CN116037078A - Novel multi-metal MOF material and preparation method and application thereof - Google Patents
Novel multi-metal MOF material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 95
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 66
- 239000002184 metal Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims description 6
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 60
- 239000013118 MOF-74-type framework Substances 0.000 claims abstract description 50
- 238000001179 sorption measurement Methods 0.000 claims abstract description 46
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 15
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 174
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 86
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 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 52
- 239000011259 mixed solution Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000003814 drug Substances 0.000 claims description 38
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 28
- 238000001291 vacuum drying Methods 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 229910001220 stainless steel Inorganic materials 0.000 claims description 24
- 239000010935 stainless steel Substances 0.000 claims description 24
- -1 alkali metal salt Chemical class 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000012467 final product Substances 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- 239000000376 reactant Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000967 suction filtration Methods 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- 230000002335 preservative effect Effects 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 66
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 16
- 239000001569 carbon dioxide Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 6
- 239000013246 bimetallic metal–organic framework Substances 0.000 abstract description 4
- 239000002841 Lewis acid Substances 0.000 abstract description 2
- 239000002585 base Substances 0.000 abstract description 2
- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 36
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 30
- 239000011734 sodium Substances 0.000 description 18
- 239000004317 sodium nitrate Substances 0.000 description 18
- 235000010344 sodium nitrate Nutrition 0.000 description 18
- 239000011777 magnesium Substances 0.000 description 17
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000004246 zinc acetate Substances 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000005431 greenhouse gas Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000009509 xiaoyin Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 241001251371 Betula chinensis Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000013114 Co-MOF-74 Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 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]
-
- 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
- B01D53/04—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 with stationary adsorbents
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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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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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
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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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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Abstract
The invention discloses a novel multi-metal MOF material, which comprises the components of M (I) x (nM) y-MOF-74, wherein M (I) is an alkali metal with a valence of I, M is an alkali metal with a valence of I, II or III, and n represents the type of the M metal. The invention has the advantages that: the metal I is added as a secondary metal site, so that the pore diameter structure of the MOF material can be regulated, and the specific surface area of the MOF material is increased; meanwhile, the components of the material have structural diversity due to the electrostatic effect of Lewis acid and metal ions; an aliovalent-state multi-metal MOF material formed by using an I-valent alkali metal as a secondary metal site is excellent in acid-base property and electrostatic effect on the material; therefore, the carbon dioxide adsorption performance is stronger, the optimal CO2 adsorption performance is as high as 8.5mmol/g under the dynamic adsorption condition, the performance is improved by nearly 15% on the basis of the MOF material Mg-MOF-74 with the optimal adsorption effect at present, and is nearly 10 times that of commercial activated carbon, and compared with a bimetallic MOF material taking II metal as a secondary metal site, the performance is more excellent.
Description
Technical Field
The invention relates to a novel multi-metal MOF material, a preparation method and application thereof, and belongs to the technical field of CO2 adsorption.
Background
With the continuous development of industrialization, global climate change is a major concern. In global climate change, the greenhouse effect belongs to a hot spot problem, and the occurrence of the greenhouse effect not only can cause the rising phenomenon of the global sea and land surfaces, but also can cause glaciers to melt, and the temperature of the seawater becomes high and the sea level rises. Research has shown that in the last decade, glacier melting speed is increased by many times compared with that of the previous glaciers, and the main factor of global temperature change caused by adverse effects on the environment is the occurrence of greenhouse gases (GHGs). Greenhouse gases commonly found include ozone, methane, CO2, fluoride, and the like. Among them, CO2 is a gas that has the greatest influence on global climate change, and compared with other gases, CO2 occupies more than sixty percent of the greenhouse effect caused by all greenhouse gases, and the residence time of CO2 gas in the air is also the longest. The main reason for the increase of the concentration of CO2 in the atmosphere is the use of fossil fuels, and the living standard of people is continuously improved, so that the consumption of energy sources by society is increasingly large, and the emission of CO2 is gradually increased. According to the data measured by the National Ocean and Atmospheric Administration (NOAA), the CO2 concentration in the atmosphere is currently rising sharply from 340ppm in 1980 to 420.99ppm in 2022.
To realize the sustainable development of economy, it is necessary to find a suitable CO2 capturing technology and CO2 adsorbent, that is, to find a novel efficient CO2 adsorbent with a large adsorption amount, which belongs to the hot spot problem.
The main low-temperature adsorbent materials at present mainly comprise carbonaceous adsorption materials, zeolite molecular sieves, metal Organic Frameworks (MOFs) and the like, and the main characteristics of the materials are that the materials can adsorb carbon dioxide at relatively low temperature (generally below 200 ℃). The carbonaceous adsorbing material is a porous carbonaceous material with a high specific surface area made of coal or organic matter. Comprises an adsorbent with pure carbon structures such as activated carbon, activated carbon fiber, carbon nano tube and the like. The active carbon is mainly prepared from high-carbon substances serving as raw materials through carbonization and activation, and has the characteristics of developed pore structure, large specific surface area, stable chemical property, acid and alkali resistance, strong selective adsorption capacity, easiness in regeneration after failure and the like. The activated carbon is a good potential adsorption material due to the microporous, mesoporous and macroporous structures. The carbon dioxide adsorption capacity of the modified activated carbon in the laboratory can reach 2-3mmol/g at present. While the carbon dioxide adsorption of unmodified commercial activated carbon was relatively low, only 0.89mmol/g. The zeolite molecular sieve is a hydrate of crystalline aluminosilicate containing alkali metal and alkaline earth metal oxide, is a microporous crystal material (pore size is 0.5-1.2 nm) with an open framework structure formed by connecting silicon-aluminum oxygen bridges, has selective absorption on a mixture of nitrogen and carbon dioxide, has stronger adsorption capacity on carbon dioxide, has good regeneration cycle adsorption performance, and can be used as an efficient and economic CO2 trapping adsorbent. Metal-organic frameworks (MOFs), which mainly refer to porous materials with specific network structures prepared by mixing inorganic Metal ions and organic ligands. Among materials used for MOFs materials, inorganic metal ions mainly serve as nodes formed by porous materials, and commonly used inorganic metal ions include transition metal species having low valence states, and commonly used alkali metals, other transition metals, and the like. The high specific surface area increases the carbon dioxide capturing capacity of MOFs compared to zeolite molecular sieves. Except that the maximum storage capacity of the zeolite is only one third of the MOFs at pressures less than 10 bar.
MOFs material has various unsaturated metal sites, so that MOFs can generate larger acting force with adsorbate in the adsorption process, and therefore, the MOFs material has better development prospect in the aspects of gas adsorption and separation. However, the carbon dioxide adsorption capacity of the existing MOF material is mainly 4-6mmol/g under the condition of normal temperature and normal pressure, and the material has poor stability and poor cycle performance.
So researchers modify MOFs materials to prepare MOF-74 materials, however, inorganic metal ions added in the preparation of the MOF-74 materials at present are mainly II-valence metal ions, such as Mg2+, ni2+, co2+, cu2+, zn2+ and the like. As in publication No. CN103992339a, liu Fu et al use magnesium nitrate hexahydrate to make Mg-MOF-74 materials. In publication No. CN105037444A, liu Ying et al use cobalt nitrate hexahydrate to produce pure phase rod-like Co-MOF-74 crystalline materials. In the aspect of MOF multi-metal synthesis, II metal element compounding is mainly adopted to modify a parent MOF material. The method is as follows: in the patent CN111393664a, jijun et al doped other valence II metals Cr, mn, co, ni, cu etc. in the iron source, which enables the metal active center to be 100% exposed, greatly improves the metal center utilization ratio, and is excellent in catalytic activity. In the patent with publication No. CN111848972A, luo Xubiao et al are based on MOF-808 synthesis conditions, and iron ions with different proportions are added into a Zr source to form an adsorption material through in-situ doping, so that the adsorption performance and stability of the material are improved. An Xiaoyin, lu Jinming, liu Yi, yang Jianhua, zhang Yan, zhang. Synthesis of bimetallic MOF-74 and gas adsorption separation Performance study of same [ J ]. Chemical novel material, 2020,48 (04): 185-190.DOI:10.19817/j.cnki. Issn1006-3536.2020.04.042, the bimetallic MOF material synthesized by the authors using II metals Co and Ni was Ni25Co-MOF-74, and the CO2 adsorption performance was 4.77mmol/g at normal temperature and pressure.
It can be seen that the performance of the material can be improved by introducing different secondary metal sites, but the research in the field of multi-metal MOF mainly comprises doping two II-valence metals, and the CO2 adsorption performance, stability and circularity are still to be improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel multi-metal MOF material and application thereof in CO2 adsorption, wherein the multi-metal MOF material is prepared by adopting a method of adding I-valent alkali metal as a secondary metal site, the method is convenient to operate, the I-valent alkali metal is low in price, and the prepared multi-metal MOF material is excellent in carbon dioxide adsorption performance, good in circularity and strong in stability.
The invention is realized by the following scheme: a novel multi-metal MOF material comprises the components of M (I) x (nM) y-MOF-74, wherein M (I) is an alkali metal with a valence of I, M is an alkali metal with a valence of II or III, n represents the type of M metal, x+y=1, x is more than 0, y is more than 0, and n is more than or equal to 1.
The preparation method of the novel multi-metal MOF material comprises the following steps:
firstly, respectively quantitatively weighing an I-valence alkali metal salt, one or more II-valence metal salts and 2, 5-dihydroxyterephthalic acid to prepare a medicine A;
step two, adding DMF, methanol and deionized water into the medicine A obtained in the step one to prepare a mixed solution A;
step three, placing the mixed solution A obtained in the step two on a magnetic stirrer to stir for a plurality of hours until the medicine is completely dissolved, and obtaining a mixed solution B;
transferring the mixed solution B obtained in the step three into a reaction kettle, then placing the reaction kettle into a constant-temperature drying box, performing hydrothermal reaction for 22-30 h at 110-140 ℃, and taking out the reaction kettle after the reaction kettle is cooled to room temperature;
and fifthly, removing the solution in the reaction kettle through suction filtration, putting the obtained product into a vacuum drying oven to be dried, placing a sample into a beaker, soaking the sample in methanol for 2-5 days at room temperature, continuously replacing the methanol for removing DMF and unreacted reactants, and drying the finally obtained product in the vacuum drying oven at 80-100 ℃ for 6-12 hours to obtain the final product M (I) x (nM) y-MOF-74 material.
The metal salt with valence I in the first step is alkali metal salt, and the metal salt with valence II and III is one of nitrate, chloride or acetate.
The molar ratio of the total amount of the metal salt to the 2, 5-dihydroxyterephthalic acid in the step one is 2-3: 0.78..
The volume ratio of DMF, methanol and deionized water added in the second step is V:V= (10-15): 1:1.
the volume ratio of the amount of the metal element substance to DMF in the second step is 2.5 mmol/61.5 mL.
And step three, the reaction kettle is a stainless steel water heating reaction kettle with a lining made of polytetrafluoroethylene.
And in the third step, the temperature of the solution in the magnetic stirring treatment process is not more than 40 ℃, the drying time in the vacuum drying oven in the fifth step is 4-6 h, in the fifth step, the beaker is sealed by using a preservative film in the process of soaking the sample in the methanol, and the number of times of replacing the methanol in the fifth step is 3.
An application of a novel multi-metal MOF material in CO2 adsorption.
The beneficial effects of the invention are as follows:
1. the invention discloses a novel multi-metal MOF material, which is characterized in that lithium nitrate, sodium nitrate and potassium nitrate are introduced as an I-valence metal source, magnesium nitrate, nickel nitrate, zinc nitrate, cobalt nitrate, copper nitrate, zinc acetate, zinc nitrate, and the like are respectively used as II-valence metal salts, and M (I) x (nM) y-MOF-74 crystal materials are successfully prepared and subjected to CO 2 The adsorption performance experimental test and partial characterization can be obtained through experimental results, and the multi-metal MOF material prepared by the invention has good CO 2 Adsorption Property, mg under experimental conditions of 298K,1bar 0.5 Na 0.5 CO of-MOF-74 2 The adsorption capacity is highest, 8.5mmol/g, which is nearly 10 times that of commercial activated carbon (0.89 mmol/g), and the cycle performance is stable.
2. According to the novel multi-metal MOF material, the I valence metal is added to serve as a secondary metal site, so that the aperture structure of the MOF material can be adjusted, and the specific surface area of the MOF material is increased; meanwhile, the components of the material have structural diversity due to the electrostatic effect of Lewis acid and metal ions; an aliovalent-state multi-metal MOF material formed by using an I-valent alkali metal as a secondary metal site is excellent in acid-base property and electrostatic effect on the material; therefore, the carbon dioxide adsorption performance is stronger, under the dynamic adsorption condition, the optimal CO2 adsorption performance is as high as 8.5mmol/g, the adsorption performance is improved by nearly 15% on the basis of the MOF material Mg-MOF-74 with the optimal adsorption effect at present, the adsorption performance is nearly 10 times that of commercial activated carbon, compared with a bimetallic MOF material taking II metal as a secondary metal site, the performance is more excellent, the bimetallic MOF material synthesized by II metal Co and Ni in the background art An Xiaoyin and the like is Ni25Co-MOF-74, the CO2 adsorption performance at normal temperature and normal pressure is 4.77mmol/g, and the adsorption performance is only 56% of Mg0.5Na0.5-MOF-74 in the application.
Drawings
FIG. 1 is a graph of CO2 adsorption breakthrough for M (I) x (nM) y-MOF-74 material.
FIG. 2 is an XRD pattern for an M (I) x (nM) y-MOF-74 material.
FIG. 3 is a graph of the cyclic stability performance of CO2 adsorption experiments for M (I) x (nM) y-MOF-74.
Detailed Description
The invention is further described in connection with fig. 1-3, but the scope of the invention is not limited to this.
In the following description, well-known functions and constructions are not described in detail for clarity of understanding, since they would obscure the invention with unnecessary detail, it is to be understood that in the development of any actual embodiment, numerous implementation details must be made to achieve the developer's specific goals, such as compliance with system-related or business-related constraints, that will vary from one embodiment to another, and that will be appreciated that such a development effort may be complex and time-consuming, but will be merely routine for one of ordinary skill in the art.
Example 1:
this example is a comparative example, a method of synthesizing a metal organic framework material Mg-MOF-74, by:
firstly, respectively weighing quantitative magnesium nitrate, sodium nitrate and 2, 5-dihydroxyterephthalic acid to prepare a medicine A; wherein, 10mmol of magnesium nitrate and 3.12mmol of 2, 5-dihydroxyterephthalic acid;
step two, adding a volume ratio of V to V=15 to the medicine A obtained in the step one: 1:1, DMF, methanol and deionized water to prepare a mixed solution A; wherein, the added DMF, methanol and deionized water are 246ml,16.4ml and 16.4ml respectively;
step three, placing the mixed solution A obtained in the step two on a magnetic stirrer to stir for a plurality of hours until the medicine is completely dissolved, and obtaining a mixed solution B;
transferring the mixed solution B obtained in the step three into a stainless steel water heating reaction kettle with a polytetrafluoroethylene lining, then placing the stainless steel water heating reaction kettle into a constant-temperature drying oven, performing hydrothermal reaction for 24 hours at 125 ℃, and taking out the reaction kettle after the reaction kettle is cooled to room temperature;
and fifthly, removing the solution in the reaction kettle through suction filtration, putting the obtained product into a vacuum drying oven to dry for a plurality of hours, placing a sample into a beaker, soaking the sample in methanol at room temperature for 3 days, continuously replacing the methanol for removing DMF and unreacted reactants during the period, and drying the finally obtained product in the vacuum drying oven at the temperature of 100 ℃ for 12 hours to obtain the final product, thereby obtaining the Mg-MOF-74 material.
Example 2:
the synthetic metal organic framework material Mg of the embodiment 0.5 Na 0.5 -MOF-74 by the steps of:
firstly, respectively weighing quantitative magnesium nitrate, sodium nitrate and 2, 5-dihydroxyterephthalic acid to prepare a medicine A; wherein, 5mmol of magnesium nitrate, 5mmol of sodium nitrate and 3.12mmol of 2, 5-dihydroxyterephthalic acid;
step two, adding a volume ratio of V to V=10 to the medicine A obtained in the step one: 1:1, DMF, methanol and deionized water to prepare a mixed solution A; wherein, the added DMF, methanol and deionized water are 246ml,16.4ml and 16.4ml respectively;
step three, placing the mixed solution A obtained in the step two on a magnetic stirrer to stir for a plurality of hours until the medicine is completely dissolved, and obtaining a mixed solution B;
transferring the mixed solution B obtained in the step three into a stainless steel water heating reaction kettle with a polytetrafluoroethylene lining, then placing the stainless steel water heating reaction kettle into a constant-temperature drying oven, performing hydrothermal reaction for 24 hours at 125 ℃, and taking out the reaction kettle after the reaction kettle is cooled to room temperature;
step five, removing the solution in the reaction kettle through suction filtration, putting the obtained product into a vacuum drying oven to dry for a plurality of hours, placing a sample into a beaker, soaking the sample in methanol at room temperature for 3 days, continuously replacing the methanol during the period for removing DMF and unreacted reactants, and drying the finally obtained product in the vacuum drying oven at the temperature of 100 ℃ for 12 hours to obtain the final product, thus obtaining Mg 0.5 Na 0.5 -MOF-74 material.
Example 3:
the synthetic metal organic framework material of the embodimentMg 0.5 Na 0.5 -MOF-74 by the steps of:
firstly, respectively weighing quantitative magnesium nitrate, sodium nitrate and 2, 5-dihydroxyterephthalic acid to prepare a medicine A; wherein, 5mmol of magnesium nitrate, 5mmol of sodium nitrate and 3.12mmol of 2, 5-dihydroxyterephthalic acid;
step two, adding a volume ratio of V to V=13: 1:1, DMF, methanol and deionized water to prepare a mixed solution A; wherein, the added DMF, methanol and deionized water are 246ml,16.4ml and 16.4ml respectively;
step three, placing the mixed solution A obtained in the step two on a magnetic stirrer to stir for a plurality of hours until the medicine is completely dissolved, and obtaining a mixed solution B;
transferring the mixed solution B obtained in the step three into a stainless steel water heating reaction kettle with a polytetrafluoroethylene lining, then placing the stainless steel water heating reaction kettle into a constant-temperature drying oven, performing hydrothermal reaction for 24 hours at 125 ℃, and taking out the reaction kettle after the reaction kettle is cooled to room temperature;
step five, removing the solution in the reaction kettle through suction filtration, putting the obtained product into a vacuum drying oven to dry for a plurality of hours, placing a sample into a beaker, soaking the sample in methanol at room temperature for 3 days, continuously replacing the methanol during the period for removing DMF and unreacted reactants, and drying the finally obtained product in the vacuum drying oven at the temperature of 100 ℃ for 12 hours to obtain the final product, thus obtaining Mg 0.5 Na 0.5 -MOF-74 material.
Example 4:
the synthetic metal organic framework material Mg of the embodiment 0.5 Na 0.5 -MOF-74 process by the steps of:
firstly, respectively weighing quantitative magnesium nitrate, sodium nitrate and 2, 5-dihydroxyterephthalic acid to prepare a medicine A; wherein, 5mmol of magnesium nitrate, 5mmol of sodium nitrate and 3.12mmol of 2, 5-dihydroxyterephthalic acid;
step two, adding a volume ratio of V to V=15 to the medicine A obtained in the step one: 1:1, DMF, methanol and deionized water to prepare a mixed solution A; wherein, the added DMF, methanol and deionized water are 246ml,16.4ml and 16.4ml respectively;
step three, placing the mixed solution A obtained in the step two on a magnetic stirrer to stir for a plurality of hours until the medicine is completely dissolved, and obtaining a mixed solution B;
transferring the mixed solution B obtained in the step three into a stainless steel water heating reaction kettle with a polytetrafluoroethylene lining, then placing the stainless steel water heating reaction kettle into a constant-temperature drying oven, performing hydrothermal reaction for 24 hours at 125 ℃, and taking out the reaction kettle after the reaction kettle is cooled to room temperature;
step five, removing the solution in the reaction kettle through suction filtration, putting the obtained product into a vacuum drying oven to dry for a plurality of hours, placing a sample into a beaker, soaking the sample in methanol at room temperature for 3 days, continuously replacing the methanol during the period for removing DMF and unreacted reactants, and drying the finally obtained product in the vacuum drying oven at the temperature of 100 ℃ for 12 hours to obtain the final product, thus obtaining Mg 0.5 Na 0.5 -MOF-74 material.
Example 5:
the synthetic metal organic framework material Mg of the embodiment 0.5 Li 0.5 -MOF-74 by the steps of:
firstly, respectively weighing quantitative magnesium nitrate, lithium nitrate and 2, 5-dihydroxyterephthalic acid to prepare a medicine A; wherein, 0.5mmol of magnesium nitrate, 0.5mmol of lithium nitrate and 3.12mmol of 2, 5-dihydroxyterephthalic acid;
step two, adding a volume ratio of V to V=15 to the medicine A obtained in the step one: 1:1, DMF, methanol and deionized water to prepare a mixed solution A; wherein, the added DMF, methanol and deionized water are 246ml,16.4ml and 16.4ml respectively;
step three, placing the mixed solution A obtained in the step two on a magnetic stirrer to stir for a plurality of hours until the medicine is completely dissolved, and obtaining a mixed solution B;
transferring the mixed solution B obtained in the step three into a stainless steel water heating reaction kettle with a polytetrafluoroethylene lining, then placing the stainless steel water heating reaction kettle into a constant-temperature drying oven, performing hydrothermal reaction for 24 hours at 125 ℃, and taking out the reaction kettle after the reaction kettle is cooled to room temperature;
step five, removing the solution in the reaction kettle through suction filtration, putting the obtained product into a vacuum drying oven to dry for a plurality of hours, placing a sample into a beaker, soaking the sample in methanol at room temperature for 3 days, continuously replacing the methanol during the period for removing DMF and unreacted reactants, and drying the finally obtained product in the vacuum drying oven at the temperature of 100 ℃ for 12 hours to obtain the final product, thus obtaining Mg 0.5 Li 0.5 -MOF-74 material.
Example 6:
the synthetic metal organic framework material Mg of the embodiment 0.9 K 0.1 -MOF-74 by the steps of:
firstly, respectively weighing quantitative magnesium nitrate, potassium nitrate and 2, 5-dihydroxyterephthalic acid to prepare a medicine A; wherein, 9mmol of magnesium nitrate, 1mmol of potassium nitrate and 3.12mmol of 2, 5-dihydroxyterephthalic acid;
step two, adding a volume ratio of V to V=15 to the medicine A obtained in the step one: 1:1, DMF, methanol and deionized water to prepare a mixed solution A; wherein, the added DMF, methanol and deionized water are 246ml,16.4ml and 16.4ml respectively;
step three, placing the mixed solution A obtained in the step two on a magnetic stirrer to stir for a plurality of hours until the medicine is completely dissolved, and obtaining a mixed solution B;
transferring the mixed solution B obtained in the step three into a stainless steel water heating reaction kettle with a polytetrafluoroethylene lining, then placing the stainless steel water heating reaction kettle into a constant-temperature drying oven, performing hydrothermal reaction for 24 hours at 125 ℃, and taking out the reaction kettle after the reaction kettle is cooled to room temperature;
step five, removing the solution in the reaction kettle through suction filtration, putting the obtained product into a vacuum drying oven to dry for a plurality of hours, placing a sample into a beaker, soaking the sample in methanol at room temperature for 3 days, continuously replacing the methanol during the period for removing DMF and unreacted reactants, and drying the finally obtained product in the vacuum drying oven at the temperature of 100 ℃ for 12 hours to obtain the final product, thus obtaining Mg 0.9 K 0.1 -MOF-74 material.
Example 7:
the synthetic metal organic framework material Ni of the embodiment 0.5 Na 0.5 -MOF-74 by the steps of:
firstly, respectively weighing quantitative nickel nitrate, sodium nitrate and 2, 5-dihydroxyterephthalic acid to prepare a medicine A; wherein, nickel nitrate 0.5mmol, sodium nitrate 5mmol,2, 5-dihydroxyterephthalic acid 3.12mmol;
step two, adding a volume ratio of V to V=15 to the medicine A obtained in the step one: 1:1, DMF, methanol and deionized water to prepare a mixed solution A; wherein, the added DMF, methanol and deionized water are 246ml,16.4ml and 16.4ml respectively;
step three, placing the mixed solution A obtained in the step two on a magnetic stirrer to stir for a plurality of hours until the medicine is completely dissolved, and obtaining a mixed solution B;
transferring the mixed solution B obtained in the step three into a stainless steel water heating reaction kettle with a polytetrafluoroethylene lining, then placing the stainless steel water heating reaction kettle into a constant-temperature drying oven, performing hydrothermal reaction for 24 hours at 125 ℃, and taking out the reaction kettle after the reaction kettle is cooled to room temperature;
step five, removing the solution in the reaction kettle through suction filtration, putting the obtained product into a vacuum drying oven to be dried for a plurality of hours, placing a sample into a beaker, soaking the sample in methanol at room temperature for 3 days, continuously replacing the methanol during the period for removing DMF and unreacted reactants, and drying the finally obtained product in the vacuum drying oven at the temperature of 100 ℃ for 12 hours to obtain the final product, thus obtaining Ni 0.5 Na 0.5 -MOF-74 material.
Example 8:
a synthetic metal organic framework material Zn of the present embodiment 0.5 Na 0.5 -MOF-74 by the steps of:
firstly, respectively weighing quantitative zinc acetate, sodium nitrate and 2, 5-dihydroxyterephthalic acid to prepare a medicine A; wherein, 5mmol of zinc acetate, 0.5mmol of sodium nitrate and 3.12mmol of 2, 5-dihydroxyterephthalic acid;
step two, adding a volume ratio of V to V=15 to the medicine A obtained in the step one: 1:1, DMF, methanol and deionized water to prepare a mixed solution A; wherein, the added DMF, methanol and deionized water are 246ml,16.4ml and 16.4ml respectively;
step three, placing the mixed solution A obtained in the step two on a magnetic stirrer to stir for a plurality of hours until the medicine is completely dissolved, and obtaining a mixed solution B;
transferring the mixed solution B obtained in the step three into a stainless steel water heating reaction kettle with a polytetrafluoroethylene lining, then placing the stainless steel water heating reaction kettle into a constant-temperature drying oven, performing hydrothermal reaction for 24 hours at 125 ℃, and taking out the reaction kettle after the reaction kettle is cooled to room temperature;
step five, removing the solution in the reaction kettle through suction filtration, putting the obtained product into a vacuum drying oven to dry for a plurality of hours, placing a sample into a beaker, soaking the sample in methanol at room temperature for 3 days, continuously replacing the methanol during the period for removing DMF and unreacted reactants, and drying the finally obtained product in the vacuum drying oven at the temperature of 100 ℃ for 12 hours to obtain the final product, thus obtaining Zn 0.5 Na0.5-MOF-74 material.
Example 9:
a synthetic metal organic framework material Ga of the present embodiment 0.5 Na 0.5 -MOF-74 by the steps of:
firstly, respectively weighing quantitative gallium nitrate, sodium nitrate and 2, 5-dihydroxyterephthalic acid to prepare a medicine A; wherein 5mmol of nitric acid is grafted, 0.5mmol of sodium nitrate and 3.12mmol of 2, 5-dihydroxyterephthalic acid are grafted;
step two, adding a volume ratio of V to V=15 to the medicine A obtained in the step one: 1:1, DMF, methanol and deionized water to prepare a mixed solution A; wherein, the added DMF, methanol and deionized water are 246ml,16.4ml and 16.4ml respectively;
step three, placing the mixed solution A obtained in the step two on a magnetic stirrer to stir for a plurality of hours until the medicine is completely dissolved, and obtaining a mixed solution B;
transferring the mixed solution B obtained in the step three into a stainless steel water heating reaction kettle with a polytetrafluoroethylene lining, then placing the stainless steel water heating reaction kettle into a constant-temperature drying oven, performing hydrothermal reaction for 24 hours at 125 ℃, and taking out the reaction kettle after the reaction kettle is cooled to room temperature;
step five, removing the solution in the reaction kettle through suction filtration, putting the obtained product into a vacuum drying oven to be dried for a plurality of hours, placing a sample into a beaker, soaking the sample in methanol at room temperature for 3 days, continuously replacing the methanol during the period for removing DMF and unreacted reactants, and drying the finally obtained product in the vacuum drying oven at the temperature of 100 ℃ for 12 hours to obtain the final product, thus obtaining Ga 0.5 Na0.5-MOF-74 material.
Example 10:
the composite metal organic framework material Mg of the embodiment 0.5 Ni 0.4 Na o.1 -MOF-74 by the steps of:
firstly, respectively weighing quantitative zinc acetate, sodium nitrate and 2, 5-dihydroxyterephthalic acid to prepare a medicine A; wherein, 5mmol of magnesium nitrate, 0.4mmol of nickel nitrate, 0.1mmol of sodium nitrate and 3.12mmol of 2, 5-dihydroxyterephthalic acid;
step two, adding a volume ratio of V to V=15 to the medicine A obtained in the step one: 1:1, DMF, methanol and deionized water to prepare a mixed solution A; wherein, the added DMF, methanol and deionized water are 246ml,16.4ml and 16.4ml respectively;
step three, placing the mixed solution A obtained in the step two on a magnetic stirrer to stir for a plurality of hours until the medicine is completely dissolved, and obtaining a mixed solution B;
transferring the mixed solution B obtained in the step three into a stainless steel water heating reaction kettle with a polytetrafluoroethylene lining, then placing the stainless steel water heating reaction kettle into a constant-temperature drying oven, performing hydrothermal reaction for 24 hours at 125 ℃, and taking out the reaction kettle after the reaction kettle is cooled to room temperature;
step five, removing the solution in the reaction kettle through suction filtration, putting the obtained product into a vacuum drying oven to dry for a plurality of hours, placing a sample into a beaker, soaking the sample in methanol at room temperature for 3 days, continuously replacing the methanol during the period for removing DMF and unreacted reactants, and drying the finally obtained product in the vacuum drying oven at the temperature of 100 ℃ for 12 hours to obtain the final product, thus obtaining Mg 0.5 Ni 0.4 Na o.1 -MOF-74 material.
Example 11:
the synthetic metal organic framework material Mg of the embodiment 0.5 Na 0.4 K o.1 -MOF-74 by the steps of:
firstly, respectively weighing quantitative zinc acetate, sodium nitrate and 2, 5-dihydroxyterephthalic acid to prepare a medicine A; wherein, 5mmol of magnesium nitrate, 0.4mmol of sodium nitrate, 0.1mmol of potassium nitrate and 3.12mmol of 2, 5-dihydroxyterephthalic acid;
step two, adding a volume ratio of V to V=15 to the medicine A obtained in the step one: 1:1, DMF, methanol and deionized water to prepare a mixed solution A; wherein, the added DMF, methanol and deionized water are 246ml,16.4ml and 16.4ml respectively;
step three, placing the mixed solution A obtained in the step two on a magnetic stirrer to stir for a plurality of hours until the medicine is completely dissolved, and obtaining a mixed solution B;
transferring the mixed solution B obtained in the step three into a stainless steel water heating reaction kettle with a polytetrafluoroethylene lining, then placing the stainless steel water heating reaction kettle into a constant-temperature drying oven, performing hydrothermal reaction for 24 hours at 125 ℃, and taking out the reaction kettle after the reaction kettle is cooled to room temperature;
step five, removing the solution in the reaction kettle through suction filtration, putting the obtained product into a vacuum drying oven to dry for a plurality of hours, placing a sample into a beaker, soaking the sample in methanol at room temperature for 3 days, continuously replacing the methanol during the period for removing DMF and unreacted reactants, and drying the finally obtained product in the vacuum drying oven at the temperature of 100 ℃ for 12 hours to obtain the final product, thus obtaining Mg 0.5 Na 0.4 K o.1 -MOF-74 material.
Mg prepared in examples 2 to 4 0.5 Na 0.5 CO-MOF-74 Material 2 The dynamic adsorption performance test shows that the volume ratio V is V:V= (10-15) in the second step: 1:1, DMF, methanol and deionized water can be successfully synthesized into MOF-74 material, and the CO2 adsorption performance is close, wherein the volume ratio is 15:1:1 DMF, methanol and deionized water, the synthesized material CO 2 Adsorption performance is the mostPreferably, but the solvent consumption is relatively high, the cost performance is slightly low, and the specific proportion can be determined by practical conditions.
CO treatment of the Multimetal MOF Material prepared in examples 4-11 2 The dynamic adsorption performance test results are shown in Table 1, in which Mg 0.5 Na 0.5 The highest adsorption performance of the-MOF-74 is 8.5mmol/g, compared with the prior CO 2 The monometal MOF material (Mg-MOF-74, 7.34 mmol/g) with the best adsorption performance is improved by nearly 15 percent, and then Mg is added 0.9 K 0.1 -MOF-74>Mg 0.5 Li 0.5 -MOF-74>Ni 0.9 Na 0.1 -MOF-74. The method is characterized in that I valence metals Li, na and K are added into Mg-MOF-74 as secondary metal sites, so that a rich three-dimensional honeycomb structure can be formed, the pore structure of the MOF material is regulated, and the number of micropores is increased, thereby enabling CO to be generated 2 The adsorption performance is obviously enhanced. According to the experiment of the circulation stability, the stability of the material is obviously improved by adding the valence I metal as a secondary metal site.
TABLE 1 summary of adsorption performance of Mg-MOF-74 and multimetal MOF CO2 after Synthesis
While the invention has been described and illustrated in considerable detail, it should be understood that modifications and equivalents to the above-described embodiments will become apparent to those skilled in the art, and that such modifications and improvements may be made without departing from the spirit of the invention.
Claims (10)
1. A novel multi-metal MOF material, characterized by: the component is M (I) x (nM) y-MOF-74, wherein M (I) is an alkali metal of valence I, M is an alkali metal of valence I or valence II or valence III, and n represents the type of M metal.
2. The novel multi-metal MOF material of claim 1, wherein: x+y=1, x > 0, y > 0, n > 1.
3. A preparation method of a novel multi-metal MOF material is characterized by comprising the following steps: the method comprises the following steps of:
firstly, quantitatively weighing an alkali metal salt I, one or more metal salts I, II or III and 2, 5-dihydroxyterephthalic acid respectively to prepare a medicine A;
step two, adding DMF, methanol and deionized water into the medicine A obtained in the step one to prepare a mixed solution A;
step three, placing the mixed solution A obtained in the step two on a magnetic stirrer to stir for a plurality of hours until the medicine is completely dissolved, and obtaining a mixed solution B;
transferring the mixed solution B obtained in the step three into a reaction kettle, then placing the reaction kettle into a constant-temperature drying box, performing hydrothermal reaction for 22-30 h at 110-140 ℃, and taking out the reaction kettle after the reaction kettle is cooled to room temperature;
and fifthly, removing the solution in the reaction kettle through suction filtration, putting the obtained product into a vacuum drying oven to be dried, placing a sample into a beaker, soaking the sample in methanol for 2-5 days at room temperature, continuously replacing the methanol for removing DMF and unreacted reactants, and drying the finally obtained product in the vacuum drying oven at 80-100 ℃ for 6-12 hours to obtain the final product M (I) x (nM) y-MOF-74 material.
4. The method for preparing the novel multi-metal MOF material according to claim 1, wherein the method comprises the following steps: the metal salt with valence I in the first step is alkali metal salt, and the metal salt with valence II and III is one of nitrate, chloride or acetate.
5. The method for preparing the novel multi-metal MOF material according to claim 1, wherein the method comprises the following steps: the molar ratio of the total amount of the metal salt to the 2, 5-dihydroxyterephthalic acid in the step one is 2-3: 0.78.
6. the method for preparing the novel multi-metal MOF material according to claim 1, wherein the method comprises the following steps: the volume ratio of DMF, methanol and deionized water added in the second step is V:V= (10-15): 1:1.
7. the method for preparing the novel multi-metal MOF material according to claim 1, wherein the method comprises the following steps: the volume ratio of the amount of the metal element substance to DMF in the second step is 2.5 mmol/61.5 mL.
8. The method for preparing the novel multi-metal MOF material according to claim 1, wherein the method comprises the following steps: and step three, the reaction kettle is a stainless steel water heating reaction kettle with a lining made of polytetrafluoroethylene.
9. The method for preparing the novel multi-metal MOF material according to claim 1, wherein the method comprises the following steps: and in the third step, the temperature of the solution in the magnetic stirring treatment process is not more than 40 ℃, the drying time in the vacuum drying oven in the fifth step is 4-6 h, in the fifth step, the beaker is sealed by using a preservative film in the process of soaking the sample in the methanol, and the number of times of replacing the methanol in the fifth step is 3.
10. An application of a novel multi-metal MOF material in CO2 adsorption.
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