CN112387254A - Preparation method and application of coumarin modified metal organic framework hybrid material - Google Patents
Preparation method and application of coumarin modified metal organic framework hybrid material Download PDFInfo
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- CN112387254A CN112387254A CN202011062210.5A CN202011062210A CN112387254A CN 112387254 A CN112387254 A CN 112387254A CN 202011062210 A CN202011062210 A CN 202011062210A CN 112387254 A CN112387254 A CN 112387254A
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- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 225
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 151
- 229960000956 coumarin Drugs 0.000 title claims abstract description 113
- 235000001671 coumarin Nutrition 0.000 title claims abstract description 113
- 239000000463 material Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 claims abstract description 39
- 239000000295 fuel oil Substances 0.000 claims abstract description 27
- 238000003795 desorption Methods 0.000 claims abstract description 16
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 13
- 230000023556 desulfurization Effects 0.000 claims abstract description 13
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical compound S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006471 dimerization reaction Methods 0.000 claims abstract description 10
- 150000004775 coumarins Chemical class 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 102
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 72
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical group C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 16
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 239000013207 UiO-66 Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- 230000001678 irradiating effect Effects 0.000 claims description 9
- CJIJXIFQYOPWTF-UHFFFAOYSA-N 7-hydroxycoumarin Natural products O1C(=O)C=CC2=CC(O)=CC=C21 CJIJXIFQYOPWTF-UHFFFAOYSA-N 0.000 claims description 8
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000005070 sampling Methods 0.000 claims description 8
- 238000001308 synthesis method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000013132 MOF-5 Substances 0.000 claims description 6
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 6
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 6
- SFYBRCJPMDQKHA-UHFFFAOYSA-N zinc;dinitrate;tetrahydrate Chemical compound O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SFYBRCJPMDQKHA-UHFFFAOYSA-N 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- PQLQPCFUTCUMDL-UHFFFAOYSA-N CN(C=O)C.CC=1NC=CN1 Chemical compound CN(C=O)C.CC=1NC=CN1 PQLQPCFUTCUMDL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000005595 deprotonation Effects 0.000 claims description 2
- 238000010537 deprotonation reaction Methods 0.000 claims description 2
- 230000003009 desulfurizing effect Effects 0.000 claims description 2
- -1 coumarin compound Chemical class 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 238000007142 ring opening reaction Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 abstract 1
- 239000000539 dimer Substances 0.000 abstract 1
- 238000002715 modification method Methods 0.000 abstract 1
- 238000007699 photoisomerization reaction Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 74
- 229930192474 thiophene Natural products 0.000 description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 238000002791 soaking Methods 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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Images
Classifications
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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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention discloses a preparation method and application of a coumarin modified metal organic framework hybrid material, and is based on a post-synthesis modification method, a deprotonated coumarin molecule is coordinated with an unsaturated metal site of a metal organic framework, wherein the mass ratio of the coumarin molecule to the metal organic framework is 0.1-1: 1. Coumarin has excellent photoisomerization property, can perform dimerization reaction under the irradiation of long-wave ultraviolet light with the wavelength of more than 310nm, and the generated dimer increases the specific surface area and the pore volume of the material, and has more developed micropores, thereby being beneficial to the adsorption of thiophene sulfide; after irradiation of 254nm short-wave ultraviolet light, the coumarin dimer is subjected to ring-opening cracking to form a monomer, the pore structure is recovered, and efficient desorption of thiophene sulfide is realized. The coumarin modified metal organic framework hybrid material has good application in the field of adsorption desulfurization of fuel oil.
Description
Technical Field
The invention belongs to the technical field of preparation of metal organic framework hybrid materials, and particularly relates to a preparation method and application of coumarin modified metal organic framework hybrid materials.
Background
Thiophene sulfides are widely present in fuel oils and the combustion of these substances produces sulfur-containing compounds that can cause severe corrosion of equipment and serious environmental pollution. As the desulfurization standards for fuel oils become more stringent, the removal of thiophenic sulfides from fuel oils has become a key point in the production of low sulfur fuels. Hydrodesulfurization is a common method for fuel oil desulfurization, can effectively remove thioether, disulfide and the like in fuel oil, but is difficult to remove thiophene sulfide, and adsorption separation technology is considered to be one of the most promising desulfurization technologies due to the advantages of mild reaction, simple and convenient process, low cost and the like.
The metal organic framework is a novel inorganic-organic hybrid material (MOF material), which is mainly formed by the hybridization of a polydentate organic ligand of nitrogen and oxygen of aromatic acid or alkali and an inorganic metal center through coordination bonds. In addition, the metal organic framework contains a large number of unsaturated metal sites, and can generate strong interaction with thiophene sulfides, so that the thiophene sulfides in the fuel oil can be selectively adsorbed. However, the pore structure and properties of the traditional porous material cannot be regulated, and although the traditional porous material has good adsorption capacity, the traditional porous material is difficult to form effective desorption on adsorbates, so that the practical application of adsorption desulfurization is severely limited.
Disclosure of Invention
In order to solve the existing problems, the invention provides a preparation method of a coumarin modified metal organic framework hybrid material.
The invention is realized by the following technical scheme.
A preparation method of a coumarin modified metal organic framework hybrid material comprises the following operation steps:
(1) preparing a metal organic framework;
(2) deprotonating the coumarin molecule;
(3) respectively dissolving a metal organic framework and deprotonated coumarin molecules in a solvent, stirring, heating and refluxing, filtering, washing, drying, and grafting the coumarin molecules to the metal organic framework to obtain a coumarin molecule grafted metal organic framework;
(4) and (3) irradiating the coumarin molecules with long-wave ultraviolet light with the wavelength of more than 310nm to graft the metal-organic framework, so that the coumarin molecules in the metal-organic framework are subjected to dimerization reaction, and the coumarin modified metal-organic framework hybrid material is obtained.
Specifically, in the step (1), the metal organic framework material comprises one or more of a metal organic framework material HKUST-1, a metal organic framework material UiO-66, a metal organic framework material MOF-5 and a metal organic framework material ZIF-8.
Specifically, the synthesis method of the metal organic framework HKUST-1 comprises the following steps: copper nitrate trihydrate and trimesic acid are used as raw materials, solvents are N, N-dimethylformamide, absolute ethyl alcohol and water, the reaction temperature is 80-120 ℃, the reaction time is 8-16 hours, then the raw materials are cooled to room temperature, filtered, soaked in methanol and methane for 24 hours respectively, and dried at room temperature, and the product is HKUST-1; wherein the molar ratio of the copper nitrate trihydrate, the trimesic acid, the N, N-dimethylformamide, the absolute ethyl alcohol and the water is 1: 0.5-2: 20-50: 15-80: 80-200.
The synthesis method of the metal organic framework UiO-66 comprises the following steps: zirconium tetrachloride and terephthalic acid are used as raw materials, N-dimethylformamide and acetic acid are used as solvents, the reaction temperature is 100-220 ℃, the reaction time is 10-24 hours, then the mixture is cooled to room temperature, filtered, washed for 4 times by using the N, N-dimethylformamide and methanol respectively, and dried, and the product is UiO-66; wherein the molar ratio of zirconium tetrachloride to terephthalic acid to N, N-dimethylformamide to acetic acid is 1: 1-1.5: 1000-1800: 200-800.
The synthesis method of the metal organic framework MOF-5 comprises the following steps: zinc nitrate hexahydrate and terephthalic acid are used as raw materials, a solvent is N, N-dimethylformamide, the reaction temperature is 70-150 ℃, the reaction time is 10-30 hours, then the mixture is cooled to room temperature, filtered, washed for 3 times by using the N, N-dimethylformamide, and the product is MOF-5; wherein the molar ratio of the zinc nitrate tetrahydrate, the terephthalic acid and the N, N-dimethylformamide is 1: 0.25-1: 100-300.
The synthesis method of the metal organic framework ZIF-8 comprises the following steps: zinc nitrate tetrahydrate and 2-methylimidazole are used as raw materials, N-dimethylformamide is used as a solvent, the reaction temperature is 100-180 ℃, the reaction time is 18-36 hours, the mixture is cooled to room temperature, then the mixture is filtered, and the product is ZIF-8 after being washed for 3 times by using the N, N-dimethylformamide; wherein the molar ratio of the zinc nitrate tetrahydrate to the 2-methylimidazole N, N-dimethylformamide is 1: 0.5-1.5: 200-400.
Specifically, in the step (2), the coumarin molecule is 7-hydroxycoumarin.
Specifically, in the step (2), the deprotonation process of the coumarin is as follows: dissolving coumarin molecules and sodium methoxide in methanol, and heating and refluxing, wherein the heating and refluxing reaction temperature is 50-80 ℃, and the reaction time is 2-10 h.
Specifically, in the step (3), the mass ratio of the deprotonated coumarin molecule to the metal organic framework is (0.1-1): 1.
Specifically, in the step (3), the solvent is methanol.
Specifically, in the step (3), the reaction temperature of the heating reflux reaction is 50-80 ℃, and the reaction time is 8-20 h.
The invention also provides an application of the coumarin modified metal organic framework hybrid material prepared by the method, and the coumarin modified metal organic framework hybrid material is applied to fuel oil adsorption desulfurization, wherein sulfur in the fuel oil is thiophene sulfide.
Specifically, the specific process for desulfurizing the fuel oil comprises the following steps: adding 2-10g of coumarin modified metal organic framework hybrid material into per liter of fuel oil, stirring uniformly, and sampling once every 30-50min until adsorption balance.
According to the technical scheme, the beneficial effects of the invention are as follows:
according to the invention, coumarin molecules are introduced into the metal organic framework, and the coumarin molecules are subjected to dimerization reaction under the irradiation of long-wave ultraviolet light with the wavelength of more than 310nm, so that the specific surface area and the pore volume of the metal organic framework hybrid material are increased, and meanwhile, the microporous structure of the metal organic framework hybrid material is developed, and the metal organic framework hybrid material is favorable for adsorbing thiophene sulfides; under the irradiation of 254nm short-wave ultraviolet light, the coumarin dimer is subjected to ring-opening pyrolysis to form a coumarin monomer, the specific surface area, the pore volume and the number of micropores are reduced, thiophene molecules form high-efficiency desorption, and the metal-organic framework hybrid material can be adsorbed again for use. The metal organic framework hybrid material prepared by the invention breaks through the limitation that the structure of the traditional porous material is not adjustable and has good regeneration performance.
Drawings
FIG. 1 is a schematic diagram of coumarin dimer formation and ring-opening cleavage reactions on a metal-organic framework.
FIG. 2 is a scanning electron microscope image of a coumarin modified metal organic framework hybrid material prepared in example 4 of the present invention;
FIG. 3 shows N before and after irradiation of 330nm long-wave ultraviolet light on the coumarin modified metal-organic framework hybrid material prepared in example 4 of the present invention2Adsorption-desorption isotherms;
FIG. 4 is a distribution diagram of the aperture of the hybrid material with coumarin modified metal-organic frameworks, which is prepared by the method of embodiment 4, before and after irradiation by ultraviolet light with a long wave of 330 nm;
fig. 5 shows the ultraviolet-visible diffuse reflection spectrum of the coumarin modified metal organic framework hybrid material prepared in example 4 of the present invention after irradiation with 330nm long-wave ultraviolet light at different times.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Preparation of metal organic framework HKUST-1: 2.077g of copper nitrate trihydrate was dissolved in 15mL of deionized water, and 1.0g of trimesic acid was dissolved in 15mL of a mixed solution of ethanol and 15mL of N, N-Dimethylformamide (DMF). Mixing the two solutions, and reacting at 100 ℃ for 10 hours. Cooling to room temperature, removing supernatant, adding methanol solution, soaking for 24 hr, removing supernatant again, adding methane, soaking for 24 hr, and drying at room temperature to obtain HKUST-1.
Preparing a coumarin modified metal organic framework hybrid material: 0.171g of 7-hydroxycoumarin was weighed out and dissolved in 30mL of methanol, and 0.0648g of sodium methoxide was added and the mixture was refluxed at 67 ℃ for 3 hours to obtain deprotonated 7-hydroxycoumarin. Then weighing 0.684g of metal organic framework HKUST-1, dissolving in 3mL of 67 ℃ methanol, continuously adding deprotonated 7-hydroxycoumarin, reacting for 8h at 67 ℃, filtering, washing and drying to obtain a coumarin molecule grafted metal organic framework; and (3) irradiating the coumarin molecules with long-wave ultraviolet light with the wavelength of 320nm to graft the metal-organic framework, so that the coumarin molecules in the metal-organic framework are subjected to dimerization reaction, and the coumarin modified metal-organic framework hybrid material is obtained.
Application experiments: the adsorption desulfurization performance of the coumarin modified metal organic framework hybrid material is determined by a static method (the following examples are all determined by the method). Weighing 2mg of the coumarin modified metal organic framework hybrid material, dispersing in a 2mL fuel oil model (the initial thiophene content is 476 ppm), and sampling once at intervals until the adsorption is balanced. Detecting the content of the residual thiophene in the fuel oil by a gas chromatograph, filtering out the coumarin modified metal organic framework hybrid material after reaching the adsorption balance, drying, placing in a methanol/toluene mixed solution for desorption, standing after ultrasonic treatment, and detecting the content of the thiophene in the solution by the gas chromatograph.
And (3) test results: the equilibrium adsorption capacity of the coumarin molecule grafted metal organic framework on thiophene is 0.83mmol S/g, after the coumarin molecule grafted metal organic framework is irradiated by 320nm long-wave ultraviolet light, the equilibrium adsorption capacity on thiophene is increased to 0.91mmol S/g, and the increment is 9%; after irradiation of 254nm short-wave ultraviolet light, the desorption amount of thiophene is 73%, and the coumarin molecule grafted metal organic framework can be recycled.
Example 2
Preparation of metal organic framework HKUST-1: 2.077g of copper nitrate trihydrate was dissolved in 15mL of deionized water, and 1.0g of trimesic acid was dissolved in 15mL of a mixed solution of ethanol and 15mL of N, N-Dimethylformamide (DMF). Mixing the two solutions, and reacting at 100 ℃ for 10 hours. Cooling to room temperature, removing supernatant, adding methanol solution, soaking for 24 hr, removing supernatant again, adding methane, soaking for 24 hr, and drying at room temperature to obtain HKUST-1.
Preparing a coumarin modified metal organic framework hybrid material: 0.342g of 7-hydroxycoumarin is weighed out and dissolved in 30mL of methanol, 0.0648g of sodium methoxide is added, and the mixture is refluxed at 67 ℃ for 3h to obtain deprotonated 7-hydroxycoumarin. Then weighing 0.684g of metal organic framework HKUST-1, dissolving in 3mL of 67 ℃ methanol, adding deprotonated 7-hydroxycoumarin, reacting at 67 ℃ for 8h, filtering, washing and drying to obtain a coumarin molecule grafted metal organic framework; and irradiating the coumarin molecules with long-wave ultraviolet light with the wavelength of 330nm to graft the metal-organic framework, so that the coumarin molecules in the metal-organic framework are subjected to dimerization reaction, and the coumarin modified metal-organic framework hybrid material is obtained.
Application experiments: and (3) determining the adsorption desulfurization performance of the coumarin modified metal organic framework hybrid material by adopting a static method. Weighing 2mg of the coumarin modified metal organic framework hybrid material, dispersing in a 2mL fuel oil model (the initial thiophene content is 476 ppm), and sampling once at intervals until the adsorption is balanced. Detecting the content of the residual thiophene in the fuel oil by a gas chromatograph, filtering out the hybrid material and drying after reaching the adsorption balance, placing the hybrid material in a methanol/toluene mixed solution for desorption, standing after ultrasonic treatment, and detecting the content of the thiophene in the solution by the gas chromatograph.
And (3) test results: the equilibrium adsorption capacity of the coumarin molecule grafted metal organic framework on thiophene is 0.69mmol S/g, after the coumarin molecule grafted metal organic framework is irradiated by ultraviolet light with the wavelength of 330nm, the equilibrium adsorption capacity on thiophene is increased to 0.85mmol S/g, and the increment is 9%; after irradiation of 254nm short-wave ultraviolet light, the desorption amount of thiophene is 77%, and the coumarin molecule grafted metal organic framework can be recycled.
Example 3
Preparation of metal organic framework HKUST-1: 2.077g of copper nitrate trihydrate was dissolved in 15mL of deionized water, and 1.0g of trimesic acid was dissolved in 15mL of a mixed solution of ethanol and 15mL of N, N-Dimethylformamide (DMF). Mixing the two solutions, and reacting at 100 ℃ for 10 hours. Cooling to room temperature, removing supernatant, adding methanol solution, soaking for 24 hr, removing supernatant again, adding methane, soaking for 24 hr, and drying at room temperature to obtain HKUST-1.
Preparing a coumarin modified metal organic framework hybrid material: 0.513g of 7-hydroxycoumarin is weighed out and dissolved in 30mL of methanol, 0.0648g of sodium methoxide is added, and the mixture is refluxed at 67 ℃ for 3h to obtain deprotonated 7-hydroxycoumarin. Then weighing 0.684g of metal organic framework HKUST-1, dissolving in 3mL of 67 ℃ methanol, adding deprotonated 7-hydroxycoumarin, reacting at 67 ℃ for 8h, filtering, washing and drying to obtain a coumarin molecule grafted metal organic framework; and irradiating the coumarin molecules with long-wave ultraviolet light with the wavelength of 330nm to graft the metal-organic framework, so that the coumarin molecules in the metal-organic framework are subjected to dimerization reaction, and the coumarin modified metal-organic framework hybrid material is obtained.
Application experiments: and (3) determining the adsorption desulfurization performance of the coumarin modified metal organic framework hybrid material by adopting a static method. Weighing 2mg of the coumarin modified metal organic framework hybrid material, dispersing in a 2mL fuel oil model (the initial thiophene content is 476 ppm), and sampling once at intervals until the adsorption is balanced. Detecting the content of the residual thiophene in the fuel oil by a gas chromatograph, filtering out the hybrid material and drying after reaching the adsorption balance, placing the hybrid material in a methanol/toluene mixed solution for desorption, standing after ultrasonic treatment, and detecting the content of the thiophene in the solution by the gas chromatograph.
And (3) test results: the equilibrium adsorption capacity of the coumarin molecule grafted metal organic framework on thiophene is 0.53mmol S/g, after the coumarin molecule grafted metal organic framework is subjected to 340nm long-wave ultraviolet irradiation, the equilibrium adsorption capacity on thiophene is increased to 0.70mmol S/g, and the increment is 32%; after irradiation of 254nm short-wave ultraviolet light, the desorption amount of thiophene is 59%, and the coumarin molecule grafted metal organic framework can be recycled.
Example 4
Preparation of metal organic framework HKUST-1: 2.077g of copper nitrate trihydrate was dissolved in 15mL of deionized water, and 1.0g of trimesic acid was dissolved in 15mL of a mixed solution of ethanol and 15mL of N, N-Dimethylformamide (DMF). Mixing the two solutions, and reacting at 100 ℃ for 10 hours. Cooling to room temperature, removing supernatant, adding methanol solution, soaking for 24 hr, removing supernatant again, adding methane, soaking for 24 hr, and drying at room temperature to obtain HKUST-1.
Preparing a coumarin modified metal organic framework hybrid material: 0.684g of 7-hydroxycoumarin are weighed out and dissolved in 30mL of methanol, 0.0648g of sodium methoxide are added, and the mixture is refluxed at 67 ℃ for 3h to obtain deprotonated 7-hydroxycoumarin. Then weighing 0.684g of metal organic framework HKUST-1, dissolving in 3mL of 67 ℃ methanol, adding deprotonated 7-hydroxycoumarin, reacting at 67 ℃ for 8h, filtering, washing and drying to obtain a coumarin molecule grafted metal organic framework; and irradiating the coumarin molecules with long-wave ultraviolet light with the wavelength of 330nm to graft the metal-organic framework, so that the coumarin molecules in the metal-organic framework are subjected to dimerization reaction, and the coumarin modified metal-organic framework hybrid material is obtained.
Application experiments: and (3) determining the adsorption desulfurization performance of the coumarin modified metal organic framework hybrid material by adopting a static method. Weighing 2mg of the coumarin modified metal organic framework hybrid material, dispersing in a 2mL fuel oil model (the initial thiophene content is 476 ppm), and sampling once at intervals until the adsorption is balanced. Detecting the content of the residual thiophene in the fuel oil by a gas chromatograph, filtering out the hybrid material and drying after reaching the adsorption balance, placing the hybrid material in a methanol/toluene mixed solution for desorption, standing after ultrasonic treatment, and detecting the content of the thiophene in the solution by the gas chromatograph.
And (3) test results: the equilibrium adsorption capacity of the coumarin molecule grafted metal organic framework on thiophene is 0.41mmol S/g, after the coumarin molecule grafted metal organic framework is subjected to 340nm long-wave ultraviolet irradiation, the equilibrium adsorption capacity on thiophene is increased to 0.59mmol S/g, and the increment is 44%; after irradiation of 254nm short-wave ultraviolet light, the desorption amount of thiophene is 80%, and the coumarin molecule grafted metal organic framework can be recycled.
Example 5
Preparation of the metal organic framework UiO-66: 0.1165g of zirconium tetrachloride and 0.0830g of terephthalic acid are weighed and dissolved in 51.05mL of N, N-dimethylformamide, then 11.45mL of acetic acid is added, the mixture is stirred and dissolved, the reaction is carried out for 16h at 120 ℃, the temperature is cooled to room temperature, the centrifugation is carried out, the washing is carried out for 4 times by using 25mL of DMMF, then the washing is carried out for 4 times by using methanol, and the drying is carried out, thus obtaining the metal organic framework UiO-66.
Preparing a coumarin modified metal organic framework hybrid material: 0.342g of 7-hydroxycoumarin is weighed out and dissolved in 30mL of methanol, 0.0648g of sodium methoxide is added, and the mixture is refluxed at 67 ℃ for 3h to obtain deprotonated 7-hydroxycoumarin. Then, 0.684g of metal organic framework UiO-66 is weighed and dissolved in 3mL of methanol at 67 ℃, deprotonated 7-hydroxycoumarin is added into the methanol, the mixture reacts for 8 hours at 67 ℃, and the metal organic framework grafted by coumarin molecules is obtained after filtration, washing and drying; and irradiating the coumarin molecules with long-wave ultraviolet light with the wavelength of 330nm to graft the metal-organic framework, so that the coumarin molecules in the metal-organic framework are subjected to dimerization reaction, and the coumarin modified metal-organic framework hybrid material is obtained.
Application experiments: and (3) determining the adsorption desulfurization performance of the coumarin modified metal organic framework hybrid material by adopting a static method. Weighing 2mg of the coumarin modified metal organic framework hybrid material, dispersing in a 2mL fuel oil model (the initial thiophene content is 476 ppm), and sampling once at intervals until the adsorption is balanced. Detecting the content of the residual thiophene in the fuel oil by a gas chromatograph, filtering out the hybrid material and drying after reaching the adsorption balance, placing the hybrid material in a methanol/toluene mixed solution for desorption, standing after ultrasonic treatment, and detecting the content of the thiophene in the solution by the gas chromatograph.
And (3) test results: the equilibrium adsorption capacity of the coumarin molecule grafted metal organic framework on thiophene is 0.53mmol S/g, after the coumarin molecule grafted metal organic framework is subjected to 340nm long-wave ultraviolet irradiation, the equilibrium adsorption capacity on thiophene is increased to 0.66mmol S/g, and the increment is 25%; after irradiation of 254nm short-wave ultraviolet light, the desorption amount of thiophene is 62%, and the coumarin molecule grafted metal organic framework can be recycled.
Example 6
Preparation of the metal organic framework UiO-66: 0.1165g of zirconium tetrachloride and 0.0830g of terephthalic acid are weighed and dissolved in 51.05mL of N, N-dimethylformamide, then 11.45mL of acetic acid is added, the mixture is stirred and dissolved, the reaction is carried out for 16h at 120 ℃, the temperature is cooled to room temperature, the centrifugation is carried out, the washing is carried out for 4 times by using 25mL of DMMF, then the washing is carried out for 4 times by using methanol, and the drying is carried out, thus obtaining the metal organic framework UiO-66.
Preparing a coumarin modified metal organic framework hybrid material: 0.684g of 7-hydroxycoumarin are weighed out and dissolved in 30mL of methanol, 0.0648g of sodium methoxide are added, and the mixture is refluxed at 67 ℃ for 3h to obtain deprotonated 7-hydroxycoumarin. Then, 0.684g of metal organic framework UiO-66 is weighed and dissolved in 3mL of methanol at 67 ℃, deprotonated 7-hydroxycoumarin is added into the methanol, the mixture reacts for 8 hours at 67 ℃, and the metal organic framework grafted by coumarin molecules is obtained after filtration, washing and drying; and irradiating the coumarin molecules with long-wave ultraviolet light with the wavelength of 330nm to graft the metal-organic framework, so that the coumarin molecules in the metal-organic framework are subjected to dimerization reaction, and the coumarin modified metal-organic framework hybrid material is obtained.
Application experiments: and (3) determining the adsorption desulfurization performance of the coumarin modified metal organic framework hybrid material by adopting a static method. Weighing 2mg of the coumarin modified metal organic framework hybrid material, dispersing in a 2mL fuel oil model (the initial thiophene content is 476 ppm), and sampling once at intervals until the adsorption is balanced. Detecting the content of the residual thiophene in the fuel oil by a gas chromatograph, filtering out the hybrid material and drying after reaching the adsorption balance, placing the hybrid material in a methanol/toluene mixed solution for desorption, standing after ultrasonic treatment, and detecting the content of the thiophene in the solution by the gas chromatograph.
And (3) test results: the equilibrium adsorption capacity of the coumarin molecule grafted metal organic framework on thiophene is 0.30mmol S/g, after the coumarin molecule grafted metal organic framework is subjected to 340nm long-wave ultraviolet irradiation, the equilibrium adsorption capacity on thiophene is increased to 0.38mmol S/g, and the increment is 27%; after irradiation of 254nm short-wave ultraviolet light, the desorption amount of thiophene is 43%, and the coumarin molecule grafted metal organic framework can be recycled.
It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art should understand that they can make various changes, modifications, additions and substitutions within the spirit and scope of the present invention.
Claims (10)
1. The preparation method of the coumarin modified metal organic framework hybrid material is characterized by comprising the following operation steps:
(1) preparing a metal organic framework;
(2) deprotonating the coumarin molecule;
(3) respectively dissolving a metal organic framework and deprotonated coumarin molecules in a solvent, stirring, heating and refluxing, filtering, washing, drying, and grafting the coumarin molecules to the metal organic framework to obtain a coumarin molecule grafted metal organic framework;
(4) and (3) irradiating the coumarin molecules with long-wave ultraviolet light with the wavelength of more than 310nm to graft the metal-organic framework, so that the coumarin molecules in the metal-organic framework are subjected to dimerization reaction, and the coumarin modified metal-organic framework hybrid material is obtained.
2. The method for preparing the coumarin modified metal organic framework hybrid material as claimed in claim 1, wherein in the step (1), the metal organic framework material comprises one or more of metal organic framework material HKUST-1, metal organic framework material UiO-66, metal organic framework material MOF-5 and metal organic framework material ZIF-8.
3. The preparation method of the coumarin modified metal organic framework hybrid material as claimed in claim 2, wherein the coumarin modified metal organic framework hybrid material is prepared by reacting a coumarin compound with a metal organic framework compound,
the synthesis method of the metal organic framework HKUST-1 comprises the following steps: copper nitrate trihydrate and trimesic acid are used as raw materials, solvents are N, N-dimethylformamide, absolute ethyl alcohol and water, the reaction temperature is 80-120 ℃, the reaction time is 8-16 hours, then the raw materials are cooled to room temperature, filtered, soaked in methanol and methane for 24 hours respectively, and dried at room temperature, and the product is HKUST-1; wherein the molar ratio of copper nitrate trihydrate, trimesic acid, N-dimethylformamide, absolute ethyl alcohol and water is 1: 0.5-2: 20-50: 15-80: 80-200;
the synthesis method of the metal organic framework UiO-66 comprises the following steps: zirconium tetrachloride and terephthalic acid are used as raw materials, N-dimethylformamide and acetic acid are used as solvents, the reaction temperature is 100-220 ℃, the reaction time is 10-24 hours, then the mixture is cooled to room temperature, filtered, washed for 4 times by using the N, N-dimethylformamide and methanol respectively, and dried, and the product is UiO-66; wherein the molar ratio of zirconium tetrachloride to terephthalic acid to N, N-dimethylformamide to acetic acid is 1: 1-1.5: 1000-1800: 200-800;
the synthesis method of the metal organic framework MOF-5 comprises the following steps: zinc nitrate hexahydrate and terephthalic acid are used as raw materials, a solvent is N, N-dimethylformamide, the reaction temperature is 70-150 ℃, the reaction time is 10-30 hours, then the mixture is cooled to room temperature, filtered, washed for 3 times by using the N, N-dimethylformamide, and the product is MOF-5; wherein the molar ratio of zinc nitrate tetrahydrate, terephthalic acid and N, N-dimethylformamide is 1: 0.25-1: 100-300;
the synthesis method of the metal organic framework ZIF-8 comprises the following steps: zinc nitrate tetrahydrate and 2-methylimidazole are used as raw materials, N-dimethylformamide is used as a solvent, the reaction temperature is 100-180 ℃, the reaction time is 18-36 hours, the mixture is cooled to room temperature, then the mixture is filtered, and the product is ZIF-8 after being washed for 3 times by using the N, N-dimethylformamide; wherein the molar ratio of the zinc nitrate tetrahydrate to the 2-methylimidazole N, N-dimethylformamide is 1: 0.5-1.5: 200-400.
4. The method for preparing a coumarin modified metal organic framework hybrid material according to claim 1, wherein in the step (2), the coumarin molecule is 7-hydroxycoumarin.
5. The method for preparing the coumarin modified metal organic framework hybrid material according to claim 4, wherein in the step (2), the deprotonation process of the coumarin is as follows: dissolving coumarin molecules and sodium methoxide in methanol, and heating and refluxing, wherein the heating and refluxing reaction temperature is 50-80 ℃, and the reaction time is 2-10 h.
6. The preparation method of the coumarin modified metal organic framework hybrid material as claimed in claim 1, wherein in the step (3), the mass ratio of the deprotonated coumarin molecule to the metal organic framework is (0.1-1): 1.
7. The method for preparing a coumarin modified metal organic framework hybrid material according to claim 1, wherein in the step (3), the solvent is methanol.
8. The preparation method of the coumarin modified metal organic framework hybrid material as claimed in claim 1, wherein in the step (3), the reaction temperature of the heating reflux reaction is 50-80 ℃, and the reaction time is 8-20 h.
9. The application of the coumarin modified metal organic framework hybrid material prepared by the method as claimed in claim 1 is characterized in that the coumarin modified metal organic framework hybrid material is applied to adsorption desulfurization of fuel oil, and sulfur in the fuel oil is thiophene sulfide.
10. The use of claim 8, wherein the specific process for desulfurizing fuel oil is as follows: adding 2-10g of coumarin modified metal organic framework hybrid material into per liter of fuel oil, stirring uniformly, sampling once every 30-50min until adsorption balance, filtering to obtain the coumarin modified metal organic framework hybrid material adsorbed with thiophene sulfide, and irradiating the coumarin modified metal organic framework hybrid material with 254nm short-wave ultraviolet light to complete thiophene sulfide desorption.
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