CN111303440B - Aliphatic tertiary amine functional zirconium-based metal organic framework material and preparation method thereof - Google Patents
Aliphatic tertiary amine functional zirconium-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 functional zirconium-based metal organic framework material and a preparation method thereof. Firstly, preparing a formyl functionalized zirconium-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 under an acidic condition; 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 invention reacts to obtain tertiary amine functional zirconium-based metal organic framework material; the method has simple synthesis, easily obtained raw materials and convenient large-scale preparation; the selection method is ingenious and flexible, and the size of the pore channel of the material can be effectively controlled.
Description
Technical Field
The invention belongs to the technical field of metal organic synthesis, and particularly relates to an aliphatic tertiary amine functional zirconium-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 relatively simple primary amine and secondary amine has been widely studied, however, the introduction of tertiary amine with stronger basicity is less reported, and the introduction of aliphatic tertiary amine is more difficult, and at present, no broad-spectrum practical and effective method for introducing various aliphatic amines 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 zirconium-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 zirconium-based metal organic framework material is prepared by the following steps:
and 2, dispersing the formyl functional zirconium-based metal organic framework material in a formamido compound, adding formic acid, performing ultrasonic oscillation, performing a second heating reaction, cooling to room temperature, performing suction filtration, and washing a filter cake with a low-boiling-point organic solvent B to obtain the aliphatic tertiary amine functional zirconium-based metal organic framework material.
Further, the formyl functionalized organic ligand in the step 1 is 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-carboxylic acid or 2' -formyl- [1,1':4', 1' -terphenyl ] -4, 4' -dicarboxylic acid; the zirconium salt is anhydrous zirconium tetrachloride or zirconyl chloride; the specific acid is any one of glacial acetic acid, hydrochloric acid, benzoic acid or L-proline; the low-boiling-point organic solvent A in the step 1 is any one of acetone, methanol, diethyl ether or dichloromethane.
Further, in the step 2, the formylamine compound is any one of N, N-dimethylformamide, N-diethylformamide, N-dipropylformamide, N-dibutylformamide, N-formylpiperidine or N-formylmorpholine; the low-boiling-point organic solvent B in the step 2 is any one of acetone, diethyl ether or dichloromethane.
Further, the mole ratio of the formyl functionalized organic ligand to the zirconium salt in the step 1 is 1: 1-1.5; the mole ratio of the formyl functional organic ligand to the specific acid is 1: 5-15; the using amount of formic acid in the step 2 is 1-5 times of the molar weight of the formyl functionalized zirconium-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 reaction temperature of the first heating reaction in the step 1 is 70-80 ℃, and the reaction time of the first heating reaction is 24-36 hours; the oscillation time of the ultrasonic oscillation is 30 min; the reaction temperature of the second heating reaction in the step 2 is 120-160 ℃, and the reaction time of the second heating reaction is 24-48 h. The first heating reaction in the step 1 avoids side reaction of formyl radicals, and meanwhile, the formyl functional zirconium-based metal organic framework material can be effectively synthesized; the heating reaction in step 2 ensures the structural integrity of the material and simultaneously achieves a higher modification ratio.
A preparation method of an aliphatic tertiary amine functionalized zirconium-based metal organic framework material comprises the following steps:
and 2, dispersing the formyl functional zirconium-based metal organic framework material in a formamido compound, adding formic acid, performing ultrasonic oscillation, performing a second heating reaction, cooling to room temperature, performing suction filtration, and washing a filter cake with a low-boiling-point organic solvent B to obtain the aliphatic tertiary amine functional zirconium-based metal organic framework material.
Further, the formyl functionalized organic ligand in the step 1 is 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-carboxylic acid or 2' -formyl- [1,1':4', 1' -terphenyl ] -4, 4' -dicarboxylic acid; the zirconium salt is anhydrous zirconium tetrachloride or zirconyl chloride; the specific acid is any one of glacial acetic acid, hydrochloric acid, benzoic acid or L-proline; the low-boiling-point organic solvent A in the step 1 is any one of acetone, methanol, diethyl ether or dichloromethane.
Further, in the step 2, the formylamine compound is any one of N, N-dimethylformamide, N-diethylformamide, N-dipropylformamide, N-dibutylformamide, N-formylpiperidine or N-formylmorpholine; the low-boiling-point organic solvent B in the step 2 is any one of acetone, diethyl ether or dichloromethane.
Further, the mole ratio of the formyl functionalized organic ligand to the zirconium salt in the step 1 is 1: 1-1.5; the mole ratio of the formyl functional organic ligand to the specific acid is 1: 5-15; the using amount of formic acid in the step 2 is 1-5 times of the molar weight of the formyl functionalized zirconium-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 reaction temperature of the first heating reaction in the step 1 is 70-80 ℃, and the reaction time of the first heating reaction is 24-36 hours; the oscillation time of the ultrasonic oscillation is 30 min; the reaction temperature of the second heating reaction in the step 2 is 120-160 ℃, and the reaction time of the second heating reaction is 24-48 h.
The synthetic route is as follows:
compared with the prior art, the invention has the following advantages:
the synthesis reproducibility of the formyl functionalized zirconium-based metal organic framework material is improved, and the proportion of post-modification is improved; formic acid is an indispensable reducing agent in the reaction, and meanwhile, the proportion of tertiary amine functionalization of the MOFs material is improved, and the phenomenon that the structure of the material is damaged by too strong acid is effectively avoided. The MOFs materials with two different channels are modified to obtain different tertiary amine functionalized materials, and the flexibility of the invention is presented.
Reacting to obtain an aliphatic tertiary amine functionalized zirconium-based metal organic framework material; the method has simple synthesis, easily obtained raw materials and convenient large-scale preparation; the selection method is ingenious and flexible, and the size of the pore channel of the material 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 shows UiO-66-CHO and UiO-66-CH2N(CH3)2An X-ray powder diffraction (PXRD) pattern of (a);
FIG. 2 is a Scanning Electron Microscope (SEM) image of UiO-66-CHO;
FIG. 3 shows UiO-66-CH2N(CH3)2Scanning Electron Microscope (SEM) images of (a).
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, acetic anhydride, anhydrous zirconium chloride, zirconium oxychloride (analytical grade, national pharmaceutical group chemical); glacial acetic acid (analytically pure, majon chemical reagents works, Tianjin); n, N-dimethylformamide (99.5%, analytical purity, njn chemical reagents ltd, tianjin); hydrochloric acid HCl (98%, gagao gao qiao chemical limited); anhydrous methanol, diethyl ether, dichloromethane, acetone (analytically pure, shentai chemical reagents science and technology limited, 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 box, SH2-D (III) circulating water type vacuum pump, and a stainless steel reaction kettle (Steud City Waishi Limited liability company); CP214 electronic balance (aohaus instruments ltd).
Example 1
Weighing 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid (64mg,0.33mmol), anhydrous zirconium chloride (77mg,0.33mmol) and glacial acetic acid (396mg,6.6mmol) into a polytetrafluoroethylene lining of 23mL, adding N, N-dimethylformamide of 3mL, oscillating the reaction solution in ultrasonic wave for 30min, sealing the polytetrafluoroethylene lining with a stainless steel sleeve, and placing the sealed polytetrafluoroethylene lining in an oven preheated to 80 ℃ for heating for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of N, N-dimethylformamide for a small amount, then repeatedly washed by 20mL of methanol for a small amount, and the filtering is continued until a product is dried; thus obtaining white solid formyl functionalized UiO-66-CHO with 82mg and 81% yield. FIG. 1 (bottom) shows the X-ray powder diffraction (PXRD) pattern of UiO-66-CHO. FIG. 2 shows a Scanning Electron Microscope (SEM) image of UiO-66-CHO.
Adding UiO-66-CHO (50mg,0.16mmol calculated by ligand) and 3mL of N, N-dimethylformamide (neutralized HCOOH) (65 mu L,1.6mmol) into 23mL of polytetrafluoroethylene lining, oscillating in ultrasonic wave for 30min to disperse uniformly, sealing a stainless steel sleeve, and then placing in an oven preheated to 120 ℃ for heating for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of methanol for a few times, and the filtering is continued until a product is dried; obtaining white solid formyl functionalized UiO-66-CH2N(CH3)248mg, and the tertiary amine modification ratio is 95%. As shown in FIG. 1 (top), is UiO-66-CH2N(CH3)2X-ray powder diffraction (PXRD) pattern of (a). As shown in FIG. 3, is UiO-66-CH2N(CH3)2Scanning Electron Microscope (SEM) images of (a).
Example 2
Weighing 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid (64mg,0.33mmol), anhydrous zirconium chloride (77mg,0.33mmol) and concentrated hydrochloric acid (0.5mL, 5.9mmol), putting into 23mL of polytetrafluoroethylene lining, adding 3mL of N, N-dimethylformamide, oscillating the reaction solution in ultrasonic waves for 30min, sealing the polytetrafluoroethylene lining with a stainless steel sleeve, and placing in an oven preheated to 80 ℃ for heating for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of N, N-dimethylformamide for a small amount, then repeatedly washed by 20mL of methanol for a small amount, and the filtering is continued until a product is dried; thus obtaining white solid formyl functionalized UiO-66-CHO with yield of 73 mg.
Adding UO-66-CHO (50mg,0.16mmol calculated by ligand) and 3mL of N, N-diethylformamide neutralized HCOOH (130 muL, 3.2mmol) into 23mL of polytetrafluoroethylene lining, oscillating in ultrasonic wave for 30min to disperse uniformly, sealing with a stainless steel sleeve, and heating in an oven preheated to 120 ℃ for 36 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of methanol for a few times, and the filtering is continued until a product is dried; obtaining white solid UiO-66-CH2N(CH2CH3)239mg, and the tertiary amine modification ratio is 85%.
Example 3
Weighing 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid (64mg,0.33mmol), anhydrous zirconium chloride (77mg,0.33mmol) and benzoic acid (403mg, 3.3mmol) into a polytetrafluoroethylene lining of 23mL, adding N, N-dimethylformamide of 3mL, oscillating the reaction solution in ultrasonic wave for 30min, sealing the polytetrafluoroethylene lining with a stainless steel sleeve, and heating in an oven preheated to 80 ℃ for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of N, N-dimethylformamide for a small amount, then repeatedly washed by 20mL of methanol for a small amount, and the filtering is continued until a product is dried; thus obtaining white solid formyl functionalized UiO-66-CHO with 65mg and 64 percent of yield.
Adding UO-66-CHO (50mg,0.16mmol calculated by ligand) and 3mL of N, N-dipropyl formamide neutralized HCOOH (130 muL, 3.2mmol) into 23mL of polytetrafluoroethylene lining, oscillating for 30min in ultrasonic wave to disperse uniformly, sealing a stainless steel sleeve, and placing in an oven preheated to 120 ℃ for heating for 36 h; after the heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, the reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of methanol for a few times, and thenContinuing suction filtering until the product is dried; obtaining white solid UiO-66-CH2N(CH2CH2CH3)236mg, tertiary amine modification ratio 71%.
Example 4
Weighing 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid (64mg,0.33mmol), anhydrous zirconium chloride (77mg,0.33mmol) and glacial acetic acid (396mg,6.6mmol) into a polytetrafluoroethylene lining of 23mL, adding N, N-dimethylformamide of 3mL, oscillating the reaction solution in ultrasonic wave for 30min, sealing the polytetrafluoroethylene lining with a stainless steel sleeve, and placing the sealed polytetrafluoroethylene lining in an oven preheated to 80 ℃ for heating for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of N, N-dimethylformamide for a small amount, then repeatedly washed by 20mL of methanol for a small amount, and the filtering is continued until a product is dried; thus obtaining white solid formyl functionalized UiO-66-CHO with 82mg and 81% yield.
Adding UO-66-CHO (50mg,0.16mmol calculated by ligand) and 3mL of N, N-dibutylformamide neutralized HCOOH (130 muL, 3.2mmol) into 23mL of polytetrafluoroethylene lining, oscillating in ultrasonic wave for 30min to disperse uniformly, sealing with a stainless steel sleeve, and heating in an oven preheated to 120 ℃ for 36 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of methanol for a few times, and the filtering is continued until a product is dried; obtaining white solid UiO-66-CH2N(CH2CH2CH2CH3)246mg, tertiary amine modification ratio 40%.
Example 5
Weighing 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid (64mg,0.33mmol), anhydrous zirconium chloride (77mg,0.33mmol) and glacial acetic acid (396mg,6.6mmol) into a polytetrafluoroethylene lining of 23mL, adding N, N-dimethylformamide of 3mL, oscillating the reaction solution in ultrasonic wave for 30min, sealing the polytetrafluoroethylene lining with a stainless steel sleeve, and placing the sealed polytetrafluoroethylene lining in an oven preheated to 80 ℃ for heating for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of N, N-dimethylformamide for a small amount, then repeatedly washed by 20mL of methanol for a small amount, and the filtering is continued until a product is dried; thus obtaining white solid formyl functionalized UiO-66-CHO with 82mg and 81% yield.
Adding UiO-66-CHO (50mg,0.16mmol calculated by ligand) and 3mL of N-formylpiperidine neutralized HCOOH (130 muL, 3.2mmol) into 23mL of polytetrafluoroethylene lining, oscillating in ultrasonic wave for 30min to disperse uniformly, sealing with a stainless steel sleeve, and heating in an oven preheated to 120 ℃ for 36 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of methanol for a few times, and the filtering is continued until a product is dried; obtaining white solid UiO-66-CH2N(CH2)543mg, tertiary amine modification ratio 77%.
Example 6
Weighing 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid (64mg,0.33mmol), anhydrous zirconium chloride (77mg,0.33mmol) and glacial acetic acid (396mg,6.6mmol) into a polytetrafluoroethylene lining of 23mL, adding N, N-dimethylformamide of 3mL, oscillating the reaction solution in ultrasonic wave for 30min, sealing the polytetrafluoroethylene lining with a stainless steel sleeve, and placing the sealed polytetrafluoroethylene lining in an oven preheated to 80 ℃ for heating for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of N, N-dimethylformamide for a small amount, then repeatedly washed by 20mL of methanol for a small amount, and the filtering is continued until a product is dried; thus obtaining white solid formyl functionalized UiO-66-CHO with 82mg and 81% yield.
Adding UiO-66-CHO (50mg,0.16mmol calculated by ligand) and 3mL of N-formylmorpholine neutralized HCOOH (130 muL, 3.2mmol) into 23mL of polytetrafluoroethylene lining, oscillating in ultrasonic wave for 30min to disperse uniformly, sealing with a stainless steel sleeve, and heating in an oven preheated to 120 ℃ for 36 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of methanol for a few times, and the filtering is continued until a product is dried; obtaining white solid UiO-66-CH2N(CH)2O, 45mg, and the tertiary amine modification ratio is 78%.
Example 7
2' -formyl- [1,1':4', 1' -terphenyl ] -4, 4' -dicarboxylic acid (60mg,0.17mmol), anhydrous zirconium chloride (61mg,0.26mmol) and glacial acetic acid (204mg,3.4mmol,20eq) are put into a polytetrafluoroethylene lining of 23mL, N-dimethylformamide of 3mL is added, the reaction solution is shaken in ultrasonic waves for 30min, then the polytetrafluoroethylene lining is sealed by a stainless steel sleeve and placed in an oven preheated to 80 ℃ for heating for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of N, N-dimethylformamide for a small amount, then repeatedly washed by 20mL of acetone for a small amount, and the filtering is continued until a product is dried; thus obtaining white solid formyl functionalized UiO-68-CHO with yield of 81 percent of 74 mg.
Adding UO-68-CHO (50mg,0.16mmol calculated by ligand) and 3mL of N, N-dimethylformamide (neutralizing HCOOH) (130 mu L,3.2mmol) into 23mL of polytetrafluoroethylene lining, oscillating in ultrasonic wave for 30min, dispersing uniformly, sealing with a stainless steel sleeve, and heating in an oven preheated to 120 ℃ for 36 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by a small amount of 20mL acetone for many times, and the filtering is continued until a product is dried; obtaining white solid UiO-66-CH2N(CH3)239mg, the tertiary amine modification ratio is 100%.
Example 8
2' -formyl- [1,1':4', 1' -terphenyl ] -4, 4' -dicarboxylic acid (60mg,0.17mmol), anhydrous zirconium chloride (61mg,0.26mmol) and concentrated hydrochloric acid (0.5mL, 5.9mmol, 35eq) are put into a polytetrafluoroethylene lining of 23mL, N-dimethylformamide of 3mL is added, the reaction solution is vibrated for 30min in ultrasonic waves, then the polytetrafluoroethylene lining is sealed by a stainless steel sleeve and placed in an oven preheated to 80 ℃ for heating for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of N, N-dimethylformamide for a small amount, then repeatedly washed by 20mL of acetone for a small amount, and the filtering is continued until a product is dried; thus obtaining white solid formyl functionalized UiO-68-CHO with yield of 85 mg.
To 23mL of polytetrafluoroethylene liner was added UiO-68-CHO (50mg,0.16 m)mol is calculated by ligand), 3mL of N, N-diethylformamide is used for neutralizing HCOOH (130 mu L,3.2mmol), the mixture is vibrated in ultrasonic waves for 30min and uniformly dispersed, and the mixture is placed in an oven preheated to 120 ℃ for heating for 36h after being sealed by a stainless steel sleeve; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by a small amount of 20mL acetone for many times, and the filtering is continued until a product is dried; obtaining white solid UiO-66-CH2N(CH2CH3)242mg, and the tertiary amine modification ratio is 91%.
Example 9
2' -formyl- [1,1':4', 1' -terphenyl ] -4, 4' -dicarboxylic acid (60mg,0.17mmol), anhydrous zirconium chloride (61mg,0.26mmol) and benzoic acid (403mg, 3.4mmol,20eq) are put into a polytetrafluoroethylene lining of 23mL, N-dimethylformamide of 3mL is added, the reaction solution is shaken in ultrasonic waves for 30min, then the polytetrafluoroethylene lining is sealed by a stainless steel sleeve and placed in an oven preheated to 80 ℃ for heating for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of N, N-dimethylformamide for a small amount, then repeatedly washed by 20mL of acetone for a small amount, and the filtering is continued until a product is dried; thus obtaining white solid formyl functionalized UiO-68-CHO with 65mg and 71 percent of yield.
Adding UO-68-CHO (50mg,0.16mmol calculated by ligand) and 3mL of N, N-dipropyl formamide to neutralize HCOOH (130 muL, 3.2mmol) into 23mL of polytetrafluoroethylene lining, oscillating for 30min in ultrasonic wave to disperse uniformly, sealing with a stainless steel sleeve, and heating in an oven preheated to 120 ℃ for 36 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by a small amount of 20mL acetone for many times, and the filtering is continued until a product is dried; obtaining white solid UiO-66-CH2N(CH2CH2CH3)236mg, and the tertiary amine modification ratio is 88%.
Example 10
2' -formyl- [1,1':4', 1' -terphenyl ] -4, 4' -dicarboxylic acid (60mg,0.17mmol), anhydrous zirconium chloride (61mg,0.26mmol), L-proline (196mg, 1.7mmol, 10eq) and concentrated hydrochloric acid (0.1mL, 1.2mmol, 7eq) were placed in 23mL of polytetrafluoroethylene lining, 3mL of N, N-dimethylformamide was added, the reaction solution was shaken in ultrasonic waves for 30min, then the polytetrafluoroethylene lining was sealed with a stainless steel sleeve and placed in an oven preheated to 80 ℃ to be heated for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of N, N-dimethylformamide for a small amount, then repeatedly washed by 20mL of acetone for a small amount, and the filtering is continued until a product is dried; thus obtaining white solid formyl functionalized UiO-68-CHO with 65mg and 71 percent of yield.
Adding UO-68-CHO (50mg,0.16mmol calculated by ligand) and 3mL of N, N-dibutylformamide neutralized HCOOH (130 muL, 3.2mmol) into 23mL of polytetrafluoroethylene lining, oscillating in ultrasonic wave for 30min to disperse uniformly, sealing with a stainless steel sleeve, and heating in an oven preheated to 120 ℃ for 36 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by a small amount of 20mL acetone for many times, and the filtering is continued until a product is dried; obtaining white solid UiO-66-CH2N(CH2CH2CH2CH3)233mg, tertiary amine modification ratio 83%.
Example 11
2' -formyl- [1,1':4', 1' -terphenyl ] -4, 4' -dicarboxylic acid (60mg,0.17mmol), anhydrous zirconium chloride (61mg,0.26mmol), L-proline (196mg, 1.7mmol, 10eq) and concentrated hydrochloric acid (0.1mL, 1.2mmol, 7eq) were placed in 23mL of polytetrafluoroethylene lining, 3mL of N, N-dimethylformamide was added, the reaction solution was shaken in ultrasonic waves for 30min, then the polytetrafluoroethylene lining was sealed with a stainless steel sleeve and placed in an oven preheated to 80 ℃ to be heated for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of N, N-dimethylformamide for a small amount, then repeatedly washed by 20mL of acetone for a small amount, and the filtering is continued until a product is dried; thus obtaining white solid formyl functionalized UiO-68-CHO with 65mg and 71 percent of yield.
To 23mL of polytetrafluoro liner was added UiO-68-CHO (50mg,0.16mmol as ligand), 3mL of N-formylpiperidine and 3mL of neutralized HCOOH (130. mu.L, 3.2mmol)) Vibrating in ultrasonic wave for 30min to disperse uniformly, sealing with a stainless steel sleeve, and heating in an oven preheated to 120 ℃ for 36 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by a small amount of 20mL acetone for many times, and the filtering is continued until a product is dried; obtaining white solid UiO-66-CH2N(CH2)536mg, and the tertiary amine modification ratio is 88%.
Example 12
2' -formyl- [1,1':4', 1' -terphenyl ] -4, 4' -dicarboxylic acid (60mg,0.17mmol), anhydrous zirconium chloride (61mg,0.26mmol), L-proline (196mg, 1.7mmol, 10eq) and concentrated hydrochloric acid (0.1mL, 1.2mmol, 7eq) were placed in 23mL of polytetrafluoroethylene lining, 3mL of N, N-dimethylformamide was added, the reaction solution was shaken in ultrasonic waves for 30min, then the polytetrafluoroethylene lining was sealed with a stainless steel sleeve and placed in an oven preheated to 80 ℃ to be heated for 24 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by 20mL of N, N-dimethylformamide for a small amount, then repeatedly washed by 20mL of acetone for a small amount, and the filtering is continued until a product is dried; thus obtaining white solid formyl functionalized UiO-68-CHO with 65mg and 71 percent of yield.
Adding UO-68-CHO (50mg,0.16mmol calculated by ligand) and 3mL of N-formylmorpholine neutralized HCOOH (130 muL, 3.2mmol) into 23mL of polytetrafluoroethylene lining, oscillating in ultrasonic wave for 30min to disperse uniformly, sealing with a stainless steel sleeve, and heating in an oven preheated to 120 ℃ for 36 h; after heating is stopped, the reaction kettle is naturally cooled to room temperature in an oven, reaction liquid is filtered by a glass funnel, a filter cake is repeatedly washed by a small amount of 20mL acetone for many times, and the filtering is continued until a product is dried; obtaining white solid UiO-66-CH2N(CH2)5O, 36mg, and the tertiary amine modification ratio is 84%.
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 zirconium-based metal organic framework material is characterized in that: is prepared by the following steps:
step 1, dissolving a formyl functionalized organic ligand and a zirconium salt in N, N-dimethylformamide to form a reaction solution, adding a specific acid into the reaction solution, performing ultrasonic oscillation, performing a first heating reaction, cooling to room temperature, performing suction filtration, and washing a filter cake with a low-boiling-point organic solvent A to obtain a formyl functionalized zirconium-based metal organic framework material;
dispersing the formyl functional zirconium-based metal organic framework material in a formamido compound, adding formic acid, performing ultrasonic oscillation, performing a second heating reaction, cooling to room temperature, performing suction filtration, and washing a filter cake with a low-boiling-point organic solvent B to obtain an aliphatic tertiary amine functional zirconium-based metal organic framework material;
in the step 1, the formyl functional organic ligand is 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid.
2. The aliphatic tertiary amine functionalized zirconium based metal organic framework material of claim 1, wherein: the zirconium salt in the step 1 is anhydrous zirconium tetrachloride or zirconyl chloride; the specific acid is any one of glacial acetic acid, hydrochloric acid, benzoic acid or L-proline; the low-boiling-point organic solvent A in the step 1 is any one of acetone, methanol, diethyl ether or dichloromethane.
3. The aliphatic tertiary amine functionalized zirconium based metal organic framework material of claim 1, wherein: the formylamine compound in the step 2 is any one of N, N-dimethylformamide, N-diethylformamide, N-dipropylformamide, N-dibutylformamide, N-formylpiperidine or N-formylmorpholine; the low-boiling-point organic solvent B in the step 2 is any one of acetone, diethyl ether or dichloromethane.
4. The aliphatic tertiary amine functionalized zirconium based metal organic framework material of claim 1, wherein: in the step 1, the mole ratio of the formyl functional organic ligand to the zirconium salt is 1: 1-1.5; the mole ratio of the formyl functional organic ligand to the specific acid is 1: 5-15; the using amount of formic acid in the step 2 is 1-5 times of the molar weight of the formyl functionalized zirconium-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.
5. The aliphatic tertiary amine functionalized zirconium based metal organic framework material of claim 1, wherein: the reaction temperature of the first heating reaction in the step 1 is 70-80 ℃, and the reaction time of the first heating reaction is 24-36 hours; the oscillation time of the ultrasonic oscillation is 30 min; the reaction temperature of the second heating reaction in the step 2 is 120-160 ℃, and the reaction time of the second heating reaction is 24-48 h.
6. A preparation method of an aliphatic tertiary amine functionalized zirconium-based metal organic framework material is characterized by comprising the following steps: the method comprises the following steps:
step 1, dissolving a formyl functionalized organic ligand and a zirconium salt in N, N-dimethylformamide to form a reaction solution, adding a specific acid into the reaction solution, performing ultrasonic oscillation, performing a first heating reaction, cooling to room temperature, performing suction filtration, and washing a filter cake with a low-boiling-point organic solvent A to obtain a formyl functionalized zirconium-based metal organic framework material;
dispersing the formyl functional zirconium-based metal organic framework material in a formamido compound, adding formic acid, performing ultrasonic oscillation, performing a second heating reaction, cooling to room temperature, performing suction filtration, and washing a filter cake with a low-boiling-point organic solvent B to obtain an aliphatic tertiary amine functional zirconium-based metal organic framework material;
in the step 1, the formyl functional organic ligand is 1-oxo-1, 3-dihydro-3-hydroxybenzofuran-5-formic acid.
7. The method of claim 6, wherein the method comprises the steps of: the zirconium salt in the step 1 is anhydrous zirconium tetrachloride or zirconyl chloride; the specific acid is any one of glacial acetic acid, hydrochloric acid, benzoic acid or L-proline; the low-boiling-point organic solvent A in the step 1 is any one of acetone, methanol, diethyl ether or dichloromethane.
8. The method of claim 6, wherein the method comprises the steps of: the formylamine compound in the step 2 is any one of N, N-dimethylformamide, N-diethylformamide, N-dipropylformamide, N-dibutylformamide, N-formylpiperidine or N-formylmorpholine; the low-boiling-point organic solvent B in the step 2 is any one of acetone, diethyl ether or dichloromethane.
9. The method of claim 6, wherein the method comprises the steps of: in the step 1, the mole ratio of the formyl functional organic ligand to the zirconium salt is 1: 1-1.5; the mole ratio of the formyl functional organic ligand to the specific acid is 1: 5-15; the using amount of formic acid in the step 2 is 1-5 times of the molar weight of the formyl functionalized zirconium-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.
10. The method of claim 6, wherein the method comprises the steps of: the reaction temperature of the first heating reaction in the step 1 is 70-80 ℃, and the reaction time of the first heating reaction is 24-36 hours; the oscillation time of the ultrasonic oscillation is 30 min; the reaction temperature of the second heating reaction in the step 2 is 120-160 ℃, and the reaction time of the second heating reaction is 24-48 h.
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