CN109734740A - A kind of borate family metal organic framework compound and preparation method thereof - Google Patents
A kind of borate family metal organic framework compound and preparation method thereof Download PDFInfo
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- CN109734740A CN109734740A CN201910158671.3A CN201910158671A CN109734740A CN 109734740 A CN109734740 A CN 109734740A CN 201910158671 A CN201910158671 A CN 201910158671A CN 109734740 A CN109734740 A CN 109734740A
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Abstract
The invention belongs to new material technology field, it is related to a kind of borate family metal organic framework compound and preparation method thereof, first by dissolving metal salts in n,N-Dimethylformamide, then boric acid and 2-methylimidazole is dissolved in 1~500ml ultrapure water；The solution that the two obtains is mixed to be transferred in reaction kettle in proportion and is sealed after mixing evenly, room temperature is down to again after being warming up to 150~200 DEG C of reactions, is dried under vacuum after successively filtering washing, obtains borate family metal organic frame monocrystalline；Its preparation process is simple, easy and safe to operate, at low cost, and the borate metal organic framework of preparation can be used for gas storage, be catalyzed and derive the porous carbon materials of boracic, metal boride.
Description
Technical field:
The invention belongs to new material technology field, it is related to a kind of borate family metal organic framework compound and its preparation side
Method.
Background technique:
Metal-organic framework (Metal-Organic Frameworks, abbreviation MOFs) be it is a kind of by inorganic metal from
The porous network structure that sub (or metal cluster) and organic ligand are self-assembly of by coordination, therefore also known as porous polycomplexation
Close object.Since material has cellular structure abundant, MOFs specific surface area and porosity with higher makes MOFs in gas
Body absorption, stores, separation, drug delivery, and the fields such as catalysis show huge potential application.(Park K S,Ni Z,A
P,et al.Exceptional chemical and thermal stability of zeolitic imidazolate
frameworks.Proceedings of the National Academy of Sciences,2006,103(27):
10186-10191；Banerjee R,Phan A,Wang B,et al.High-throughput synthesis of
zeolitic imidazolate frameworks and application to CO2capture.Science,2008,
319(5865):939-943)。
In recent years, the compound of boron and its boron showed multifrequency nature and function, in biology due to unique design feature
Chemistry, material science, catalytic chemistry etc. have a wide range of applications.In recent years, pertinent literature emerged one after another, such as nitrogen
Change boron and shows unique catalysis characteristics (Grant J T, Carrero C A, Goeltl F, et in catalytic field
al.Selective oxidative dehydrogenation of propane to propene using boron
Nitride catalysts.Science, 2016,354 (6319): 1570-1573), the unique CO of BIF series2Capture characteristic
(Zheng S,Wu T,Zhang J,et al.Porous metal carboxylate boron imidazolate
frameworks.Angewandte Chemie,2010,122(31):5490-5494.)
Up to the present, in the metal-organic framework material of only BIF series containing boron element (Zhang J, Wu T,
Zhou C,et al.Zeolitic boron imidazolate frameworks.Angewandte Chemie,2009,121
(14): 2580-2583 the ligand using boracic), is needed in such MOFs in synthesis process, but the chemical structure of boron is very
Stablize, ligand synthesis process is complicated.Therefore, Yao Fengfu boracic MOFs material, just must overcome the above problem, develop a kind of convenience
Synthesis boracic MOFs variation route.
Summary of the invention:
It is an object of the invention to overcome disadvantage of the existing technology, design, which provides, a kind of prepares boron using solvent-thermal method
The preparation method of Barbiturates metal organic framework compound.
To achieve the goals above, the chemical formula expression of borate family metal organic framework compound of the present invention are as follows:
Zn2(BO3)C8H12N4, monocrystalline cell parameter are as follows: and tetragonal crystal system, Pba2 space group, Alpha=90 °, beta=90 °, gama=90 °,Z=2,Steric bulk structure is three-dimensional structure.
The detailed process that the present invention prepares borate family metal organic framework compound comprises the following steps that
1) by 0.0001~10.0mol dissolving metal salts in 1~500ml n,N-Dimethylformamide (DMF),
2) 0.001~10.0mol boric acid and 0.001~10.0mol 2-methylimidazole are dissolved in 1~500ml ultrapure water
In；
3) solution that step 1) and step 2) obtain is mixed to be transferred in reaction kettle according to the ratio of volume ratio 1:1 and is stirred
Sealing after uniformly is warming up to 150~200 DEG C with the rate of 1~5 DEG C/min and reacts 6~168 hours, then with 0.2~5 DEG C/min
Rate is down to room temperature, successively carries out after 3~5 suction filtration are washed 60~80 DEG C of dry 12h under vacuum, obtains borate family metal
Organic frame monocrystalline.
Metal salt of the present invention is the inorganic metal salts, preferably zinc nitrate, zinc sulfate such as nitrate, sulfate or chloride
Or zinc chloride.
Boric acid and 2-methylimidazole of the present invention are commercially produced product, 98% or more purity.
Compared with prior art, the present invention its preparation process is simple, easy and safe to operate, at low cost, the borate of preparation
Metal-organic framework can be used for gas storage, be catalyzed and derive the porous carbon materials of boracic, metal boride etc..
Detailed description of the invention:
Fig. 1 is the digital photograph of the monocrystalline of zinc borate organic frame compound prepared by the embodiment of the present invention 1.
Fig. 2 is the structural unit of zinc borate organic frame compound prepared by the embodiment of the present invention 1.
Fig. 3 is the X-ray diffraction spectrogram of zinc borate organic frame compound prepared by the embodiment of the present invention 1.
Fig. 4 is the thermogravimetric spectrum under air and nitrogen of zinc borate organic frame compound prepared by the embodiment of the present invention 1
Figure.
Specific embodiment:
Below with reference to embodiment, the present invention will be further described, but not limited to this.
Raw material used in the embodiment of the present invention is commercial products, is further processed without any；The instrument is such as
Without specified otherwise, commercially obtain.
Embodiment 1:
The process that the present embodiment prepares borate family metal organic framework compound includes the following steps:
1) 2g zinc nitrate is dissolved in the N,N-dimethylformamide solution of 35ml；
2) by 2.2g 2-methylimidazole, 4.3g boric acid is successively dissolved in the ultrapure water of 35ml；
3) by the zinc nitrate solution in step 1) and the 2-methylimidazole in step 2), boric acid is transferred to the reaction of 100ml
It in kettle polytetrafluoroethyllining lining, stirs evenly, seals；
4) reaction kettle in step 3) is transferred in baking oven, is warming up to 160 DEG C with 5 DEG C/min of rate and reacts 120 hours,
Then room temperature is cooled to 0.4 DEG C/min；
5) by the crystal generated in step 4) with ultrapure water filtering and washing three times, be transferred to 60 DEG C of dryings of vacuum oven
Zinc borate organic frame compound is prepared in 12h.
The digital photograph of the monocrystalline of zinc borate organic frame compound manufactured in the present embodiment is as shown in Figure 1, can by Fig. 1
Know, the structure of crystal is very complete, occurs without apparent defect；Its structural unit as shown in Fig. 2, boron element with borate
Mode is successfully coordinated in MOFs structure；Its X-ray diffraction spectrogram is as shown in figure 3, the crystallinity of monocrystalline is very high, and does not have
There is impurity；Its thermogravimetric spectrogram under air and nitrogen is as shown in figure 4, as can be seen from Figure, manufactured in the present embodimentization
Closing object has extraordinary thermal stability.
Embodiment 2:
The process that the present embodiment prepares borate family metal organic framework compound includes the following steps:
1) 1g zinc nitrate is dissolved in the N,N-dimethylformamide solution of 15ml；
2) by 1.1g 2-methylimidazole, 2.1g boric acid is successively dissolved in the ultrapure water of 15ml；
3) by the zinc nitrate solution in step 1) and the 2-methylimidazole in step 2), boric acid is transferred to the reaction kettle of 50ml
It in polytetrafluoroethyllining lining, stirs evenly, seals；
4) reaction kettle in step 3) is transferred in baking oven, is warming up to 150 DEG C with 3 DEG C/min of rate and reacts 96 hours,
Then room temperature is cooled to 5 DEG C/min；
5) by the crystal generated in step 4) with ultrapure water filtering and washing three times, be transferred to 60 DEG C of dryings of vacuum oven
12h。
Embodiment 3:
The process that the present embodiment prepares borate family metal organic framework compound includes the following steps:
1) 0.5g zinc nitrate is dissolved in the N,N-dimethylformamide solution of 15ml；
2) by 0.6g 2-methylimidazole, 0.75g boric acid is successively dissolved in the ultrapure water of 15ml；
3) by the zinc nitrate solution in step 1) and the 2-methylimidazole in step 2), boric acid is transferred to the reaction kettle of 50ml
It in polytetrafluoroethyllining lining, stirs evenly, seals；
4) reaction kettle in step 3) is transferred in baking oven, is warming up to 200 DEG C with 5 DEG C/min of rate and reacts 72 hours,
Then room temperature is cooled to 1 DEG C/min；
5) by the crystal generated in step 4) with ultrapure water filtering and washing three times, be transferred to 80 DEG C of dryings of vacuum oven
12h。
Embodiment 4:
The process that the present embodiment prepares borate family metal organic framework compound includes the following steps:
1) 1.0g zinc chloride is dissolved in the N,N-dimethylformamide solution of 15ml；
2) by 1.5g 2-methylimidazole, 1.75g boric acid is successively dissolved in the ultrapure water of 15ml；
3) by the zinc nitrate solution in step 1) and the 2-methylimidazole in step 2), boric acid is transferred to the reaction kettle of 50ml
It in polytetrafluoroethyllining lining, stirs evenly, seals；
4) reaction kettle in step 3) is transferred in baking oven, is warming up to 180 DEG C with 3 DEG C/min of rate and reacts 120 hours,
Then room temperature is cooled to 3 DEG C/min；
5) by the crystal generated in step 4) with ultrapure water filtering and washing three times, be transferred to 80 DEG C of dryings of vacuum oven
12h。
Embodiment 5:
The process that the present embodiment prepares borate family metal organic framework compound includes the following steps:
1) 2.0g zinc sulfate is dissolved in the N,N-dimethylformamide solution of 35ml；
2) by 2.2g 2-methylimidazole, 3.1g boric acid is successively dissolved in the ultrapure water of 35ml；
3) by the zinc nitrate solution in step 1) and the 2-methylimidazole in step 2), boric acid is transferred to the reaction of 100ml
It in kettle polytetrafluoroethyllining lining, stirs evenly, seals；
4) reaction kettle in step 3) is transferred in baking oven, it is small to be warming up to 150 DEG C of reactions 144 with 0.5 DEG C/min of rate
When, room temperature is then cooled to 0.5 DEG C/min；
5) by the crystal generated in step 4) with ultrapure water filtering and washing three times, be transferred to 60 DEG C of dryings of vacuum oven
12h。
Embodiment 6:
The process that the present embodiment prepares borate family metal organic framework compound includes the following steps:
1) 0.5g cobalt nitrate is dissolved in the N,N-dimethylformamide solution of 15ml；
2) by 0.6g 2-methylimidazole, 0.75g boric acid is successively dissolved in the ultrapure water of 15ml；
3) by the zinc nitrate solution in step 1) and the 2-methylimidazole in step 2), boric acid is transferred to the reaction kettle of 50ml
It in polytetrafluoroethyllining lining, stirs evenly, seals；
4) reaction kettle in step 3) is transferred in baking oven, is warming up to 180 DEG C with 3 DEG C/min of rate and reacts 72 hours,
Then room temperature is cooled to 2 DEG C/min；
5) by the crystal generated in step 4) with milli-Q water three times, be transferred to 80 DEG C of vacuum oven dry 12h.
Embodiment 7:
The process that the present embodiment prepares borate family metal organic framework compound includes the following steps:
1) 1.5g copper nitrate is dissolved in the N,N-dimethylformamide solution of 35ml；
2) by 1.6g 2-methylimidazole, 2.3g boric acid is successively dissolved in the ultrapure water of 35ml；
3) by the zinc nitrate solution in step 1) and the 2-methylimidazole in step 2), boric acid is transferred to the reaction of 100ml
It in kettle polytetrafluoroethyllining lining, stirs evenly, seals；
4) reaction kettle in step 3) is transferred in baking oven, is warming up to 200 DEG C with 5 DEG C/min of rate and reacts 48 hours,
Then room temperature is cooled to 2 DEG C/min；
5) by the crystal generated in step 4) with ultrapure water filtering and washing three times, be transferred to 80 DEG C of dryings of vacuum oven
12h。
Embodiment 8:
The process that the present embodiment prepares borate family metal organic framework compound includes the following steps:
1) 1.7g nickel nitrate is dissolved in the N,N-dimethylformamide solution of 35ml；
2) by 2.0g 2-methylimidazole, 2.3g boric acid is successively dissolved in the ultrapure water of 35ml；
3) by the zinc nitrate solution in step 1) and the 2-methylimidazole in step 2), boric acid is transferred to the reaction of 100ml
It in kettle polytetrafluoroethyllining lining, stirs evenly, seals；
4) reaction kettle in step 3) is transferred in baking oven, it is small to be warming up to 150 DEG C of reactions 60 with 0.5 DEG C/min of rate
When, room temperature is then cooled to 1 DEG C/min；
5) by the crystal generated in step 4) with ultrapure water filtering and washing three times, be transferred to 60 DEG C of dryings of vacuum oven
12h。
Embodiment 9:
The process that the present embodiment prepares borate family metal organic framework compound includes the following steps:
1) 0.7g frerrous chloride is dissolved in the N,N-dimethylformamide solution of 15ml；
2) by 1.0g 2-methylimidazole, 1.3g boric acid is successively dissolved in the ultrapure water of 15ml；
3) by the zinc nitrate solution in step 1) and the 2-methylimidazole in step 2), boric acid is transferred to the reaction kettle of 50ml
It in polytetrafluoroethyllining lining, stirs evenly, seals；
4) reaction kettle in step 3) is transferred in baking oven, is warming up to 180 DEG C with 5 DEG C/min of rate and reacts 60 hours,
Then room temperature is cooled to 3 DEG C/min；
5) by the crystal generated in step 4) with ultrapure water filtering and washing three times, be transferred to 80 DEG C of dryings of vacuum oven
12h。
Claims (4)
1. a kind of borate family metal organic framework compound, it is characterised in that its chemical formula expression are as follows: Zn2(BO3)C8H12N4,
Its monocrystalline cell parameter are as follows: tetragonal crystal system, Pba2 space group,
Alpha=90 °, beta=90 °, gama=90 °, Z=2,Steric bulk knot
Structure is three-dimensional structure.
2. a kind of preparation method of borate family metal organic framework compound as described in claim 1, it is characterised in that specific
Process includes the following steps:
1) by 0.0001~10.0mol dissolving metal salts in 1~500ml N,N-dimethylformamide；
2) 0.001~10.0mol boric acid and 0.001~10.0mol 2-methylimidazole are dissolved in 1~500ml ultrapure water；
3) solution that step 1) and step 2) obtain is mixed to be transferred in reaction kettle according to the ratio of volume ratio 1:1 and is stirred evenly
After seal, be warming up to 150~200 DEG C with the rate of 1~5 DEG C/min and react 6~168 hours, then with 0.2~5 DEG C/min rate
It is down to room temperature, 60~80 DEG C of dry 12h under vacuum is successively carried out after 3~5 suction filtration are washed, it is organic to obtain borate family metal
Frame monocrystalline.
3. the preparation method of borate family metal organic framework compound according to claim 2, it is characterised in that the gold
Category salt is zinc nitrate, zinc sulfate or zinc chloride.
4. the preparation method of borate family metal organic framework compound according to claim 2, it is characterised in that the boron
Acid and 2-methylimidazole are commercially produced product, 98% or more purity.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111155143A (en) * | 2020-01-07 | 2020-05-15 | 中国科学院化学研究所 | Preparation method of two-dimensional layered metal organic framework nano material |
| CN113149014A (en) * | 2021-04-30 | 2021-07-23 | 景德镇陶瓷大学 | Method for preparing boron carbide powder by adopting organic carbon source |
| CN114522713A (en) * | 2022-02-23 | 2022-05-24 | 中国石油大学(华东) | Preparation method and application of cobalt nanoparticle/boron nitride composite material |
| CN114957681A (en) * | 2022-04-18 | 2022-08-30 | 苏州大学 | Neutron shielding material based on metal boron-imidazole framework and preparation method thereof |
| CN114957681B (en) * | 2022-04-18 | 2024-05-10 | 苏州大学 | Neutron shielding material based on metal boron-imidazole framework and preparation method thereof |
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| CN102962036A (en) * | 2012-10-30 | 2013-03-13 | 中国科学院大连化学物理研究所 | Porous metal organic framework material based on transition metal cobalt and preparation method thereof |
| CN104525125A (en) * | 2014-12-17 | 2015-04-22 | 江苏科技大学 | Supported metal organic skeleton/graphene oxide hydrogen storage material and preparation method thereof |
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| CN102962036A (en) * | 2012-10-30 | 2013-03-13 | 中国科学院大连化学物理研究所 | Porous metal organic framework material based on transition metal cobalt and preparation method thereof |
| CN104525125A (en) * | 2014-12-17 | 2015-04-22 | 江苏科技大学 | Supported metal organic skeleton/graphene oxide hydrogen storage material and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111155143A (en) * | 2020-01-07 | 2020-05-15 | 中国科学院化学研究所 | Preparation method of two-dimensional layered metal organic framework nano material |
| CN111155143B (en) * | 2020-01-07 | 2021-06-01 | 中国科学院化学研究所 | Preparation method of two-dimensional layered metal organic framework nano material |
| CN113149014A (en) * | 2021-04-30 | 2021-07-23 | 景德镇陶瓷大学 | Method for preparing boron carbide powder by adopting organic carbon source |
| CN114522713A (en) * | 2022-02-23 | 2022-05-24 | 中国石油大学(华东) | Preparation method and application of cobalt nanoparticle/boron nitride composite material |
| CN114522713B (en) * | 2022-02-23 | 2023-04-14 | 中国石油大学(华东) | Preparation method and application of cobalt nanoparticle/boron nitride composite material |
| CN114957681A (en) * | 2022-04-18 | 2022-08-30 | 苏州大学 | Neutron shielding material based on metal boron-imidazole framework and preparation method thereof |
| CN114957681B (en) * | 2022-04-18 | 2024-05-10 | 苏州大学 | Neutron shielding material based on metal boron-imidazole framework and preparation method thereof |
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