CN110903489B - Method for preparing hydrophobic strongly acidic MOFs based on alkylation reaction - Google Patents
Method for preparing hydrophobic strongly acidic MOFs based on alkylation reaction Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 44
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 22
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 15
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- MNURPFVONZPVLA-UHFFFAOYSA-N 2-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1Cl MNURPFVONZPVLA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 4
- 239000013207 UiO-66 Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000013178 MIL-101(Cr) Substances 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 239000003377 acid catalyst Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- 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]
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/618—
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- 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
- B01J2531/62—Chromium
Abstract
A method for preparing hydrophobic strongly acidic MOFs based on alkylation reaction belongs to the technical field of catalytic materials. The method comprises the steps of carrying out alkylation reaction on metal organic framework Materials (MOFs) and chlorobenzene sulfonic acid under the action of a catalyst, grafting sulfonic acid groups, and generating hydrophobic strong-acid MOFs. The hydrophobicity of the MOFs was controlled by adjusting the increase in the length of the carbon chain before the sulfonic acid and the support. The catalyst prepared by the invention has ultrahigh hydrophobicity, higher acid density and better cyclicity, has simple preparation steps and low equipment requirement, uses MOFs as an acidic carrier, is easy to industrialize, expands the variety of acid catalysts, can be used for a plurality of acid catalytic reactions, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of catalytic materials, and particularly relates to a method for preparing hydrophobic strongly acidic MOFs based on alkylation reaction.
Background
Metal-Organic Frameworks (MOFs) are crystalline materials containing a network structure and high order formed by Metal ions or Metal clusters through multidentate Organic ligands as connectors, and are widely used in the fields of catalysis, separation, gas storage, photoelectromagnetism and the like because of the advantages of structural diversity, high specific surface area, high porosity, adjustability and the like.
The MOFs preparation method is simple and mainly comprises a precipitation method, a hydrothermal solvent synthesis method, a mixing and stirring synthesis method, microwave synthesis, ultrasonic synthesis and the like. When the MOFs is used as an acid catalyst, a mixing stirring synthesis method is mostly adopted at present, and a sulfonation method is mainly adopted, but chlorosulfonic acid is a hydrophilic sulfonated substance, so that the obtained sulfonated MOFs material is easy to adsorb water in the reaction, and the activity and the cycle performance are not high. Therefore, in order to solve the above problems and to solve the diversity of reaction requirements, it is important to design and synthesize a hydrophobic strongly acidic MOFs having strong acidity and strong hydrophobicity.
Disclosure of Invention
The invention aims to provide hydrophobic strongly acidic MOFs and a preparation method for synthesizing a novel hydrophobic strongly acidic metal organic framework material by adopting an alkylation reaction based on the MOFs.
The invention is realized by the following technical scheme:
on the one hand, the preparation method for preparing the hydrophobic strongly acidic MOFs based on the alkylation reaction comprises the following steps: the MOFs and chlorobenzene sulfonic acid are subjected to alkylation reaction under the action of a catalyst, sulfonic acid groups are grafted, and hydrophobic strong-acid MOFs are generated.
Furthermore, the weight ratio of the MOFs to the chlorobenzene sulfonic acid is 1: 2-1: 5.
Further, the mass ratio of the MOFs to the catalyst is 1: 0.5.
Further, the alkylation reaction step comprises: adding MOFs, chlorobenzenesulfonic acid and a catalyst in proportion for premixing, adding a proper amount of solvent dichloromethane into the premix, stirring at the reaction temperature of 30 ℃, reacting for 1h, separating, washing and drying to prepare the hydrophobic strong-acid MOFs.
Further, MOFs are UIO-66(Zr) and MIL-101 (Cr).
Further, the catalyst is AlCl3And FeCl3。
On the other hand, the hydrophobic strongly acidic MOFs prepared by the preparation method is provided.
The invention has the beneficial effects that:
1. compared with the prior art, the hydrophobic strong-acid metal organic framework material has the advantages of a common acidic metal organic framework, has hydrophobicity, can effectively isolate reaction sites and byproducts, improves the conversion rate and selectivity of reaction, has good cyclicity and stability, and is beneficial to industrial continuous production.
2. The hydrophobic strong-acid metal organic framework material disclosed by the invention is simple in preparation steps, low in equipment requirement, easy to industrialize and wide in application prospect.
Detailed Description
The following examples are presented in tabular form to further illustrate the practice of the invention. The embodiments are merely exemplary and are not to be construed as limiting.
Take example 3 in table 1 as an example: 1g of UIO-66(Zr), 2g of chlorobenzenesulfonic acid and 60ml of dichloromethane are weighed into a 100ml three-neck flask, and the mixture is heated to the temperature of0.5g of AlCl was added at 30 ℃3As an alkylation catalyst, the reaction was carried out for 1 hour, and after filtration and washing, the reaction mixture was dried at 80 ℃ overnight. The specific surface area of the sample measured by a volumetric adsorption apparatus was 408.4m2g-1The sulfur content in the sample was 2.27 wt% by elemental analysis and the acid content of the sample was 0.71 mmoleg by acid-base titration-1And the hydrophobicity of the sample was measured with a water contact angle measuring instrument, the contact angle being 129 °. The reaction conditions and sample properties of examples 1 to 10 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1 preparation examples of hydrophobic strongly acidic MOFs
As can be seen from the table, the specific surface area of the hydrophobic strongly acidic MOFs prepared in examples 1-10 is 261m2g-1The sulfur content is more than 2.2 wt%, the acid density is more than 0.71mmol/g, the contact angle can reach more than 110 degrees, and the catalyst has the advantages of large specific surface area, strong acidity and good hydrophobicity.
Compared with the embodiment, the difference of the comparative examples 1-2 is that hydrophobic chlorobenzenesulfonic acid is changed into hydrophilic chlorosulfonic acid, sulfonic acid groups are directly grafted to MOFs, and the space size of the sulfonic acid groups is smaller than that of benzenesulfonic acid groups, so that the specific surface area of the obtained catalyst is larger. Due to the hydrophilicity of the sulfonic acid groups, the resulting catalyst contact angle is small, below 90 °. These sulfonated MOFs readily adsorb water during the reaction, resulting in poor activity and cycle performance.
Therefore, the hydrophobic strong-acid metal organic framework material prepared by the invention has very good performance.
Claims (4)
1. A method for preparing hydrophobic strongly acidic MOFs based on alkylation reaction is characterized by comprising the following steps: carrying out alkylation reaction on MOFs and chlorobenzene sulfonic acid under the action of a catalyst, grafting sulfonic acid groups, and generating hydrophobic strong-acid MOFs;
the weight ratio of the MOFs to the chlorobenzenesulfonic acid is 1: 2-1: 5;
the mass ratio of the MOFs to the catalyst is 1: 0.5;
the alkylation reaction step comprises: adding MOFs, chlorobenzenesulfonic acid and a catalyst in proportion for premixing, adding a proper amount of solvent dichloromethane into the premix, stirring at the reaction temperature of 30 ℃, reacting for 1h, separating, washing and drying to prepare the hydrophobic strong-acid MOFs.
2. The method according to claim 1, characterized in that said MOFs are UIO-66(Zr) and MIL-101 (Cr).
3. The method of claim 1, wherein the catalyst is AlCl3And FeCl3。
4. Hydrophobic strongly acidic MOFs, characterized in that they are prepared by the preparation method according to any one of claims 1 to 3.
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| US5026942A (en) * | 1988-10-05 | 1991-06-25 | Catalytica, Inc. | Process for selective diisopropylation of naphthyl compounds using shape selective acidic crystalline molecular sieve catalysts |
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| CN108435209A (en) * | 2018-04-08 | 2018-08-24 | 南昌大学 | A kind of preparation method of hydrophobic highly acid Carbon Materials |
| CN108499579A (en) * | 2018-04-20 | 2018-09-07 | 东南大学 | The preparation of solid acid catalyst based on Zr-MOF and its application process |
| CN110085909A (en) * | 2019-05-05 | 2019-08-02 | 中南大学 | A kind of composite solid electrolyte material and its preparation method and application |
| CN110156014A (en) * | 2019-05-28 | 2019-08-23 | 南昌大学 | It is a kind of based on alkylated reaction prepare hydrophobic strong acid Carbon Materials method and its hydrophobic strong acid Carbon Materials |
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- 2019-11-26 CN CN201911172533.7A patent/CN110903489B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5026942A (en) * | 1988-10-05 | 1991-06-25 | Catalytica, Inc. | Process for selective diisopropylation of naphthyl compounds using shape selective acidic crystalline molecular sieve catalysts |
| CN106513014A (en) * | 2016-09-22 | 2017-03-22 | 江苏大学 | Hierarchical-pore carbon-supported acidic solid catalyst and preparation method thereof |
| CN107163233A (en) * | 2017-05-19 | 2017-09-15 | 浙江帝恒实业有限公司 | A kind of plasticizer and preparation method thereof |
| CN108435209A (en) * | 2018-04-08 | 2018-08-24 | 南昌大学 | A kind of preparation method of hydrophobic highly acid Carbon Materials |
| CN108499579A (en) * | 2018-04-20 | 2018-09-07 | 东南大学 | The preparation of solid acid catalyst based on Zr-MOF and its application process |
| CN110085909A (en) * | 2019-05-05 | 2019-08-02 | 中南大学 | A kind of composite solid electrolyte material and its preparation method and application |
| CN110156014A (en) * | 2019-05-28 | 2019-08-23 | 南昌大学 | It is a kind of based on alkylated reaction prepare hydrophobic strong acid Carbon Materials method and its hydrophobic strong acid Carbon Materials |
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