CN108816287B - Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material and preparation and application thereof - Google Patents

Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material and preparation and application thereof Download PDF

Info

Publication number
CN108816287B
CN108816287B CN201810499706.5A CN201810499706A CN108816287B CN 108816287 B CN108816287 B CN 108816287B CN 201810499706 A CN201810499706 A CN 201810499706A CN 108816287 B CN108816287 B CN 108816287B
Authority
CN
China
Prior art keywords
uio
ionic liquid
functionalized ionic
composite material
carboxyl functionalized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201810499706.5A
Other languages
Chinese (zh)
Other versions
CN108816287A (en
Inventor
叶长燊
齐兆洋
邱挺
李玲
王红星
黄智贤
杨臣
王晓达
陈锦溢
林小城
杨金杯
王清莲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fuzhou University
Original Assignee
Fuzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuzhou University filed Critical Fuzhou University
Priority to CN201810499706.5A priority Critical patent/CN108816287B/en
Publication of CN108816287A publication Critical patent/CN108816287A/en
Application granted granted Critical
Publication of CN108816287B publication Critical patent/CN108816287B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • 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]
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • 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
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49—Esterification or transesterification
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention belongs to the technical field of light industry and chemical materials, and provides an Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material, and preparation and application thereof, wherein a metal organic framework material Uio-66 is used as a carrier, a carboxyl functionalized ionic liquid is used as an active component, and the carboxyl functionalized ionic liquid is subjected to coordination bonding with a zirconium metal cluster through carboxyl while being synthesized into Uio-66, and is immobilized in a hole cage of Uio-66 in situ to prepare the composite material. The composite material has the characteristics of high catalytic activity, high mass transfer rate, good selectivity, easiness in recovery and separation, environmental friendliness, wide industrial application prospect and the like besides good physical stability and chemical stability. The composite material prepared by the invention is used as a catalyst for esterification reaction and ester exchange reaction of various acids and alcohols, and has good effect; the adsorbent has obvious adsorption effect on heavy metal ions contained in liquid.

Description

Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material and preparation and application thereof
Technical Field
The invention relates to the technical field of composite material synthesis, in particular to an Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material and preparation and application thereof.
Background
Ionic Liquid (Ionic Liquid) is a compound which is composed of organic cations and organic or inorganic anions and is in a Liquid state at room temperature or near room temperature, has the advantages of designability, strong thermal stability, wide Liquid temperature range, strong conductivity and the like, and is widely applied to various fields of chemical research. At present, the liquid ionic liquid is widely applied in the fields of green organic synthesis, separation and purification, electrochemistry and the like, and better results are obtained. However, in the practical application process, the problems of high cost, difficult industrial application and the like caused by large dosage of the ionic liquid, difficult product separation and catalyst recovery exist at the same time. This has prompted the immobilization of ionic liquids to become a very important research hotspot. At present, commonly used carriers for immobilizing ionic liquids include: silica gel (Garene B. Chemical Communications, 2004, 1768-.
Metal organic framework Materials (MOFs) have the characteristics of large specific surface area, permanent pore structure, easy modification and the like, can be used as excellent ionic liquid immobilized carriers, and have the advantages that the immobilized functional ionic liquid is realized by using porous MOF Materials with metal center coordination unsaturation as carriers by Luo. Journal of Materials Chemistry A, 2013, 1, 6530-6534 and the like through the action of coordination bonds, but the frameworks of many MOF Materials lack metal coordination unsaturation points, so the application of the method is limited. Yuan (Yuan. Chinese patent, CN 106693899A) and the like synthesize and load the functionalized ionic liquid on a metal organic framework material by adopting a bottle-in-bottle shipbuilding method, and the functionalized ionic liquid is used as a catalyst for adsorption-oxidation-extraction to remove sulfur-containing substances in gasoline. However, the 'shipbuilding in bottles' method has strict requirements on the diameter of a pore cage of the MOF material, and has poor adsorption and catalytic effects on macromolecular substances. Therefore, the research on a novel method for loading the ionic liquid on the MOF material is gradually a hot point.
Disclosure of Invention
The invention aims to provide Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material and preparation and application thereof, aiming at the defects of the prior art. The composite material disclosed by the invention has the characteristics of high catalytic activity, high mass transfer rate, good selectivity, easiness in recovery and separation, environmental friendliness, wide industrial application prospect and the like besides good physical stability and chemical stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material comprises the steps of taking a metal organic framework material Uio-66 as a carrier and carboxyl functionalized ionic liquid as an active component, carrying out coordination bonding on the carboxyl functionalized ionic liquid and a zirconium metal cluster through carboxyl while synthesizing Uio-66, and carrying out in-situ immobilization in a hole cage of Uio-66 to prepare Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material.
The synthesis method is shown in figure 1.
In the preparation method of the invention, the functional group of the carboxyl functionalized ionic liquid is one of monocarboxyl, dicarboxyl and tricarboxy; the parent of the carboxyl functionalized ionic liquid is at least one of quaternary ammonium salt ions, quaternary phosphonium salt ions, imidazole salt ions and pyridine salt ions.
The preparation method of the invention specifically comprises the following steps: ultrasonically dissolving carboxyl functionalized ionic liquid, terephthalic acid and zirconium chloride in a DMF system, dispersing for 0.5h, crystallizing for 24h at the temperature of 100-140 ℃, centrifuging, washing and drying the obtained product to obtain the in-situ immobilized IL @ Uio-66 composite material.
In the preparation method, the molar ratio of the terephthalic acid to the zirconium chloride is 0.5-2: 1, and the molar ratio of the carboxyl functionalized ionic liquid to the zirconium chloride is 0.5-2: 1.
Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material prepared by the method.
The Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material prepared by the method is used as a catalyst for catalytic esterification reaction and acid catalytic ester exchange reaction of various acids and alcohols, and the dosage of the catalyst is 1-2.5% of the mass of a reactant; the adsorbent is used in the adsorption process of heavy metal ions in liquid, and the dosage of the adsorbent is 0.1-10 g/L.
The invention has the beneficial effects that:
1) the carboxyl functionalized ionic liquid is immobilized on Uio-66 with high physical stability and chemical stability through an in-situ synthesis method, and the composite material has the characteristics of high catalytic activity, high mass transfer rate, good selectivity, easiness in recovery and separation, environmental friendliness, wide industrial application prospect and the like besides good physical stability and chemical stability;
2) the composite material prepared by the invention is used as a catalyst for catalytic esterification reaction and ester exchange reaction of various acids and alcohols, and has good effect; the adsorbent has obvious adsorption effect on heavy metal ions in liquid.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the present invention;
FIG. 2 is an X-ray diffraction pattern of the composite material produced in example 1;
FIG. 3 is an infrared spectrum of a composite material produced in example 1; (a) is IL; (b) uio-66; (c) IL @ Uio-66.
Detailed description of the invention
The invention is further illustrated by the following specific examples. The scope of the invention is not limited to the following examples.
Example 1
(1) Preparation of monocarboxylic functionalized ionic liquids
Accurately weighing 0.1mol of chloroacetic acid, adding the chloroacetic acid into a 100ml round-bottom flask, dropwise adding 0.1mol of 1-methylimidazole under the condition of mechanical stirring, reacting for 8 hours at 70 ℃, washing with ethanol, and drying in vacuum to obtain a white solid; dissolving the white solid in a small amount of deionized water, adding sulfuric acid with the same amount of substance, magnetically stirring for 8h at 70 ℃, washing with ethyl acetate, and vacuum drying to obtain 1-carboxymethyl-3-methylimidazole bisulfate;
(2) preparation of in-situ immobilized single carboxyl functionalized IL @ Uio-66
0.0603g of terephthalic acid is accurately weighed in 42ml of DMF, then 0.0848g of zirconium chloride is rapidly added, ultrasonic treatment is carried out for 30min, 0.15g of the synthesized 1-carboxymethyl-3-methylimidazole hydrogen sulfate is added, after ultrasonic treatment is carried out for 30min, the mixture is placed in a 100ml of polytetrafluoroethylene lining, reaction is carried out for 24h at 120 ℃, centrifugal separation is carried out after natural cooling, DMF and methanol are respectively washed for three times, and vacuum drying is carried out, thus obtaining the monocarboxylic functionalized IL @ Uio-66 composite material. X-ray diffraction detection shows that the synthesized composite material has the crystal structure characteristics of Uio-66 (figure 2); the infrared spectrum showed that the ionic liquid was successfully immobilized on Uio-66 (FIG. 3).
Example 2
(1) Preparation of dicarboxyl functionalized ionic liquid
Accurately weighing 0.1mol of 1-methylimidazole, adding the 1-methylimidazole into a 100ml round-bottom flask, dropwise adding a proper amount of bromosuccinic acid dissolved in methanol under the condition of mechanical stirring, reacting for 8 hours at the temperature of 80 ℃, and obtaining orange viscous liquid after reduced pressure distillation, ethyl acetate washing and vacuum drying; dissolving the orange viscous liquid in a small amount of deionized water, adding sulfuric acid with the same amount of substances, magnetically stirring for 8 hours at 70 ℃, washing with ethyl acetate, and drying in vacuum to obtain 1-bromo-1, 2-dicarboxyethyl-3-methylimidazole bisulfate;
(2) preparation of in-situ immobilized double-carboxyl functionalized IL @ Uio-66
0.0603g of terephthalic acid is accurately weighed in 42ml of DMF, then 0.0848g of zirconium chloride is rapidly added, ultrasonic treatment is carried out for 30min, 0.15g of the synthesized 1-bromo-1, 2-dicarboxyethyl-3-methylimidazolium hydrogen sulfate is added, after ultrasonic treatment for 30min, the obtained product is put into a 100ml of polytetrafluoroethylene lining, reaction is carried out for 24h at 120 ℃, centrifugal separation is carried out after natural cooling, DMF and methanol are respectively washed for three times, and vacuum drying is carried out, thus obtaining the dicarboxyl functionalized IL @ Uio-66 composite material.
Application example 1
2.2g of the in-situ immobilized dicarboxyl functionalized IL @ Uio-66 catalyst prepared in example 2, 74g of propionic acid and 72g of n-propanol were added into a reaction apparatus, a certain amount of water-carrying agent was added, the reaction temperature was 100 ℃, magnetic stirring was performed, the reaction was performed for 6 hours, the propionic acid conversion was 95%, and the selectivity was 100%.
Application example 2
3.0g of the in-situ immobilized dicarboxyl functionalized IL @ Uio-66 catalyst prepared in example 2, 192g of ethanol and 8.0g of cottonseed oil are added into a high-pressure reaction kettle, the reaction temperature is 100 ℃, the reaction pressure is 0.8MPa, the reaction time is 2 hours, and pure biodiesel is obtained by filtering, standing, layering and pressure reduction and flow distribution operations, wherein the yield of the biodiesel reaches 92.57%.
Application example 3
Using water as solvent to prepare Co2+As a 50ppm simulated solution, 1.0g of the in situ immobilized monocarboxyl functionalized IL @ Uio-66 composite material prepared in example 1 was placed as an adsorbent in 100mL of the simulated solution, reacted in a constant temperature oscillator at 25 ℃ for 2h, and the Co content of the separated simulated sample was measured2+Content of Co is calculated2+The removal rate of (A) reaches 99%.
Application example 4
Using water as solvent to prepare Mn2+1.0g of the in situ immobilized monocarboxyl functionalized IL @ Uio-66 composite material prepared in example 1 as an adsorbent in 50ppm of a simulated solution was placed in 100mL of the simulated solution, reacted in a constant temperature oscillator at 25 ℃ for 2h, and the Mn of the separated simulated sample was determined2+Content of Mn is calculated2+The removal rate of (A) reaches 98%.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (4)

1, Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material preparation method, characterized by: the preparation method comprises the steps of taking metal organic framework materials Uio-66 as carriers and carboxyl functionalized ionic liquid as active components, synthesizing Uio-66, and simultaneously carrying out coordination bonding on the carboxyl functionalized ionic liquid and zirconium metal clusters through carboxyl groups and carrying in situ in Uio-66 pore cages to prepare the Uio-66 in situ carried carboxyl functionalized ionic liquid composite material;
the functional group of the carboxyl functionalized ionic liquid is one of monocarboxyl, dicarboxyl and tricarboxy; the parent body of the carboxyl functionalized ionic liquid is at least one of quaternary ammonium salt ions, quaternary phosphonium salt ions, imidazole salt ions and pyridine salt ions;
ultrasonically dissolving carboxyl functionalized ionic liquid, terephthalic acid and zirconium chloride in a DMF (dimethyl formamide) system, dispersing for 0.5h, crystallizing for 24h at the temperature of 100-140 ℃, and centrifuging, washing and drying the obtained product to obtain an in-situ immobilized IL @ Uio-66 composite material; the molar ratio of the terephthalic acid to the zirconium chloride is 0.5-2: 1, and the molar ratio of the carboxyl functionalized ionic liquid to the zirconium chloride is 0.5-2: 1.
2. Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material prepared by the preparation method of claim 1.
3. Use of the Uio-66 in situ immobilized carboxyl-functionalized ionic liquid composite of claim 2 as a catalyst in esterification and transesterification reactions of various acids and alcohols.
4. Use of the Uio-66 in situ immobilized carboxyl functionalized ionic liquid composite material of claim 2 as an adsorbent in heavy metal ion adsorption in liquids.
CN201810499706.5A 2018-05-23 2018-05-23 Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material and preparation and application thereof Expired - Fee Related CN108816287B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810499706.5A CN108816287B (en) 2018-05-23 2018-05-23 Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material and preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810499706.5A CN108816287B (en) 2018-05-23 2018-05-23 Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material and preparation and application thereof

Publications (2)

Publication Number Publication Date
CN108816287A CN108816287A (en) 2018-11-16
CN108816287B true CN108816287B (en) 2020-12-25

Family

ID=64148490

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810499706.5A Expired - Fee Related CN108816287B (en) 2018-05-23 2018-05-23 Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material and preparation and application thereof

Country Status (1)

Country Link
CN (1) CN108816287B (en)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109569521B (en) * 2018-12-10 2021-09-14 南昌航空大学 Rhodanine functionalized MOFs adsorbent and preparation method and application thereof
CN109663614A (en) * 2019-01-08 2019-04-23 太原理工大学 Carboxyl-functional imidazole ion liquid/MIL-101 composite catalyst and preparation method thereof
CN110041533B (en) * 2019-05-29 2020-08-11 福州大学 Method for preparing functionalized metal organic framework material by ionic liquid ligand displacement method
CN110368903B (en) * 2019-06-10 2022-03-15 青岛职业技术学院 Method for enriching polyunsaturated fatty acid in grease
CN110331001B (en) * 2019-07-11 2021-08-31 福建师范大学福清分校 Preparation method and application of iron-based metal organic framework immobilized ionic liquid
CN110496608A (en) * 2019-08-13 2019-11-26 辽宁大学 A kind of poly ion liquid@metal organic framework composite material xPILs@MIL-101 and its preparation method and application
CN111471188B (en) * 2020-04-30 2022-04-01 福州大学 Preparation and application of amino-functionalized MOFs (metal-organic frameworks) material capable of adsorbing lead ions in high capacity
CN112592485B (en) * 2020-12-04 2021-11-30 福州大学 Preparation of polyion liquid functionalized MOFs material and application of polyion liquid functionalized MOFs material in synthesis of isopulegol
CN113926304B (en) * 2021-03-22 2024-01-16 青岛大学 Low-temperature mercury-removing adsorbent for coal-fired flue gas
CN113788865B (en) * 2021-06-29 2024-03-19 华南理工大学 Method for preparing fructose by catalyzing glucose isomerization through ionic liquid loaded by organic metal framework material
CN113769790B (en) * 2021-09-17 2023-10-24 福州大学 Carboxyl functionalized ILs@MOFs composite material and preparation method and application thereof
CN113908810A (en) * 2021-11-05 2022-01-11 中山大学 Biochar immobilized ionic liquid adsorption material and preparation method and application thereof
CN114573854B (en) * 2022-03-16 2023-08-04 江苏大学 Preparation method of quaternary phosphonium third-class porous ionic liquid
CN116328736A (en) * 2022-11-23 2023-06-27 中国原子能科学研究院 MOF composite adsorbent loaded with imidazole-4, 5-dicarboxylic acid and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104289174A (en) * 2014-09-10 2015-01-21 济南大学 Preparation method of ionic liquid loaded type bentonite absorbent
CN105777643A (en) * 2014-12-22 2016-07-20 南京化工职业技术学院 Method using immobilized ionic liquid as catalyst to synthesize lubricant base oil
CN106423075A (en) * 2016-11-14 2017-02-22 齐鲁工业大学 Silica gel immobilization functionalized ionic liquid adsorbing agent, preparation method and application
CN107857886A (en) * 2017-11-21 2018-03-30 江南大学 A kind of Zr MOF preparation method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104289174A (en) * 2014-09-10 2015-01-21 济南大学 Preparation method of ionic liquid loaded type bentonite absorbent
CN105777643A (en) * 2014-12-22 2016-07-20 南京化工职业技术学院 Method using immobilized ionic liquid as catalyst to synthesize lubricant base oil
CN106423075A (en) * 2016-11-14 2017-02-22 齐鲁工业大学 Silica gel immobilization functionalized ionic liquid adsorbing agent, preparation method and application
CN107857886A (en) * 2017-11-21 2018-03-30 江南大学 A kind of Zr MOF preparation method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A Modulator-Induced Defect-Formation Strategy to give Hierarchically Porous Metal–Organic Frameworks with High Stability;Guorui Cai et al;《Angew. Chem. Int. Ed.》;20161208;第56卷;第563页右栏第2段，Scheme 1. *
Bing-Jian Yao et al.Chemically Cross-Linked MOF Membrane Generated from Imidazolium-Based Ionic Liquid-Decorated UiO-66 Type NMOF and Its Application toward CO2 Separation and Conversion.《ACS Appl. Mater. Interfaces》.2017,第9卷 *
Chemically Cross-Linked MOF Membrane Generated from Imidazolium-Based Ionic Liquid-Decorated UiO-66 Type NMOF and Its Application toward CO2 Separation and Conversion;Bing-Jian Yao et al;《ACS Appl. Mater. Interfaces》;20171013;第9卷;第38920页右栏末段至第38921页第2段，Scheme 1. *

Also Published As

Publication number Publication date
CN108816287A (en) 2018-11-16

Similar Documents

Publication Publication Date Title
CN108816287B (en) Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material and preparation and application thereof
CN102962036B (en) Porous metal organic frameworks based on transition metals cobalt and preparation method thereof
CN108619921B (en) Ionic liquid modified graphene oxide/polymer composite membrane and preparation and application thereof
CN103316714A (en) Catalyst for photo-catalytically decomposing water to produce hydrogen and preparation method of catalyst
CN110560170B (en) Pd @ MOF material, preparation method thereof and application thereof in biphenyl preparation
CN113275041B (en) Preparation of COF-316/CAT-1 composite material and photocatalytic carbon dioxide reduction
CN110041533B (en) Method for preparing functionalized metal organic framework material by ionic liquid ligand displacement method
CN110252407B (en) Method for preparing core-shell structure catalyst by carboxyl functionalized ionic liquid
CN104525260A (en) Polymeric solid acid catalyst for esterification reaction and preparation method thereof
CN106694050A (en) Preparation method of visible-light-induced photocatalyst with core-shell structure
CN105688993A (en) Load type polymeric acidic ionic liquid catalyst and preparation method and application thereof
CN112934267A (en) Alkylated hydrophobic MOFs material and application thereof in cyclohexene hydration
CN103638970B (en) A kind of method of marsh gas purifying in fixing bed
CN111875493B (en) Method for synthesizing borneol by using imidazole acidic ionic liquid
CN105964306A (en) Poly(ionic liquid)-based magnetic nanoparticle and its preparation method and use in three-ingredient reaction
CN108250381B (en) Preparation method and application of selenium-containing phenolic resin microspheres
CN103709010B (en) A kind of by tetrahydrobenzene, carboxylic acid and water Reactive Synthesis hexalin method
CN110052116A (en) A kind of method of fumaric acid-based carbon-dioxide absorbent and absorption and desorption carbon dioxide
CN107188804B (en) Method for catalytically synthesizing methyl oleate by using composite phosphotungstate
CN112295546B (en) Zinc complex with porous structure and preparation method thereof
CN114560964A (en) Synthetic method and application of carboxyl functional polyion liquid
Wang et al. Amino-functionalized MIL type metal organic frameworks as heterogeneous catalysts for asymmetric electrocarboxylation of (1-chloroethyl) benzene with CO2
CN106831583A (en) N, N dialkyl group substituted pyrazolecarboxylic ionic liquid, preparation method and its method for catalyzing and synthesizing propene carbonate
CN110201717B (en) Preparation method and application of copper-based metal organic polyhedral composite material
Ma et al. Preparation, characterization and application of sulfonated mesoporous hollow carbon microspheres

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20201225

CF01 Termination of patent right due to non-payment of annual fee