CN110951086B - Preparation method of hydrophobic strong-acid MOFs - Google Patents
Preparation method of hydrophobic strong-acid MOFs Download PDFInfo
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- CN110951086B CN110951086B CN201911171915.8A CN201911171915A CN110951086B CN 110951086 B CN110951086 B CN 110951086B CN 201911171915 A CN201911171915 A CN 201911171915A CN 110951086 B CN110951086 B CN 110951086B
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 34
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 21
- 239000002253 acid Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 7
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical group [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000013178 MIL-101(Cr) Substances 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229950000244 sulfanilic acid Drugs 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- NRZRRZAVMCAKEP-UHFFFAOYSA-N naphthionic acid Chemical compound C1=CC=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 NRZRRZAVMCAKEP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 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 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- -1 sulfamic acid compound Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- 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
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of hydrophobic strongly acidic MOFs, belonging to the technical field of catalytic materials. The method comprises the following steps: the MOFs and sulfamic acid compounds are subjected to diazo reduction reaction in an acidic solvent in the presence of a catalyst to generate hydrophobic strongly acidic MOFs. The catalyst prepared by the invention has higher hydrophobicity and acid density, better cyclicity and stability, simple preparation steps, low equipment requirement, easy industrialization, wide application prospect and the like, and can be used for a plurality of catalytic reactions.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a preparation method of hydrophobic strongly acidic MOFs.
Background
Acid catalytic reaction is one of the very important reactions in the chemical industry, and a large amount of liquid acids such as sulfuric acid are used in the current industrial production process. However, these liquid acid catalysts are liable to cause corrosion of equipment during production, require a special neutralization step to separate the acid from the product, and cannot be recycled, so that a large amount of liquid acid catalysts are discarded every year, causing problems such as increase in production cost and environmental pollution. Compared with liquid acid, the solid acid catalyst has the advantages of no toxicity, environmental friendliness, difficulty in corroding equipment, recyclability and the like, so that more researches and applications are obtained.
The currently commonly used solid catalyst comprises zeolite molecular sieve, resin, metal oxide, carbon-based solid acid and the like, and has better performance effect. However, these catalysts still have the problems of unstable activity, easy carbon deposition and inactivation, poor hydrothermal stability and the like. Especially in reactions involving water, such as: fructose hydrolysis reaction, esterification reaction and the like, water generated by the reaction is easy to adsorb on acid sites of the catalyst, so that the contact of the catalyst and a reaction substrate is influenced, and the activity and the cyclicity of the catalyst are reduced. It becomes necessary to increase the hydrophobicity of the catalyst.
MOFs formed by self-assembly of inorganic metal centers and organic ligands are attracting attention because of their high specific surface area, controllable pore size and structure, Lewis acid sites in the metal centers, and hydrophobic and lipophilic nature of the organic structures themselves, and some MOFs (e.g., MIL-101(Cr)) have been produced in large quantities and have potential for industrial applications. However, as such, the MOFs have relatively single active sites, weak acidity and low acid density, so that the catalytic performance of the MOFs cannot meet the production requirement when the MOFs are directly used. Therefore, how to solve the above problems is important to design and synthesize hydrophobic strong-acid MOFs with strong acidity, high acid density, good catalytic activity and cycling stability based on MOFs capable of mass production.
Disclosure of Invention
The invention aims to provide a preparation method of a novel high-activity recyclable hydrophobic strong-acid catalyst designed and synthesized based on MOFs capable of being produced in batches.
The invention is realized by the following technical scheme.
On one hand, the preparation method of the hydrophobic strongly acidic MOFs is provided, and comprises the following steps:
the preparation method comprises the steps of premixing MOFs and sulfamic acid compounds according to the weight ratio of 1: 4-1: 10, premixing the sulfamic acid compounds and oxidizing agents according to the mol ratio of 1:1, adding a solvent and hydrochloric acid into the premix, reacting at the temperature of 60-80 ℃, stirring for 10min, separating, washing and drying to obtain the hydrophobic strong-acid MOFs.
Further, the sulfamic acid compound is sulfamic acid, sulfanilic acid, 4-amino-1-naphthalene sulfonic acid.
Further, the oxidant is sodium nitrite or isoamyl nitrite.
Further, the solvent is water or ethanol or a mixture of the two.
Further, the mass ratio of the solvent to the MOFs is 120: 1;
further, the mass ratio of the hydrochloric acid to the material is 0.7: 1.
further, the MOFs is MIL-101 (Cr).
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 MOFs provided by the invention has the advantages of a common solid acid catalyst, also has rich pore channel structures and hydrophobicity and lipophilicity, can effectively isolate reaction sites and byproducts, improves the conversion rate and selectivity of the reaction, has good cyclicity and stability, and is beneficial to industrial continuous production.
2. The hydrophobic strong-acid MOFs disclosed by the invention is simple in preparation steps, low in equipment requirement, easy to industrialize, capable of being used for multiple catalytic reactions and wide in application prospect.
Detailed Description
The present invention is further described in the following examples, which should not be construed as limiting the scope of the invention, but rather as providing the following examples which are set forth to illustrate and not limit the scope of the invention.
Preparation of hydrophobic strongly acidic MOFs: taking example 2 in table 1 as an example: weighing 4.0g of p-sulfamic acid and 1.76g of sodium hydroxide into a 250ml three-neck flask, adding 120ml of water, heating to 60 ℃ under magnetic stirring, measuring and adjusting the pH value to be more than 7 after reactants are completely dissolved, and then sequentially adding 1g of MIL-101(Cr) and 2.88g of sodium nitrite; slowly dropping 0.16mol of hydrochloric acid into the reaction solution, stirring, reacting for 10min, filtering, washing, and drying at 80 ℃ overnight. The specific surface area of the sample measured by a volumetric adsorption apparatus was 2676.5m2g-1The sulfur content of the sample measured by an element analyzer was 2.3 wt%, and the acid amount measured by an acid-base titration test was 0.72 mmoleg-1And the hydrophobicity of the sample was measured with a contact angle measuring instrument, the contact angle being 99 °. The reaction conditions and sample properties of examples 1 to 7 and comparative example 1 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 1-7 is 1682m2g-1Above, the sulfur content is above 2.1 wt%, and the acid content is 0.66mmol g-1The contact angle can reach more than 99 degrees, and the water-soluble polyurethane paint has large specific surface area, strong acidity and good hydrophobicity.
Comparative example 1 differs from the example in that hydrophilic chlorosulfonic acid was changed from hydrophobic sulfanilic acid, and in that the sulfonic acid group was directly grafted to MIL-101. Due to the hydrophilic nature of the sulfonic acid groups, the resulting catalyst contact angle was small, only 86 °. 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 (8)
1. A preparation method of hydrophobic strongly acidic MOFs is characterized by comprising the following steps:
the preparation method comprises the steps of premixing MOFs and sulfamic acid compounds according to the weight ratio of 1: 4-1: 10, premixing the sulfamic acid compounds and oxidizing agents according to the mol ratio of 1:1, adding a solvent and hydrochloric acid into the premix, reacting at the temperature of 60-80 ℃, stirring for 10min, separating, washing and drying to obtain the hydrophobic strong-acid MOFs.
2. The production method according to claim 1, wherein the sulfamic acid-based compound is sulfamic acid, sulfanilic acid, or 4-amino-1-naphthalenesulfonic acid.
3. The production method according to claim 1, wherein the oxidizing agent is sodium nitrite or isoamyl nitrite.
4. The method according to claim 1, wherein the solvent is water or ethanol or a mixture thereof.
5. The preparation method according to claim 1, wherein the mass ratio of the solvent to the MOFs is 120: 1.
6. the preparation method according to claim 1, wherein the mass ratio of hydrochloric acid to MOFs is 0.7: 1.
7. the method according to claim 1, wherein said MOFs is MIL-101 (Cr).
8. Hydrophobic strongly acidic MOFs, characterized in that they are prepared by the preparation method of any one of claims 1 to 7.
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| CN110951086B true CN110951086B (en) | 2021-06-22 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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