CN104788507B - A kind of mg-doped metal organic frame DMMg0.5Mn0.5F monocrystal materials and preparation method thereof - Google Patents
A kind of mg-doped metal organic frame DMMg0.5Mn0.5F monocrystal materials and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of mg-doped metal organic frame DMMg0.5Mn0.5F monocrystal materials and preparation method thereof, mg-doped metal organic frame DMMg0.5Mn0.5F monocrystal materials be by size be 1.5 × 1.5 × 1.5~2.0 × 2.0 × 2.0 mm3, and the molar percentage of magnesium ion and manganese ion is 1 in compound:1 DMMg0.5Mn0.5F monocrystalline is constituted.Agents useful for same is commercial product, is prepared without cumbersome；Acquisition novel metal organic frame monocrystal material and larger-sized monocrystalline are combined using hydro-thermal method and liquid phase method；Process controllability is strong, easy to operate, and obtained product purity is high.Mg-doped DMMnF monocrystal materials obtained by the present invention, are expected to be widely used in terms of novel metal organic frame semiconductor, information storage and optics.
Description
Technical field
The present invention relates to a kind of mg-doped metal-organic framework monocrystal material and preparation method thereof, a kind of Mg is specifically referred to
Adulterate [(CH3)2NH2]Mn(HCOO)3Monocrystal material（It is abbreviated as DMMg0.5Mn0.5F, DM are [(CH3)2NH2]+1, F is
[(HCOO)3]-3）And preparation method thereof.
Technical background
Metal-organic framework（Metal-Organic Frameworks, MOFs）Material is because in catalysis, hydrogen storage and optics member
There is potential application value in terms of part and receive significant attention, be a focus in current New function investigation of materials field.
Flexible, skeleton flexibility, easily cutting property and easily formation high anisotropy and low lattice are prepared because organic compound has
Advantage in terms of symmetrical structure, people attempt ferroelectricity organic matter and magnetic transition metal ions binding in recent years, if
Count out the new multi-ferroic material based on metal-organic hybrid.
The discovery of magnetoelectric effect in DMMnF materials, shows organic ferroelectricity being combined with magnetic metal ion, it will
The exploration space of multi-ferroic material and magnetoelectric effect is expanded significantly.DMMnF preparation method mainly has hydro-thermal method, liquid phase method
Deng.Hydro-thermal method refers in sealed pressure vessel, using water as solvent, and in 100~400 °C of temperature, pressure is more than 0.1MPa
Until under conditions of tens to hundreds of MPa, making predecessor（Raw material）React and crystallize.I.e. provide one in atmospheric conditions without
The special physicochemical environment that method is obtained, makes predecessor sufficiently be dissolved in reaction system, forms atom or molecule
Growth unit, nucleation is simultaneously crystallized.Hydro-thermal method has reaction speed fast, the advantages of product purity height, better crystallinity degree, reunion are lacked.Mesh
Before, more than the DMMnF materials synthesized by hydro-thermal method based on powder crystallite and small monocrystalline, still, as device apply by
Greatly limitation, therefore how to better control over the growth of DMMnF monocrystalline so that the size of monocrystalline, which reaches, is easy to wanting for making devices
Ask, and widen its industry application and have very important significance.
As people go deep into metal-organic framework materials research, people just make great efforts to multiferroic MOFs base monocrystalline materials
The magneto-electric coupled mechanism of material is sufficiently studied, it is desirable to can be changed by being combined, adulterating some metallic elements in DMMnF
The magnetic structure and electronic structure of Mn, and Effective Regulation is carried out to its magnetoelectric effect, so as to widen MOFs materials significantly
Application value.At present, a kind of Mg doping [(CH3)2NH2]Mn(HCOO)3Monocrystal material and preparation method thereof is not yet reported that.
The content of the invention
The purpose of the present invention is for the new Mg doping DMMnF monocrystal materials of acquisition and larger-sized DMMg0.5Mn0.5F
Monocrystalline, while the DMMg0.5Mn0.5The preparation method of F monocrystalline is simple, conveniently there is provided a kind of mg-doped metal-organic framework
DMMnF monocrystal materials and preparation method thereof.
The technical scheme is that：
A kind of mg-doped metal-organic framework DMMg0.5Mn0.5F monocrystal materials be by size be 1.5 × 1.5 × 1.5~
2.0×2.0×2.0 mm3, and the molar percentage of magnesium ion and manganese ion is 1 in compound:1 DMMg0.5Mn0.5F is mono-
Crystalline substance composition.
Described DMMg0.5Mn0.5F monocrystalline is colourless transparent crystal, and chemical formula is [(CH3)2NH2]Mg0.5Mn0.5
(HCOO)3。
The mg-doped metal-organic framework DMMg0.5Mn0.5The preparation method of F monocrystal materials, it is characterised in that including
Following step：
（1）The concentrated sulfuric acid, acetone, absolute ethyl alcohol and deionized water are sequentially added in beaker, is cleaned by ultrasonic 15 minutes respectively,
To remove residual metal ions and organic matter in beaker, the beaker after cleaning is saved backup；
（2）By magnesium chloride and manganese chloride according to 1：1 mol ratio weighs mixing, and distillation is dissolved in DMF
In water, stirring makes it fully dissolve；The volume ratio of wherein DMF and distilled water is 1：1；Per mole of magnesium chloride and manganese chloride mixture
Required distillation water consumption is 6mL；
（3）By step（2）Gained mixed solution loads in reactor, and 135~145 °C are heated to after sealing and is carried out instead
Should, and 60~72 hours are incubated, then naturally cool to room temperature；
（4）By step（3）Reacted saturation clear liquid pipette takes out and loads step（1）In the beaker cleaned,
Then beaker is put into climatic chamber；30 sections of temperature lowering curves are set, temperature range is 28~22 °C, every section of 0.5 °C of temperature difference,
Every section of temperature range is incubated 2.5~3 hours, and humidity is 45~55%；
（5）The crystal grain of beaker bottom is washed 3 times with absolute ethyl alcohol, obtaining magnesium within 10 minutes in 60 °C of vacuum drying mixes
Miscellaneous metal-organic framework DMMg0.5Mn0.5F monocrystal materials.
The model WHS-70B models of described climatic chamber.The step（4）In humidity by humidifier and constant temperature
Constant humidity cabinet is controlled.
Beneficial effect：
In preparation process of the present invention, agents useful for same is commercial product, is prepared without cumbersome；Utilize hydro-thermal method and liquid phase method phase
With reference to the larger-sized monocrystalline of acquisition and novel magnesium doping metals-organic frame monocrystal material；Process controllability is strong, easily behaviour
Make, obtained product purity is high.
DMMg obtained by the present invention0.5Mn0.5F materials, be expected to novel metal-organic frame semiconductor, information storage and
It is widely used in terms of optics.
Brief description of the drawings
Fig. 1 is to use DMMg produced by the present invention0.5Mn0.5F monocrystalline digital photographs；
Fig. 2 is to use DMMg produced by the present invention0.5Mn0.5X-ray diffraction (XRD) spectrogram of F monocrystalline；
Fig. 3 is to use DMMg produced by the present invention0.5Mn0.5F monocrystalline spectrograms, wherein（a）It is with produced by the present invention
DMMg0.5Mn0.5F monocrystalline XPS is composed entirely, and (b) is to use DMMg produced by the present invention0.5Mn0.5F monocrystalline Mn2p XPS spectrum figure；(c) it is
Use DMMg produced by the present invention0.5Mn0.5F monocrystalline Mg1s XPS spectrum figure.
Embodiment
The present invention is further illustrated below in conjunction with example.
The present invention prepares DMMg0.5Mn0.5F monocrystal materials are to be combined method using hydro-thermal method and liquid phase method.In beaker
The concentrated sulfuric acid, acetone, absolute ethyl alcohol and deionized water are sequentially added, respectively excusing from death cleaning 15 minutes, to remove residual gold in beaker
Belong to the impurity such as ion, organic matter, the beaker after cleaning is saved backup.By magnesium chloride and manganese chloride according to 1：1 mol ratio claims
2.5 mmol are taken, with 15 mL DMFs（DMF）It is dissolved in 15 mL distilled water, stirring makes it fully dissolve；Its
Middle DMF and distilled water volume ratio are 1：1.The mixed solution is loaded in reactor, 135~145 ° are heated to after sealing
C is reacted, and is incubated 60~72 hours, then naturally cools to room temperature.Reacted saturation clear liquid is taken out with pipette
And load step（1）In the beaker cleaned, then beaker is put into climatic chamber；Set 30 sections of temperature lowering curves, temperature
Interval is 28~22 °C, every section of 0.5 °C of temperature difference, and every section of temperature range is incubated 2.5~3 hours, and humidity is 45~55%.By beaker
The crystal grain of bottom is washed 3 times with absolute ethyl alcohol, and the DMMg for obtaining water white transparency for 10 minutes is dried in vacuo in 60 °C0.5Mn0.5F
Cubic crystal.
Embodiment 1
By magnesium chloride and manganese chloride according to 1：1 mol ratio weighs 2.5 mmol, with 15 mL DMFs
（DMF）It is dissolved in 15 mL distilled water, stirring makes it fully dissolve；The volume ratio of wherein DMF and distilled water is 1：1.This is mixed
Solution loads in reactor, and 140 °C are heated to after sealing and is reacted, and is incubated 60 hours, then naturally cools to room
Temperature.Reacted saturation clear liquid pipette is taken out and loads step（1）In the beaker cleaned, beaker is then put into perseverance
In constant temperature and humidity case；30 sections of temperature lowering curves are set, temperature range is 28~22 °C, every section of 0.5 °C of temperature difference, every section of temperature range insulation
2.5 hours, humidity was 50%.The crystal grain of beaker bottom is washed 3 times with absolute ethyl alcohol, is dried in vacuo 10 minutes in 60 °C
Obtain the DMMg of water white transparency0.5Mn0.5F cubic crystals.
Gained crystal is directly observed under digital camera（Such as Fig. 1）, it can be found that crystal is in water white transparency, size is
1.5 × 1.5 × 1.5~2.0 × 2.0 × 2.0 mm3Cubic crystal.Fig. 2 powder XRD analysis shows product
DMMg0.5Mn0.5F with it is basically identical undoped with DMMnF（Corresponding to CCDC：246991, Cambridge crystal data center）, Fig. 2's is interior
Illustration shows that crystal, along (012) direction oriented growth, forms monocrystalline.In Powder XRD pattern without find magnesium formate and
The diffraction maximum of other impurity, shows that magnesium elements are entered in the lattice of DMMnF crystal by successfully doping.Fig. 3 a XPS can in composing entirely
To find out DMMg0.5Mn0.5Contain N, Mg, Mn, O in F monocrystalline, C element calculates the atom for obtaining product through XPS integrating peak areas
Than close to 1：0.5：0.5：6：5, and Mg, Mn valent state are+divalent (Fig. 3 b, c), show the chemistry of products therefrom
Formula is [(CH3)2NH2]Mg0.5Mn0.5 (HCOO)3。
Embodiment 2
Such as be the same as Example 1, by magnesium chloride and manganese chloride according to 1：1 mol ratio weighs 2.5 mmol, with 15 mL N, N-
Dimethylformamide（DMF）It is dissolved in 15 mL distilled water, stirring makes it fully dissolve；The volume ratio of wherein DMF and distilled water is
1：1.The mixed solution is loaded in reactor, 140 °C are heated to after sealing and is reacted, and is incubated 65 hours, then
Naturally cool to room temperature.Reacted saturation clear liquid pipette is taken out and loads step（1）In the beaker cleaned, then
Beaker is put into climatic chamber；30 sections of temperature lowering curves are set, temperature range is 28~22 °C, every section of 0.5 °C, every section of temperature difference
Temperature range is incubated 3 hours, and humidity is 45%.The crystal grain of beaker bottom is washed 3 times with absolute ethyl alcohol, in 60 °C of vacuum
Dry the DMMg for obtaining water white transparency for 10 minutes0.5Mn0.5F cubic crystals.The pattern and structure of product with the phase of embodiment 1
Together.
Embodiment 3
Such as be the same as Example 1, by magnesium chloride and manganese chloride according to 1：1 mol ratio weighs 2.5 mmol, with 15 mL N, N-
Dimethylformamide（DMF）It is dissolved in 15 mL distilled water, stirring makes it fully dissolve；The volume ratio of wherein DMF and distilled water is
1：1.The mixed solution is loaded in reactor, 135 °C are heated to after sealing and is reacted, and is incubated 65 hours, then
Naturally cool to room temperature.Reacted saturation clear liquid pipette is taken out and loads step（1）In the beaker cleaned, then
Beaker is put into climatic chamber；30 sections of temperature lowering curves are set, temperature range is 28~22 °C, every section of 0.5 °C, every section of temperature difference
Temperature range is incubated 2.5 hours, and humidity is 45%.The crystal grain of beaker bottom is washed 3 times with absolute ethyl alcohol, it is true in 60 °C
Sky dries the DMMg for obtaining water white transparency for 10 minutes0.5Mn0.5F cubic crystals.The pattern and structure of product with the phase of embodiment 1
Together.
Embodiment 4
Such as be the same as Example 1, by magnesium chloride and manganese chloride according to 1：1 mol ratio weighs 2.5 mmol, with 15 mL N, N-
Dimethylformamide（DMF）It is dissolved in 15 mL distilled water, stirring makes it fully dissolve；The volume ratio of wherein DMF and distilled water is
1：1.The mixed solution is loaded in reactor, 145 °C are heated to after sealing and is reacted, and is incubated 60 hours, then
Naturally cool to room temperature.Reacted saturation clear liquid pipette is taken out and loads step（1）In the beaker cleaned, then
Beaker is put into climatic chamber；30 sections of temperature lowering curves are set, temperature range is 28~22 °C, every section of 0.5 °C, every section of temperature difference
Temperature range is incubated 2.5 hours, and humidity is 55%.The crystal grain of beaker bottom is washed 3 times with absolute ethyl alcohol, it is true in 60 °C
Sky dries the DMMg for obtaining water white transparency for 10 minutes0.5Mn0.5F cubic crystals.The pattern and structure of product with the phase of embodiment 1
Together.
Embodiment 5
Such as be the same as Example 1, by magnesium chloride and manganese chloride according to 1：1 mol ratio weighs 2.5 mmol, with 15 mL N, N-
Dimethylformamide（DMF）It is dissolved in 15 mL distilled water, stirring makes it fully dissolve；The volume ratio of wherein DMF and distilled water is
1：1.The mixed solution is loaded in reactor, 143 °C are heated to after sealing and is reacted, and is incubated 72 hours, then
Naturally cool to room temperature.Reacted saturation clear liquid pipette is taken out and loads step（1）In the beaker cleaned, then
Beaker is put into climatic chamber；30 sections of temperature lowering curves are set, temperature range is 28~22 °C, every section of 0.5 °C, every section of temperature difference
Temperature range is incubated 3 hours, and humidity is 50%.The crystal grain of beaker bottom is washed 3 times with absolute ethyl alcohol, in 60 °C of vacuum
Dry the DMMg for obtaining water white transparency for 10 minutes0.5Mn0.5F cubic crystals.The pattern and structure of product with the phase of embodiment 1
Together.
Claims (4)
1. a kind of mg-doped metal-organic framework DMMg0.5Mn0.5F monocrystal materials, it is characterised in that be by size be 1.5 ×
1.5 × 1.5~2.0 × 2.0 × 2.0 mm3, and the molar percentage of magnesium ion and manganese ion is 1 in compound:1
DMMg0.5Mn0.5F monocrystalline is constituted；Described DMMg0.5Mn0.5F monocrystalline is colourless transparent crystal, and chemical formula is [(CH3)2NH2]
Mg0.5Mn0.5 (HCOO)3；The θ values of X-ray diffraction peak 2 of its powder crystal at 14.54 °, 19.88 °, 21.50 °, 24.48 °,
29.29 °, 31.72 °, 37.48 °, 38.33 °, 43.27 °, 44.58 °, 48.29 °, 49.91 °, 52.21 ° and 55.54 °, its monocrystalline
The θ values of X-ray diffraction peak 2 correspond respectively to [012] for 14.54 °, 29.29 ° and 44.58 ° of diffraction maximum, and [024] and [036] is brilliant
Face, grows along same family of crystal planes [012] direction, forms monocrystalline.
2. a kind of mg-doped metal-organic framework DMMg as claimed in claim 10.5Mn0.5The preparation method of F monocrystal materials, its
It is characterised by, comprises the steps：
（1）The concentrated sulfuric acid, acetone, absolute ethyl alcohol and deionized water are sequentially added in beaker, is cleaned by ultrasonic 15 minutes respectively, to go
Except residual metal ions and organic matter in beaker, the beaker after cleaning is saved backup；
（2）By magnesium chloride and manganese chloride according to 1：1 mol ratio weighs mixing, and distilled water is dissolved in DMF
In, stirring makes it fully dissolve；The volume ratio of wherein DMF and distilled water is 1：1；Every mM of magnesium chloride and manganese chloride mixture
Required distillation water consumption is 6mL；
（3）By step（2）Gained mixed solution loads in reactor, and 135~145 °C are heated to after sealing and is reacted,
And 60~72 hours are incubated, then naturally cool to room temperature；
（4）By step（3）Reacted saturation clear liquid pipette takes out and loads step（1）In the beaker cleaned, then
Beaker is put into climatic chamber；Temperature lowering curve is set, temperature range is 28~22 °C, every section of 0.5 °C of temperature difference, every section of temperature
Interval insulation 2.5~3 hours, humidity is 45~55%；
（5）The crystal grain of beaker bottom is washed 3 times with absolute ethyl alcohol, mg-doped gold is obtained within 10 minutes in 60 °C of vacuum drying
Category-organic frame DMMg0.5Mn0.5F monocrystal materials.
3. mg-doped metal-organic framework DMMg according to claim 20.5Mn0.5The preparation method of F monocrystal materials, its
It is characterised by the model WHS-70B models of described climatic chamber.
4. mg-doped metal-organic framework DMMg according to claim 20.5Mn0.5The preparation method of F monocrystal materials, its
It is characterised by the step（4）In humidity controlled by humidifier and climatic chamber.
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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 |
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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 |
Non-Patent Citations (4)
| Title |
|---|
| Elastic relaxation behavior, magnetoelastic coupling, and order-disorder processes in multiferroic metal-organic frameworks;R. I. Thomson等;《PHYSICAL REVIEW B》;20121221;第86卷(第21期);第214304-1至214304-7页 * |
| First-order structural transition in the multiferroic perovskite-like formate [(CH3)2NH2][Mn(HCOO)3];M. Sánchez-Andújar等;《CrystEngComm》;20140213;第16卷;第3558–3566页 * |
| Hydrogen Uptake by {H[Mg(HCOO)3]NHMe2}∞ and Determination of Its H2 Adsorption Sites through Monte Carlo Simulations;Andrea Rossin等;《Langmuir》;ACS;20110707;第27卷;第10124-10131页 * |
| Multiferroic Behavior Associated with an Order-Disorder Hydrogen Bonding Transition in Metal-Organic Frameworks (MOFs) with the Perovskite ABX3 Architecture;Prashant Jain 等;《Journal of the American Chemical Society》;ACS;20090902;第131卷(第38期);第13625-13627页 * |
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Application publication date: 20150722 Assignee: Fengxian wisdom automation equipment Research Institute Co., Ltd Assignor: JIANGSU JUJIE ELECTROMECHANICAL Co.,Ltd. Contract record no.: X2021980015758 Denomination of invention: The invention relates to a magnesium doped metal organic framework dmmg0.5Mn0.5f single crystal material and a preparation method thereof Granted publication date: 20171031 License type: Exclusive License Record date: 20211222 |