CN116284824B - MOFs material and preparation method and application thereof - Google Patents
MOFs material and preparation method and application thereof Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 229940040102 levulinic acid Drugs 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 12
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims abstract description 11
- 235000003704 aspartic acid Nutrition 0.000 claims abstract description 11
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000012046 mixed solvent Substances 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 11
- 150000001299 aldehydes Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 239000013132 MOF-5 Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- ZOBPZXTWZATXDG-UHFFFAOYSA-N 1,3-thiazolidine-2,4-dione Chemical group O=C1CSC(=O)N1 ZOBPZXTWZATXDG-UHFFFAOYSA-N 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/64—Molybdenum
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a MOFs material and a preparation method and application thereof. The preparation method of the MOFs material comprises the steps of sequentially adding aspartic acid and a molybdenum source into a mixed solvent consisting of water and DMF and fully dispersing; heating, stirring and refluxing at 100-180 ℃ for 1-24 hours, cooling to room temperature after the reaction is finished, and filtering, washing and drying the obtained precipitate to obtain a matrix material containing amino; adding amino-containing matrix material, aldehyde and thioglycollic acid into DMF, stirring at room temperature for reaction for 1-12 hours, and obtaining solid which is the MOFs material. Wherein, the reflux reaction is carried out for 1-24 hours under the condition of heating and stirring at 100-180 ℃, and the reflux reaction can be replaced by the closed reaction for 1-24 hours in an autoclave at 100-180 ℃. The MOFs material provided by the invention can be directly used for catalyzing levulinic acid hydrogenation without additionally loading metal active components, so that the active components are not easy to run off, and the preparation efficiency is high.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a MOFs material and a preparation method and application thereof.
Background
Gamma valerolactone has wide application as an intermediate for resin solvents and various related compounds, as a gelling agent for lubricants, plasticizers, nonionic surfactants, lactone additives for leaded gasoline, and for dyeing cellulose esters and synthetic fibers. In addition, gamma valerolactone has vanillin and coconut flavor, one of the allowed flavors, mainly used to formulate peach, coconut, vanilla, etc.
Currently, gamma valerolactone is prepared mainly by selective hydrogenation of levulinic acid in the presence of a catalyst. The catalysts used include homogeneous catalysts and heterogeneous catalysts. Homogeneous catalysts are difficult to recycle, making the cost of preparing gamma valerolactone high. In the heterogeneous catalyst, the metal directly supported catalyst needs to additionally support a metal active component, and the biggest disadvantage is instability, and the problem that the supported metal active component is easy to run off exists in the reaction process, so that the preparation efficiency of gamma-valerolactone is low, and more heterogeneous catalysts need to be added in the preparation process to ensure the normal operation of the reaction, thereby also improving the preparation cost.
In practical production and research, metal Organic Frameworks (MOFs) are also used as heterogeneous catalysts for the catalytic preparation of gamma-valerolactone. MOFs is an organic-inorganic hybrid material composed of organic ligands and metal ions or metal clusters, has the advantages of adjustable structure, high specific surface area, rich active sites and the like, and has great application prospects in the field of catalysis. However, MOFs-type catalysts are complex to prepare, have low yields, and are costly to synthesize using noble metals.
Patent CN111423398A discloses a method for preparing gamma-valerolactone from levulinic acid, which discloses that gamma-valerolactone is prepared by catalytic hydrogenation under the action of a catalyst MOF-808, and also discloses that under the conditions that the optimal pH value is about 3.5, the catalyst dosage is 200mg, the reaction temperature is 180 ℃, and the reaction time is 4 hours, 83% yield and GVL selectivity of 76.3% are obtained. Although the preparation method of the catalytic MOF-808 is simpler than the synthesis method of the traditional MOFs type catalyst, the yield and GVL selectivity are low, namely the catalytic efficiency of the MOF-808 is low, which clearly increases the use cost.
Therefore, how to improve the catalytic action of MOFs materials in preparing gamma-valerolactone from levulinic acid is a technical problem to be solved by the technicians in the field.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to solve the problems of low preparation efficiency caused by poor stability and easy loss of active components of the existing catalyst for preparing gamma-valerolactone by catalytic hydrogenation of levulinic acid, and provides a MOFs material, a preparation method and application thereof, which can be directly used for catalyzing the hydrogenation of levulinic acid without additionally loading metal active components, so that the active components are not easy to be lost, and the preparation efficiency is high.
In order to solve the technical problems, the invention adopts the following technical scheme:
MOFs material containing thiazolidine ketone structure with chemical expression:
the invention also provides a preparation method of the MOFs material, which comprises the following steps,
sequentially adding aspartic acid and molybdenum sources into a mixed solvent consisting of water and DMF and fully dispersing;
heating, stirring and refluxing at 100-180 ℃ for 1-24 hours, cooling to room temperature after the reaction is finished, and filtering, washing and drying the obtained precipitate to obtain a matrix material containing amino;
adding amino-containing matrix material, aldehyde and thioglycollic acid into DMF, stirring at room temperature for reaction for 1-12 hours, and obtaining solid which is the MOFs material.
The invention also provides a preparation method of the MOFs material, which comprises the following steps,
sequentially adding aspartic acid and molybdenum sources into a mixed solvent consisting of water and DMF and fully dispersing;
placing the mixture in an autoclave at 100-180 ℃ for airtight reaction for 1-24 hours, cooling to room temperature after the reaction is finished, and filtering, washing and drying the obtained precipitate to obtain the amino-containing matrix material.
Adding amino-containing matrix material, aldehyde and thioglycollic acid into DMF, stirring at room temperature for reaction for 1-12 hours, and obtaining solid which is the MOFs material.
Preferably, the molar ratio of the aspartic acid to the molybdenum source is 1:0.2-5; the proportion of the matrix material, aldehyde, thioglycollic acid and DMF is as follows: 10-100 g/1 mol/0.5-10 mol: 100-500 mL.
Preferably, the molybdenum source is one or more of molybdic acid, ammonium molybdate, potassium molybdate, sodium molybdate and molybdenum oxide.
Preferably, the aldehyde is a mono-aliphatic aldehyde, di-aliphatic aldehyde, mono-aromatic aldehyde or di-aromatic aldehyde.
The invention also provides an application of the MOFs material, wherein the MOFs material is used as a catalyst for preparing gamma-valerolactone by catalytic hydrogenation of levulinic acid.
Compared with the prior art, the invention has the following advantages:
1. according to the MOFs material provided by the invention, the thiazolidinone structure containing sulfur and nitrogen heteroatoms is introduced, so that the coordination stability of the MOFs material is improved, and the stability of the catalyst is improved, so that the MOFs material has higher catalytic activity in the catalytic process, the loss of active components in the reaction process is reduced, and the catalytic efficiency is improved. The MOFs material has high activity in the hydrogenation reaction of catalyzing levulinic acid, and realizes high selectivity and high yield of gamma-valerolactone. In addition, the MOFs material is easy to recycle, the catalytic performance of the MOFs material is not obviously reduced after the MOFs material is recycled for 10 times, and the production cost can be saved.
2. The preparation method of the MOFs material provided by the invention has the advantages of simple steps, easiness in operation and contribution to industrial production.
Drawings
FIG. 1 is a diffraction pattern of XRD of MOF-1 prepared in example 1.
FIG. 2 is an infrared spectrum of MOF-1 prepared in example 1.
FIG. 3 is an XPS spectrum of MOF-1 prepared in example 1.
Detailed Description
Example 1
The preparation of MOFs material comprises the following steps,
to a round bottom flask was added 300mL of a mixed solvent (consisting of 200mL of water and 100mL of DMF), followed by 26.6g of aspartic acid and 19.6g of ammonium molybdate, followed by ultrasonic dispersion for 15 minutes.
Heating to 120 ℃, stirring, refluxing, reacting for 8 hours, cooling to room temperature, leaching the precipitate obtained by suction filtration, sequentially soaking with DMF, water and ethanol, and then drying in vacuum at 80 ℃ for 5 hours to obtain the matrix material.
Taking 5g of matrix material to disperse in 30mL of DMF, then adding 10mL of glutaraldehyde and 21mL of thioglycollic acid, and stirring at room temperature for reaction for 5 hours to obtain MOFs material, and marking the MOF-1. As shown in figure 1, the diffraction pattern of the XRD of the MOF-1 shows that the diffraction peak of the material is sharp and clear, and no obvious dispersion peak exists, which indicates that the crystallinity of the obtained MOFs material is good. Meanwhile, the XRD diffraction peak of MOF-1 is consistent with MIP-202 crystals which are identical to aspartic acid ligands, which shows that the MOFs material with fcu topological structure is prepared. Red of MOF-1The external map is shown in FIG. 2, at 1645cm -1 Stretching vibration of o=c-N occurs, which is attributed to carbonyl group in the thiazolidine ketone structure; the infrared absorption peak of the C-S bond is weak and overlaps with other peaks. The XPS pattern of MOF-1 is shown in FIG. 3, showing a distinct S2 p peak, derived from sulfur in the thiazolidine ketone structure. Taken together, XRD, infrared and XPS characterization results show that the invention successfully prepares the MOFs material containing the thiazolidinedione structure.
Example 2
In example 2, 11mL of benzaldehyde was used instead of 10mL of glutaraldehyde, and the rest was the same as in example 1. The MOFs material prepared in example 2 was designated MOF-2.
Example 3
In example 3, 13.4g of terephthalaldehyde was used instead of 10mL of glutaraldehyde, and the rest was the same as in example 1. The MOFs material prepared in example 3 was designated MOF-3.
Example 4
The preparation of MOFs material comprises the following steps,
to 300mL of the mixed solvent (composed of 200mL of water and 100mL of DMF) were added 26.6g of aspartic acid and 19.6g of ammonium molybdate in this order, followed by ultrasonic dispersion for 15 minutes.
Transferring the mixed solution into an autoclave, performing airtight reaction for 12 hours at 120 ℃, cooling to room temperature, leaching the obtained precipitate with DMF, water and ethanol in sequence, and then performing vacuum drying for 5 hours at 80 ℃ to obtain a matrix material B.
Taking 5g of matrix material to disperse in 30mL of DMF, then adding 10mL of glutaraldehyde and 21mL of thioglycollic acid, and stirring at room temperature for reaction for 5 hours to obtain MOFs material, and marking the MOF-4.
Example 5
In example 5, 11mL of benzaldehyde was used instead of 10mL of glutaraldehyde, and the rest was the same as in example 4. The MOFs material prepared in example 5 was designated MOF-5.
Example 6
In example 6, 13.4g of terephthalaldehyde was used instead of 10mL of glutaraldehyde, and the rest was the same as in example 4. The MOFs material prepared in example 6 was designated MOF-6.
The XRD diffraction patterns of the MOFs prepared in examples 2-6 were substantially identical to the XRD diffraction pattern of MOF-1 prepared in example 1, indicating that the MOF materials prepared in examples 2-6 were identical to the crystal structure of MOF-1 prepared in example 1. MOFs materials prepared in examples 1-6 were used to catalyze the hydrogenation of levulinic acid to gamma valerolactone.
2g of MOFs material prepared in each example was taken and added to an autoclave, 20mL of levulinic acid solution with the concentration of 0.5mol/L was then added, hydrogen gas was filled to 1MPa, and stirring was started after the temperature was raised to 180℃for reaction for 6 hours. After the reaction, the product was analyzed by gas chromatography. The catalytic properties of the MOFs materials prepared in examples 1-6 are shown in Table 1.
TABLE 1 catalytic Properties of different MOFs materials
| MOFs material | Levulinic acid conversion (%) | Gamma valerolactone selectivity (%) | Gamma valerolactone yield (%) |
| MOF-1 | 100 | 100 | 100 |
| MOF-2 | 100 | 99.5 | 99.5 |
| MOF-3 | 100 | 100 | 100 |
| MOF-4 | 91.8 | 100 | 91.8 |
| MOF-5 | 94.5 | 99.2 | 93.7 |
| MOF-6 | 97.2 | 100 | 97.2 |
As can be seen from Table 1, the above six MOFs materials all have high activity in catalyzing the hydrogenation of levulinic acid, and can achieve high selectivity and high yield of gamma valerolactone. Among them, MOFs materials prepared by the heating reflow method (i.e., examples 1-3) have better properties.
And (3) washing the used MOFs material with water and ethanol sequentially, and drying the MOFs material in vacuum at 80 ℃ for 5 hours to obtain the recovered MOFs material. The recovered MOF-1 is repeatedly subjected to hydrogenation reaction for catalyzing levulinic acid, and the gamma-valerolactone yield obtained by recycling for 10 times is sequentially 100%,100%,100%,100%,99.8%,99.8%,99.8%,99.5%,99.5% and 99.3%, so that the catalytic performance of the MOFs material after repeated use is not obviously reduced, and the MOFs material provided by the invention has good repeated use performance.
Therefore, the MOFs material provided by the invention has high activity in the hydrogenation reaction of the catalytic levulinic acid, and realizes high selectivity and high yield of gamma-valerolactone. In addition, the MOFs material is easy to recycle, the catalytic performance of the MOFs material is not obviously reduced after the MOFs material is recycled for 10 times, and the production cost can be saved.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (7)
1. The MOFs material is characterized by comprising a thiazolidine ketone structure, and the chemical expression of the MOFs material is as follows:
the preparation process comprises the following steps:
sequentially adding aspartic acid and molybdenum sources into a mixed solvent consisting of water and DMF and fully dispersing;
heating, stirring and refluxing for reaction for 1-24 hours at 100-180 ℃ or placing the mixture in an autoclave for airtight reaction for 1-24 hours at 100-180 ℃, cooling the mixture to room temperature after the reaction is finished, and filtering, washing and drying the obtained precipitate to obtain a matrix material containing amino;
adding amino-containing matrix material, aldehyde and thioglycollic acid into DMF, stirring at room temperature for reaction for 1-12 hours, and obtaining solid which is the MOFs material.
2. A method for preparing MOFs material according to claim 1, comprising the steps of,
sequentially adding aspartic acid and molybdenum sources into a mixed solvent consisting of water and DMF and fully dispersing;
heating, stirring and refluxing at 100-180 ℃ for 1-24 hours, cooling to room temperature after the reaction is finished, and filtering, washing and drying the obtained precipitate to obtain a matrix material containing amino;
adding amino-containing matrix material, aldehyde and thioglycollic acid into DMF, stirring at room temperature for reaction for 1-12 hours, and obtaining solid which is the MOFs material of claim 1.
3. A method for preparing MOFs material according to claim 1, comprising the steps of,
sequentially adding aspartic acid and molybdenum sources into a mixed solvent consisting of water and DMF and fully dispersing;
placing the mixture in an autoclave at 100-180 ℃ for airtight reaction for 1-24 hours, cooling the mixture to room temperature after the reaction is finished, and filtering, washing and drying the obtained precipitate to obtain a matrix material containing amino;
adding amino-containing matrix material, aldehyde and thioglycollic acid into DMF, stirring at room temperature for reaction for 1-12 hours, and obtaining solid which is the MOFs material of claim 1.
4. The method for producing MOFs materials according to claim 2 or 3, wherein,
the mol ratio of the aspartic acid to the molybdenum source is 1:0.2-5;
the proportion of the matrix material, aldehyde, thioglycollic acid and DMF is as follows: 10-100 g/1 mol/0.5-10 mol: 100-500 mL.
5. The method for producing MOFs material according to claim 2 or 3, wherein the molybdenum source is one or more of molybdic acid, ammonium molybdate, potassium molybdate, sodium molybdate, and molybdenum oxide.
6. A method of preparing MOFs materials according to claim 2 or claim 3, wherein the aldehyde is a mono-aliphatic aldehyde, a di-aliphatic aldehyde, a mono-aromatic aldehyde or a di-aromatic aldehyde.
7. Use of MOFs materials according to claim 1 as catalysts for the catalytic hydrogenation of levulinic acid to gamma valerolactone.
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| CN107382999A (en) * | 2017-08-01 | 2017-11-24 | 陕西科技大学 | Carbazolyl-containing thiazolidone and preparation method thereof |
| CN109569521A (en) * | 2018-12-10 | 2019-04-05 | 南昌航空大学 | A kind of rhodanine functionalization MOFs adsorbent and its preparation method and application |
| CN113101941A (en) * | 2021-03-25 | 2021-07-13 | 国网综合能源服务集团有限公司 | Preparation method of cobalt-molybdenum catalyst and application of cobalt-molybdenum catalyst in catalyzing levulinic acid hydrogenation reaction |
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| CN107382999A (en) * | 2017-08-01 | 2017-11-24 | 陕西科技大学 | Carbazolyl-containing thiazolidone and preparation method thereof |
| CN109569521A (en) * | 2018-12-10 | 2019-04-05 | 南昌航空大学 | A kind of rhodanine functionalization MOFs adsorbent and its preparation method and application |
| CN113101941A (en) * | 2021-03-25 | 2021-07-13 | 国网综合能源服务集团有限公司 | Preparation method of cobalt-molybdenum catalyst and application of cobalt-molybdenum catalyst in catalyzing levulinic acid hydrogenation reaction |
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