CN111234249B - Aliphatic tertiary amine functionalized chromium-based metal organic framework material and preparation method thereof - Google Patents
Aliphatic tertiary amine functionalized chromium-based metal organic framework material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of metal organic synthesis, and particularly relates to an aliphatic tertiary amine functionalized chromium-based metal organic framework material and a preparation method thereof. Firstly, preparing a formyl functionalized chromium-based metal organic framework material by taking a formyl pre-functionalized organic ligand and inorganic metal salt as raw materials and adopting a solvothermal method; and soaking the formyl functional material in a corresponding formamide organic compound, and carrying out reductive amination at a sufficient temperature by using formic acid as a reducing agent to prepare a corresponding aliphatic tertiary amine functional metal organic framework material. The method of the present invention has excellent flexibility, and can select wider conditions and substrates when introducing tertiary amine structures.
Description
Technical Field
The invention belongs to the technical field of metal organic synthesis, and particularly relates to an aliphatic tertiary amine functionalized chromium-based metal organic framework material and a preparation method thereof.
Background
Introduction of basic centers into material structures in the field of synthesis of multifunctional Metal-Organic frameworks (MOFs) has been a hot direction of research. The introduction of primary and secondary amines is relatively simple and has been widely studied, however, the introduction of tertiary amines with stronger basicity into the framework of MOFs is less reported, and the introduction of aliphatic tertiary amines is more difficult and serious, and at present, no method for introducing various aliphatic amines with broad spectrum, practicality and effectiveness is available.
Hyungwood Hahm et al reported that 2-dimethylaminoterephthalic acid and 1, 4-diazidobicyclo [2.2.2] octane are used as organic ligands and zinc nitrate is used as metal in 2015, so that aromatic tertiary amine functionalized DMOF-1 is constructed, and the synthetic route is as follows:
hyungwood Hahm et al reported in 2015 another reference aromatic tertiary amine functionalized UiO-66-NMe2The synthetic route is as follows:
from work by Hyungwoo Hahm et al, we found that they mainly used the synthesis of aromatic tertiary amine functionalized MOFs materials by using pre-functional organic ligands, and for the aromatic tertiary amines with simple structure, the influence on the synthesis of MOFs is not great, but for the aliphatic tertiary amines with longer chains is not sufficient.
Post-modification synthesis strategy is also a common strategy in the synthesis of functionalized MOFs, but only by adopting proper organic reaction and experimental conditions, the target material can be obtained. The first aliphatic tertiary amine functionalized MOFs materials were reported by Jinzhu Chen et al in 2014, and the synthetic route is as follows. The synthesis condition is potassium carbonate aqueous solution, the alkaline condition is not universal, and most MOFs materials cannot stably exist under water and alkaline conditions.
Disclosure of Invention
Aiming at the problems, the invention provides an aliphatic tertiary amine functionalized chromium-based metal organic framework material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
an aliphatic tertiary amine functionalized chromium-based metal organic framework material is prepared by the following steps:
step 1, dispersing a formyl functionalized organic ligand and chromium salt in deionized water, performing ultrasonic oscillation, performing a first heating reaction, cooling to room temperature, centrifuging to remove supernatant, washing with water, washing with a low-boiling-point organic solvent, and drying to obtain a formyl functionalized chromium-based metal organic framework material;
and 2, dispersing the formyl functionalized chromium-based metal organic framework material in a formamido compound, adding formic acid, performing ultrasonic oscillation, performing a second heating reaction, cooling to room temperature, centrifuging, washing with a low-boiling-point organic solvent, and drying to obtain the aliphatic tertiary amine functionalized chromium-based metal organic framework material.
Further, the formyl functionalized organic ligand in the step 1 is 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid; the chromium salt is chromium trichloride hexahydrate; the low-boiling-point organic solvent is any one of acetone, methanol and ethanol; in the step 2, the formamido compound is one or a mixture of several of N, N-dimethylformamide, N-diethylformamide, N-dipropylformamide, N-dibutylformamide, N-formylpiperidine or N-formylmorpholine in any proportion.
Further, the mole ratio of the formyl functionalized organic ligand to the chromium salt in the step 1 is 1: 1; the using amount of formic acid in the step 2 is 1-5 times of the molar weight of the formyl functionalized chromium-based metal organic framework material; in the step 2, the mole ratio of the formyl functionalized chromium-based metal organic framework material to the formyl amine compound is 1: 20-50. The synthesis reproducibility of the formyl functionalized chromium-based metal organic framework material is improved, and the proportion of modification after amino functionalization is improved.
Further, the oscillation time of the ultrasonic oscillation in the step 1 is 20 min; the heating temperature of the first heating reaction in the step 1 is 180-220 ℃, and the reaction time is 8 hours; the specific operation of water washing is repeated soaking and washing for 3 times by using deionized water, carrying out ultrasonic treatment for 30min, and soaking for 2 h; the specific operation of washing with the low-boiling-point organic solvent is to wash with the low-boiling-point organic solvent repeatedly for 3 times, perform ultrasonic treatment for 30min, and soak for 2 h; the drying condition is drying at 60 ℃ for 12 h. The heating reaction condition avoids side reaction of formyl radicals, and meanwhile, the formyl radical functionalized chromium-based metal organic framework material can be effectively synthesized.
Further, the oscillation time of the ultrasonic oscillation in the step 2 is 30 min; in the step 2, the second heating temperature is 120-160 ℃, and the reaction time is 24-48 h; the specific operation of washing with the low-boiling-point organic solvent in the step 2 is to repeatedly wash with the low-boiling-point organic solvent for 3 times, perform ultrasonic treatment for 30min, and soak for 6 h. The heating reaction conditions ensure the complete structure of the material and achieve higher modification ratio.
A preparation method of an aliphatic tertiary amine functionalized chromium-based metal organic framework material comprises the following steps:
step 1, dispersing a formyl functionalized organic ligand and chromium salt in deionized water, performing ultrasonic oscillation, performing a first heating reaction, cooling to room temperature, centrifuging to remove supernatant, washing with water, washing with a low-boiling-point organic solvent, and drying to obtain a formyl functionalized chromium-based metal organic framework material;
and 2, dispersing the formyl functionalized chromium-based metal organic framework material in a formamido compound, adding formic acid, performing ultrasonic oscillation, performing a second heating reaction, cooling to room temperature, centrifuging, washing with a low-boiling-point organic solvent, and drying to obtain the aliphatic tertiary amine functionalized chromium-based metal organic framework material.
Further, the formyl functionalized organic ligand in the step 1 is 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid; the chromium salt is chromium trichloride hexahydrate; the low-boiling-point organic solvent is any one of acetone, methanol and ethanol; in the step 2, the formamido compound is one or a mixture of several of N, N-dimethylformamide, N-diethylformamide, N-dipropylformamide, N-dibutylformamide, N-formylpiperidine or N-formylmorpholine in any proportion.
Further, the mole ratio of the formyl functionalized organic ligand to the chromium salt in the step 1 is 1: 1; the using amount of formic acid in the step 2 is 1-5 times of the molar weight of the formyl functionalized chromium-based metal organic framework material; in the step 2, the mole ratio of the formyl functionalized chromium-based metal organic framework material to the formyl amine compound is 1: 20-50.
Further, the oscillation time of the ultrasonic oscillation in the step 1 is 20 min; the heating temperature of the first heating reaction in the step 1 is 180-220 ℃, and the reaction time is 8 hours; the specific operation of water washing is repeated soaking and washing for 3 times by using deionized water, carrying out ultrasonic treatment for 30min, and soaking for 2 h; the specific operation of washing with the low-boiling-point organic solvent is to wash with the low-boiling-point organic solvent repeatedly for 3 times, perform ultrasonic treatment for 30min, and soak for 2 h; the drying condition is drying at 60 ℃ for 12 h.
Further, the oscillation time of the ultrasonic oscillation in the step 2 is 30 min; in the step 2, the second heating temperature is 120-160 ℃, and the reaction time is 24-48 h; the specific operation of washing with the low-boiling-point organic solvent in the step 2 is to repeatedly wash with the low-boiling-point organic solvent for 3 times, perform ultrasonic treatment for 30min, and soak for 6 h.
The invention is as follows
Compared with the prior art, the invention has the following advantages:
chromium trichloride hexahydrate is used as a chromium ion source, so that the oxidation reaction of a ligand can be avoided; the metal ions without coordination can be removed by adopting water washing; water molecules in the pore channel can be exchanged by adopting a low-boiling point solvent for washing; tertiary amines of different volume sizes can be prepared using different carboxamides.
The aliphatic tertiary amine functionalized chromium-based metal organic framework material is obtained with higher yield through the reaction; the method has simple synthesis, easily obtained raw materials and convenient large-scale preparation; the method is ingenious and flexible, and the size of the material pore canal can be effectively controlled; the reaction is carried out in acidic and corresponding organic solvents, which is beneficial to expanding the method to more MOFs materials which are unstable to water and alkali.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of MIL-101-CHO;
FIG. 2 shows MIL-101-CH2N(CH3)2Scanning Electron Microscope (SEM) images.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, chromium trichloride hexahydrate (analytical grade, national pharmaceutical group chemical); n, N-dimethylformamide (99.5%, analytical purity, njn chemical reagents ltd, tianjin); methanol, ethanol and acetone (analytical grade, Shentai chemical reagents science and technology, Inc., Tianjin); n, N-diethylformamide, N-dipropylformamide, N-dibutylformamide, N-formylpiperidine, N-formylmorpholine (Shanghai Allantin reagent Co., Ltd.).
DHG-9070A electric heating constant temperature air-blast drying oven, a polytetrafluoroethylene lining stainless steel reaction kettle and a TG-16 high-speed centrifuge (Steheny City Waxihua instruments, Ltd.); CP214 electronic balance (aohaus instruments ltd).
Example 1
Weighing 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid (64mg,0.33mmol) and chromium trichloride hexahydrate (88mg,0.33mmol) into a 23mL polytetrafluoroethylene lining, adding 3mL deionized water, oscillating the reaction liquid in ultrasonic waves for 20min, sealing the polytetrafluoroethylene lining with a stainless steel sleeve, and placing the sealed polytetrafluoroethylene lining in an oven preheated to 180 ℃ for heating for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, the reaction liquid is transferred to a 15mL centrifuge tube, and supernatant liquid is removed by centrifugation; repeatedly soaking and washing with deionized water for 3 times, adding 10mL of deionized water each time, performing ultrasonic treatment for 30min, and soaking for 2 h; repeatedly washing with methanol for 3 times, adding 10mL methanol each time, ultrasonic treating for 30min, and soaking for 2 h; after the supernatant was removed by pouring, the mixture was dried at 60 ℃ for 12 hours to obtain white solid formyl-functionalized MIL-101-CHO, 64mg, with a yield of 79%. FIG. 1 shows the MIL-101-CHO scanning electron micrograph.
Adding MIL-101-CHO (100mg,0.41mmol calculated by ligand) into 23mL of polytetrafluoroethylene lining, neutralizing HCOOH (83 μ L,2.05mmol) with N, N-dimethylformamide (3mL,38.5mmol) as shown in a MIL-101-CHO Scanning Electron Microscope (SEM) of figure 1, oscillating in ultrasonic wave for 30min to disperse uniformly, sealing with a stainless steel sleeve, and heating in an oven preheated to 120 ℃ for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, the reaction liquid is transferred to a 15mL centrifuge tube, repeatedly washed for 3 times by methanol, 10mL methanol is added each time, ultrasonic treatment is carried out for 30min, and soaking is carried out for 6 h; pouring to remove supernatant, and drying at 60 deg.C for 12 hr to obtain white solid formyl functionalized MIL-101-CH2N(CH3)281mg, the tertiary amine functionalization modification ratio is 100%. As shown in FIG. 2MIL-101-CH2N(CH3)2Scanning Electron Microscopy (SEM). Hair-like device
The way is as follows:
example 2
Weighing 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid (64mg,0.33mmol) and chromium trichloride hexahydrate (88mg,0.33mmol) into a 23mL polytetrafluoroethylene lining, adding 3mL deionized water, oscillating the reaction liquid in ultrasonic waves for 20min, sealing the polytetrafluoroethylene lining with a stainless steel sleeve, and placing the sealed polytetrafluoroethylene lining in an oven preheated to 200 ℃ for heating for 8 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, the reaction liquid is transferred to a 15mL centrifuge tube, and supernatant liquid is removed by centrifugation; repeatedly soaking and washing with deionized water for 3 times, adding 10mL of deionized water each time, performing ultrasonic treatment for 30min, and soaking for 2 h; repeatedly washing with acetone for 3 times, adding 10mL deionized water each time, performing ultrasonic treatment for 30min, and soaking for 2 h; after the supernatant was removed by pouring, the mixture was dried at 60 ℃ for 12 hours to obtain white solid formyl-functionalized MIL-101-CHO, 68mg, with a yield of 84%.
Adding MIL-101-CHO (100mg,0.41mmol calculated by ligand) and N, N-diethylformamide (4mL,35.6mmol) to neutralize HCOOH (83 mu L,2.05mmol) in 23mL of polytetrafluoroethylene lining, oscillating for 30min in ultrasonic wave to uniformly disperse, sealing a stainless steel sleeve, and then placing in an oven preheated to 140 ℃ to heat for 36 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, the reaction liquid is transferred to a 15mL centrifuge tube, repeated washing is carried out for 3 times by using ethanol, 10mL ethanol is added each time, ultrasonic treatment is carried out for 30min, and soaking is carried out for 6 h; pouring to remove supernatant, and drying at 60 deg.C for 12 hr to obtain white solid formyl functionalized MIL-101-CH2N(CH2CH3)279mg, the proportion of tertiary amine functionalized modification is 90%.
Example 3
Weighing 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid (64mg,0.33mmol) and chromium trichloride hexahydrate (88mg,0.33mmol) into a 23mL polytetrafluoroethylene lining, adding 3mL deionized water, oscillating the reaction liquid in ultrasonic waves for 20min, sealing the polytetrafluoroethylene lining with a stainless steel sleeve, and placing the sealed polytetrafluoroethylene lining in an oven preheated to 220 ℃ for heating for 8 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, the reaction liquid is transferred to a 15mL centrifuge tube, and supernatant liquid is removed by centrifugation; repeatedly soaking and washing with deionized water for 3 times, adding 10mL of deionized water each time, performing ultrasonic treatment for 30min, and soaking for 2 h; repeatedly washing with ethanol for 3 times, adding 10mL ethanol each time, ultrasonic treating for 30min, and soaking for 2 h; after the supernatant was removed by pouring, the mixture was dried at 60 ℃ for 12 hours to obtain white solid formyl-functionalized MIL-101-CHO, 63mg, with a yield of 84%.
Adding MIL-101-CHO (100mg,0.41mmol calculated by ligand) and N, N-dipropyl formamide (4mL,27.6mmol) to 23mL of polytetrafluoroethylene lining to neutralize HCOOH (83 μ L,2.05mmol), oscillating in ultrasonic wave for 30min to disperse uniformly, sealing with stainless steel sleeve, and placing in a preheating chamberHeating in an oven at 140 ℃ for 36 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, the reaction liquid is transferred to a 15mL centrifuge tube, repeated washing is carried out for 3 times by using ethanol, 10mL ethanol is added each time, ultrasonic treatment is carried out for 30min, and soaking is carried out for 6 h; pouring to remove supernatant, and drying at 60 deg.C for 12 hr to obtain white solid formyl functionalized MIL-101-CH2N(CH2CH2CH3)279mg, 84% tertiary amine functionalization modification.
Example 4
Weighing 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid (64mg,0.33mmol) and chromium trichloride hexahydrate (88mg,0.33mmol) into a 23mL polytetrafluoroethylene lining, adding 3mL deionized water, oscillating the reaction liquid in ultrasonic waves for 20min, sealing the polytetrafluoroethylene lining with a stainless steel sleeve, and placing the sealed polytetrafluoroethylene lining in an oven preheated to 220 ℃ for heating for 8 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, the reaction liquid is transferred to a 15mL centrifuge tube, and supernatant liquid is removed by centrifugation; repeatedly soaking and washing with deionized water for 3 times, adding 10mL of deionized water each time, performing ultrasonic treatment for 30min, and soaking for 2 h; repeatedly washing with methanol for 3 times, adding 10mL methanol each time, ultrasonic treating for 30min, and soaking for 2 h; after the supernatant was removed by pouring, the mixture was dried at 60 ℃ for 12 hours to obtain white solid formyl-functionalized MIL-101-CHO, 75mg, with a yield of 93%.
Adding MIL-101-CHO (100mg,0.41mmol calculated by ligand) and N, N-dibutylformamide (4mL,21.8mmol) to neutralize HCOOH (83 mu L,2.05mmol) in 23mL of polytetrafluoroethylene lining, oscillating for 30min in ultrasonic wave to uniformly disperse, sealing a stainless steel sleeve, and then placing in an oven preheated to 160 ℃ to heat for 36 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, the reaction liquid is transferred to a 15mL centrifuge tube, washing is repeatedly carried out for 3 times by using propanol, 10mL propanol is added each time, ultrasonic treatment is carried out for 30min, and soaking is carried out for 6 h; pouring to remove supernatant, and drying at 60 deg.C for 12 hr to obtain white solid formyl functionalized MIL-101-CH2N(CH2CH2CH2CH3)280mg, the tertiary amine functionalization modification ratio is 78%.
Example 5
Weighing 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid (64mg,0.33mmol) and chromium trichloride hexahydrate (88mg,0.33mmol) into a 23mL polytetrafluoroethylene lining, adding 3mL deionized water, oscillating the reaction liquid in ultrasonic waves for 20min, sealing the polytetrafluoroethylene lining with a stainless steel sleeve, and placing the sealed polytetrafluoroethylene lining in an oven preheated to 220 ℃ for heating for 8 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, the reaction liquid is transferred to a 15mL centrifuge tube, and supernatant liquid is removed by centrifugation; repeatedly soaking and washing with deionized water for 3 times, adding 10mL of deionized water each time, performing ultrasonic treatment for 30min, and soaking for 2 h; repeatedly washing with methanol for 3 times, adding 10mL methanol each time, ultrasonic treating for 30min, and soaking for 2 h. After the supernatant was removed by pouring, the mixture was dried at 60 ℃ for 12 hours to obtain white solid formyl-functionalized MIL-101-CHO, 75mg, with a yield of 93%.
Adding MIL-101-CHO (100mg,0.41mmol calculated by ligand) and N-formylpiperidine (4mL, 36mmol) into 23mL of polytetrafluoroethylene lining to neutralize HCOOH (83 mu L,2.05mmol), oscillating in ultrasonic wave for 30min to disperse uniformly, sealing with a stainless steel sleeve, and heating in an oven preheated to 120 ℃ for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, the reaction liquid is transferred to a 15mL centrifuge tube, repeatedly washed for 3 times by methanol, 10mL methanol is added each time, ultrasonic treatment is carried out for 30min, and soaking is carried out for 6 h; pouring to remove supernatant, and drying at 60 deg.C for 12 hr to obtain white solid formyl functionalized MIL-101-CH2N(CH2)585mg, the tertiary amine functionalization modification ratio is 89%.
Example 6
Weighing 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid (64mg,0.33mmol) and chromium trichloride hexahydrate (88mg,0.33mmol) into a 23mL polytetrafluoroethylene lining, adding 3mL deionized water, oscillating the reaction liquid in ultrasonic waves for 20min, sealing the polytetrafluoroethylene lining with a stainless steel sleeve, and placing the sealed polytetrafluoroethylene lining in an oven preheated to 220 ℃ for heating for 8 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, the reaction liquid is transferred to a 15mL centrifuge tube, and supernatant liquid is removed by centrifugation; repeatedly soaking and washing with deionized water for 3 times, adding 10mL of deionized water each time, performing ultrasonic treatment for 30min, and soaking for 2 h; repeatedly washing with methanol for 3 times, adding 10mL methanol each time, ultrasonic treating for 30min, and soaking for 2 h; after the supernatant was removed by pouring, the mixture was dried at 60 ℃ for 12 hours to obtain white solid formyl-functionalized MIL-101-CHO, 75mg, with a yield of 93%.
Adding MIL-101-CHO (100mg,0.41mmol calculated by ligand) and N-formyl morpholine (4mL, 39.7mmol) into 23mL of polytetrafluoroethylene lining to neutralize HCOOH (83 mu L,2.05mmol), oscillating in ultrasonic wave for 30min to disperse uniformly, sealing a stainless steel sleeve, and placing in an oven preheated to 120 ℃ to heat for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, the reaction liquid is transferred to a 15mL centrifuge tube, repeatedly washed for 3 times by methanol, 10mL methanol is added each time, ultrasonic treatment is carried out for 30min, and soaking is carried out for 6 h; pouring to remove supernatant, and drying at 60 deg.C for 12 hr to obtain white solid formyl functionalized MIL-101-CH2N(CH2)4O, 81mg, the proportion of tertiary amine functionalized modification was 88%.
Those skilled in the art will appreciate that the invention may be practiced without these specific details. Although illustrative embodiments of the present invention have been described above to facilitate the understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, and various changes may be made apparent to those skilled in the art as long as they are within the spirit and scope of the present invention as defined and defined by the appended claims, and all matters of the invention which utilize the inventive concepts are protected.
Claims (10)
1. An aliphatic tertiary amine functionalized chromium-based metal organic framework material is characterized in that: is prepared by the following steps:
step 1, dispersing a formyl functionalized organic ligand and chromium salt in deionized water, performing ultrasonic oscillation, performing a first heating reaction, cooling to room temperature, centrifuging to remove supernatant, washing with water, washing with a low-boiling-point organic solvent, and drying to obtain a formyl functionalized chromium-based metal organic framework material;
step 2, dispersing the formyl functionalized chromium-based metal organic framework material in a formamido compound, adding formic acid, performing ultrasonic oscillation, performing a second heating reaction, cooling to room temperature, centrifuging, washing with a low-boiling-point organic solvent, and drying to obtain an aliphatic tertiary amine functionalized chromium-based metal organic framework material;
the formyl functionalized organic ligand in the step 1 is 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid; the chromium salt is chromium trichloride hexahydrate;
the heating temperature of the first heating reaction in the step 1 is 180-220 ℃, and the reaction time is 8 hours.
2. The aliphatic tertiary amine functionalized chromium-based metal organic framework material of claim 1, wherein: the low-boiling-point organic solvent in the step 1 is any one of acetone, methanol and ethanol; in the step 2, the formamido compound is one or a mixture of several of N, N-dimethylformamide, N-diethylformamide, N-dipropylformamide, N-dibutylformamide, N-formylpiperidine or N-formylmorpholine in any proportion.
3. The aliphatic tertiary amine functionalized chromium-based metal organic framework material of claim 1, wherein: the mole ratio of the formyl functional organic ligand to the chromium salt in the step 1 is 1: 1; the using amount of formic acid in the step 2 is 1-5 times of the molar weight of the formyl functionalized chromium-based metal organic framework material; in the step 2, the mole ratio of the formyl functionalized chromium-based metal organic framework material to the formyl amine compound is 1: 20-50.
4. The aliphatic tertiary amine functionalized chromium-based metal organic framework material of claim 1, wherein: the oscillation time of the ultrasonic oscillation in the step 1 is 20 min; the specific operation of water washing is repeated soaking and washing for 3 times by using deionized water, carrying out ultrasonic treatment for 30min, and soaking for 2 h; the specific operation of washing with the low-boiling-point organic solvent is to wash with the low-boiling-point organic solvent repeatedly for 3 times, perform ultrasonic treatment for 30min, and soak for 2 h; the drying condition is drying at 60 ℃ for 12 h.
5. The aliphatic tertiary amine functionalized chromium-based metal organic framework material of claim 1, wherein: the oscillation time of the ultrasonic oscillation in the step 2 is 30 min; in the step 2, the second heating temperature is 120-160 ℃, and the reaction time is 24-48 h; the specific operation of washing with the low-boiling-point organic solvent in the step 2 is to repeatedly wash with the low-boiling-point organic solvent for 3 times, perform ultrasonic treatment for 30min, and soak for 6 h.
6. A preparation method of an aliphatic tertiary amine functionalized chromium-based metal organic framework material is characterized by comprising the following steps: the method comprises the following steps:
step 1, dispersing a formyl functionalized organic ligand and chromium salt in deionized water, performing ultrasonic oscillation, performing a first heating reaction, cooling to room temperature, centrifuging to remove supernatant, washing with water, washing with a low-boiling-point organic solvent, and drying to obtain a formyl functionalized chromium-based metal organic framework material;
step 2, dispersing the formyl functionalized chromium-based metal organic framework material in a formamido compound, adding formic acid, performing ultrasonic oscillation, performing a second heating reaction, cooling to room temperature, centrifuging, washing with a low-boiling-point organic solvent, and drying to obtain an aliphatic tertiary amine functionalized chromium-based metal organic framework material;
the formyl functionalized organic ligand in the step 1 is 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid; the chromium salt is chromium trichloride hexahydrate;
the heating temperature of the first heating reaction in the step 1 is 180-220 ℃, and the reaction time is 8 hours.
7. The method for preparing the aliphatic tertiary amine functionalized chromium-based metal organic framework material according to claim 6, wherein the method comprises the following steps: the low-boiling-point organic solvent in the step 1 is any one of acetone, methanol and ethanol; in the step 2, the formamido compound is one or a mixture of several of N, N-dimethylformamide, N-diethylformamide, N-dipropylformamide, N-dibutylformamide, N-formylpiperidine or N-formylmorpholine in any proportion.
8. The method for preparing the aliphatic tertiary amine functionalized chromium-based metal organic framework material according to claim 6, wherein the method comprises the following steps: the mole ratio of the formyl functional organic ligand to the chromium salt in the step 1 is 1: 1; the using amount of formic acid in the step 2 is 1-5 times of the molar weight of the formyl functionalized chromium-based metal organic framework material; in the step 2, the mole ratio of the formyl functionalized chromium-based metal organic framework material to the formyl amine compound is 1: 20-50.
9. The method for preparing the aliphatic tertiary amine functionalized chromium-based metal organic framework material according to claim 6, wherein the method comprises the following steps: the oscillation time of the ultrasonic oscillation in the step 1 is 20 min; the specific operation of water washing is repeated soaking and washing for 3 times by using deionized water, carrying out ultrasonic treatment for 30min, and soaking for 2 h; the specific operation of washing with the low-boiling-point organic solvent is to wash with the low-boiling-point organic solvent repeatedly for 3 times, perform ultrasonic treatment for 30min, and soak for 2 h; the drying condition is drying at 60 ℃ for 12 h.
10. The method for preparing the aliphatic tertiary amine functionalized chromium-based metal organic framework material according to claim 6, wherein the method comprises the following steps: the oscillation time of the ultrasonic oscillation in the step 2 is 30 min; in the step 2, the second heating temperature is 120-160 ℃, and the reaction time is 24-48 h; the specific operation of washing with the low-boiling-point organic solvent in the step 2 is to repeatedly wash with the low-boiling-point organic solvent for 3 times, perform ultrasonic treatment for 30min, and soak for 6 h.
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| CN109608655A (en) * | 2019-01-24 | 2019-04-12 | 南京大学 | A kind of bifunctional group MOFs material and the preparation method and application thereof |
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