss at the temperature below 200 ℃ is attributed to removal of solvent molecules, and the samples are completely decomposed when the temperature is raised to 457 ℃.
FIG. 3 shows that the sample Fe (II) -MOF-74-of the invention has an adsorption capacity of 118cc/g for NO at 100KPa, which is about 87.3% higher than the adsorption capacity of 63cc/g for the reference synthetic sample Fe (II) -MOF-74-of the invention, and also shows stronger adsorption performance under low pressure conditions, which is about 400% higher.
FIG. 4 is N at 77K of Fe-MOF-74 obtained in the examples 2 Isothermal adsorption profile. N at 77K 2 The determination of the adsorption curve is used to characterize the BET specific surface area and pore volume data of the material. Table 1 shows the specific surface area and pore size comparison data of Fe-MOF-74 obtained in the examples, which indicate that the two have similar BET specific surface area and pore volume.
FIG. 5 shows XPS valence analysis results of samples obtained in examples. Divalent Fe of the sample obtained by the present invention 2+ Ion content is 82.95% compared with divalent Fe in the control sample 2+ The ion content (56.1%) was 26.85% higher. 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 divalent Fe in the product by improving the synthesis method of Fe (II) -MOF-74 metal organic framework material under the aerobic environment 2+ The ion content is obviously improved, the NO adsorption performance is obviously improved, the material with improved adsorption capacity is obtained, and the material has better purification and recycling application potential of atmospheric pollutant NO.
TABLE 1 specific surface area and pore size of Fe (II) -MOF-74-invention and Fe (II) -MOF-74-control
Claims (1)
- Fe (II) -MOF-74 metal organic framework material is used for adsorbing and separating NO gas, and the specific synthesis steps of Fe (II) -MOF-74 in an aerobic environment are as follows:(1) Mixing ferrous chloride tetrahydrate, 2, 5-dihydroxyterephthalic acid, ascorbic acid, N-dimethylformamide, absolute ethyl alcohol and deionized water, putting into a polytetrafluoroethylene liner of a reaction kettle, and stirring until the mixture is completely dissolved; wherein, the feeding mole ratio of the 2, 5-dihydroxyterephthalic acid to the ferrous chloride tetrahydrate is 0.75-0.80:1, the feeding mole ratio of the ascorbic acid to the ferrous chloride tetrahydrate is 0.48-0.67:1, the feeding mole ratio of the N, N-dimethylformamide to the ferrous chloride tetrahydrate is 361.13-404.47:1, and the volume ratio of the N, N-dimethylformamide to the ethanol to the deionized water is=15:1:1;(2) Sealing the inner container filled with the mixed solution of the synthetic raw materials in the step (1) in a reaction kettle, then placing the inner container in an oven, raising the temperature to 150-170 ℃ at a heating rate of 2 ℃/min, reacting for 72 hours in an air atmosphere, and then cooling to room temperature at a cooling rate of 5 ℃/hour; taking out the obtained solid phase product, ultrasonically washing the solid phase product with N, N-dimethylformamide for three times, centrifuging to remove the N, N-dimethylformamide, adding absolute ethyl alcohol, and soaking for 3 days to remove residual unreacted raw materials and solvents, wherein the absolute ethyl alcohol is replaced every 12 hours;(3) Centrifuging the product obtained in the step (2) to remove ethanol, and then placing the product into a blast drying oven and drying the product at 100-120 ℃ for 6-8 hours in an air atmosphere to obtain a dark brown Fe (II) -MOF-74 product;(4) The product obtained in the step (3) is activated in a vacuum drying oven at 200 ℃ to obtain a green-brown Fe (II) -MOF-74 product which is applied to an NO adsorption test.
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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 |
|---|
| Porous, rigid metal(III)-carboxylate metal-organic frameworks for the delivery of nitric oxide;Jarrod F. Eubank et al.;《APL Mater》;第2卷;文献号124112 * |
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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 |