CN104788497A - Lithium doped metal-organic framework DMMnF single crystal material and preparation method thereof - Google Patents
Lithium doped metal-organic framework DMMnF single crystal material and preparation method thereof Download PDFInfo
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- CN104788497A CN104788497A CN201510101595.4A CN201510101595A CN104788497A CN 104788497 A CN104788497 A CN 104788497A CN 201510101595 A CN201510101595 A CN 201510101595A CN 104788497 A CN104788497 A CN 104788497A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
- C07F19/005—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00 without metal-C linkages
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention discloses a lithium doped metal-organic framework DM0.5Li0.5MnF single crystal material and a preparation method thereof. The lithium doped metal-organic framework DM0.5Li0.5MnF single crystal material is composed of white translucent DM0.5Li0.5MnF single crystals with a size of 1.5*1.5*1.5-2.0*2.0*2.0mm<3>, with the mole percentage of the dimethyl ammonia radical ion DM<+1> to lithium ion Li<+1> in the compound being 1:1. The used reagents are commercial products and have no need for tedious preparation, hydrothermal method and liquid phase method are combined to obtain the novel metal-organic framework single crystal material and larger size signal crystals, the process has strong controllability and is easy to operate, and the prepared product has high purity. The lithium doped DMMnF single crystal material obtained in the invention is expected to be widely used in novel metal-organic framework semiconductors, information storage and optical devices.
Description
Technical field
The present invention relates to a kind of lithium doping metal-organic framework monocrystal material and preparation method thereof, specifically refer to a kind of Li doping [(CH
3)
2nH
2] Mn (HCOO)
3monocrystal material (is abbreviated as DM
0.5li
0.5mnF, DM are [(CH
3)
2nH
2]
+ 1, F is [(HCOO)
3]
-3) and preparation method thereof.
Technical background
Metal-organic framework (Metal-Organic Frameworks, MOFs) material is subject to extensive concern because having potential using value in catalysis, Chu Qing and optical element etc., is a focus in current New function investigation of materials field.Due to organic compound have preparation flexibly, the advantage of flexible, the easy cutting of skeleton and the easy aspect such as height of formation anisotropy and low lattice symmetry structure, people attempt, by ferroelectricity organism and magnetic transition metal ionic bond, designing the novel multi-ferroic material based on metal-organic hybrid in recent years.
The discovery of magnetoelectric effect in DMMnF material, shows ferroelectricly to combine organic with magnetic metal ion, greatly will expand the exploration space of multi-ferroic material and magnetoelectric effect.The preparation method of DMMnF mainly contains hydrothermal method, liquid phase method etc.Hydrothermal method refer to sealing pressurized vessel in, using water as solvent, at temperature 100 ~ 400 ° of C, pressure be greater than 0.1MPa until tens to hundreds of MPa condition under, make precursor (raw material) react and crystallization.Namely a special physicochemical environment that cannot obtain in atmospheric conditions is provided, precursor is dissolved fully in reactive system, form atom or molecular growth primitive, nucleation crystallization.The advantages such as it is fast that hydrothermal method has speed of response, and product purity is high, better crystallinity degree, reunion are few.At present, be main by the DMMnF material of water heat transfer mainly with powder crystallite and small monocrystalline, but, be extremely restricted as device application, therefore the growth of how better control DMMnF monocrystalline, make the size of monocrystalline reach the requirement being easy to making devices, and widen its industry application have very important significance.
That studies metal-organic framework materials along with people gos deep into, people are just making great efforts to study fully the magneto-electric coupled mechanism of multiferroic MOFs base monocrystal material, wish magnetic structure and the electronic structure that can be changed DMMnF by compound, some metallic elements that adulterate, and Effective Regulation is carried out to its magnetoelectric effect, thus greatly widen the using value of MOFs material.At present, a kind of Li doping [(CH
3)
2nH
2] Mn (HCOO)
3monocrystal material and preparation method thereof is not also reported.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of lithium doping metal-organic framework DMMnF monocrystal material and preparation method thereof, this DM
0.5li
0.5the preparation method of MnF monocrystalline is simple, convenient.
Technical scheme of the present invention is:
A kind of lithium doping metal-organic framework DM
0.5li
0.5mnF monocrystal material is by being of a size of 1.5 × 1.5 × 1.5 ~ 2.0 × 2.0 × 2.0 mm
3, and diformazan ammonia radical ion DM in compound
+ 1with lithium ion Li
+ 1molar percentage be the white translucent DM of 1:1
0.5li
0.5mnF monocrystalline forms.
Described DM
0.5li
0.5mnF monocrystalline is white translucent crystal, and chemical formula is [(CH
3)
2nH
2]
0.5li
0.5mn (HCOO)
3.
Described lithium doping metal-organic framework DM
0.5li
0.5the preparation method of MnF monocrystal material comprises the steps:
(1) in beaker, add the vitriol oil, acetone, dehydrated alcohol and deionized water successively, respectively ultrasonic cleaning 15 minutes, to remove residual metal ions and organism in beaker, the beaker after cleaning is saved backup;
(2) lithium formate and Manganous chloride tetrahydrate are taken mixing according to the mol ratio of 1:2, be dissolved in distilled water with DMF, stir and make it fully dissolve; Wherein the volume ratio of DMF and distilled water is 1:1, and needed for every mole of lithium formate and Manganous chloride tetrahydrate mixture, distilled water consumption is 6mL;
(3) step (2) gained mixing solutions is loaded in reactor, be heated to 135 ~ 145 ° of C after sealing and react, and be incubated 60 ~ 72 hours, then naturally cool to room temperature;
(4) reacted for step (3) saturated clear liquid transfer pipet taken out and load in the cleaned beaker of step (1), then beaker being put into climatic chamber; Set 30 sections of temperature lowering curves, temperature range is 28 ~ 22 ° of C, every section of temperature difference 0.5 ° of C, and every section of temperature range is incubated 2.5 ~ 3 hours, and humidity is 45 ~ 55%;
(5) by the crystal grain of beaker bottom absolute ethanol washing 3 times, lithium doping metal-organic framework DM within 10 minutes, is obtained in 60 ° of C vacuum-dryings
0.5li
0.5mnF monocrystal material.
The model of described climatic chamber is WHS-70B model.Humidity in described step (4) is controlled by humidifier and climatic chamber.
Beneficial effect:
In preparation process of the present invention, agents useful for same is commerical prod, without the need to loaded down with trivial details preparation; Utilize hydrothermal method and liquid phase method to combine and obtain the larger monocrystalline of size and Novel lithium doping metals-organic frame monocrystal material; Process controllability is strong, easy to operate, and obtained product purity is high.
The DM of gained of the present invention
0.5li
0.5mnF material, is expected to store in novel metal-organic frame semi-conductor, information and be widely used in optics.
Accompanying drawing explanation
Fig. 1 is the DM obtained with the present invention
0.5li
0.5mnF monocrystalline digital photograph;
Fig. 2 is the DM obtained with the present invention
0.5li
0.5x-ray diffraction (XRD) spectrogram of MnF monocrystalline;
Fig. 3 is the DM obtained with the present invention
0.5li
0.5mnF monocrystalline spectrogram, wherein (a) is the DM obtained with the present invention
0.5li
0.5mnF monocrystalline XPS composes entirely, and (b) is the DM obtained with the present invention
0.5li
0.5the XPS spectrum figure of MnF monocrystalline Mn2p; C () is the DM obtained with the present invention
0.5li
0.5the XPS spectrum figure of MnF monocrystalline Li1s.
Embodiment
The present invention is further illustrated below in conjunction with example.
The present invention prepares DM
0.5li
0.5mnF monocrystal material adopts hydrothermal method and liquid phase method to combine method.In beaker, add the vitriol oil, acetone, dehydrated alcohol and deionized water successively, have children outside the state plan cleaning 15 minutes respectively, to remove the impurity such as residual metal ions, organism in beaker, the beaker after cleaning is saved backup.Lithium formate and Manganous chloride tetrahydrate are taken 2.5 mmol according to the mol ratio of 1:2, is dissolved in 15 mL distilled water with 15 mL DMFs (DMF), stir and make it fully dissolve; Wherein the volume ratio of DMF and distilled water is 1:1.This mixing solutions is loaded in reactor, is heated to 135 ~ 145 ° of C after sealing and reacts, and be incubated 60 ~ 72 hours, then naturally cool to room temperature.Reacted saturated clear liquid transfer pipet is taken out and loads in cleaned beaker, then beaker is put into climatic chamber; Set 30 sections of temperature lowering curves, temperature range is 28 ~ 22 ° of C, every section of temperature difference 0.5 ° of C, and every section of temperature range is incubated 2.5 ~ 3 hours, and humidity is 45 ~ 55%.By the crystal grain of beaker bottom absolute ethanol washing 3 times, within 10 minutes, obtain the DM of white translucent in 60 ° of C vacuum-dryings
0.5li
0.5mnF cubic crystal.
Embodiment 1
Lithium formate and Manganous chloride tetrahydrate are taken 2.5 mmol according to the mol ratio of 1:2, is dissolved in 15 mL distilled water with 15 mL DMFs (DMF), stir and make it fully dissolve; Wherein the volume ratio of DMF and distilled water is 1:1.This mixing solutions is loaded in reactor, is heated to 140 ° of C after sealing and reacts, and be incubated 60 hours, then naturally cool to room temperature.Reacted saturated clear liquid transfer pipet is taken out and loads in cleaned beaker, then beaker is put into climatic chamber; Set 30 sections of temperature lowering curves, temperature range is 28 ~ 22 ° of C, and every section of temperature difference 0.5 ° of C, every section of temperature range is incubated 2.5 hours, and humidity is 50%.By the crystal grain of beaker bottom absolute ethanol washing 3 times, within 10 minutes, obtain the DM of white translucent in 60 ° of C vacuum-dryings
0.5li
0.5mnF cubic crystal.
Gained crystal is directly observed (as Fig. 1) under digital camera, can find that crystal is white translucent, be of a size of 1.5 × 1.5 × 1.5 ~ 2.0 × 2.0 × 2.0 mm
3cubic crystal.The powder XRD analysis of Fig. 2 shows product D M
0.5li
0.5mnF shows crystal along (012) direction oriented growth with the interior illustration of do not adulterate DMMnF basically identical (corresponding to CCDC:246991, crystal data center, Cambridge), Fig. 2, forms monocrystalline.In Powder XRD pattern, do not find the diffraction peak of lithium formate and other impurity, show that elemental lithium is successfully adulterated and enter in the lattice of DMMnF crystal.DM can be found out during the XPS of Fig. 3 a composes entirely
0.5li
0.5containing N, Li, Mn in MnF monocrystalline, O, C element, calculates the atomic ratio of product close to 0.5:0.5:2:6:4 through XPS integrating peak areas, and the valent state of Li, Mn is respectively+1 and+divalent (Fig. 3 b, c), shows that the chemical formula of products therefrom is [(CH
3)
2nH
2]
0.5li
0.5mn (HCOO)
3.
Embodiment 2
As embodiment 1, lithium formate and Manganous chloride tetrahydrate are taken 2.5 mmol according to the mol ratio of 1:2, be dissolved in 15 mL distilled water with 15 mL DMFs (DMF), stir and make it fully dissolve; Wherein the volume ratio of DMF and distilled water is 1:1.This mixing solutions is loaded in reactor, is heated to 140 ° of C after sealing and reacts, and be incubated 60 hours, then naturally cool to room temperature.Reacted saturated clear liquid transfer pipet is taken out and loads in cleaned beaker, then beaker is put into climatic chamber; Set 30 sections of temperature lowering curves, temperature range is 28 ~ 22 ° of C, and every section of temperature difference 0.5 ° of C, every section of temperature range is incubated 2.5 hours, and humidity is 50%.By the crystal grain of beaker bottom absolute ethanol washing 3 times, within 10 minutes, obtain the DM of white translucent in 60 ° of C vacuum-dryings
0.5li
0.5mnF cubic crystal.The pattern of product is all identical with embodiment 1 with structure.
Embodiment 3
As embodiment 1, lithium formate and Manganous chloride tetrahydrate are taken 2.5 mmol according to the mol ratio of 1:2, be dissolved in 15 mL distilled water with 15 mL DMFs (DMF), stir and make it fully dissolve; Wherein the volume ratio of DMF and distilled water is 1:1.This mixing solutions is loaded in reactor, is heated to 135 ° of C after sealing and reacts, and be incubated 65 hours, then naturally cool to room temperature.Reacted saturated clear liquid transfer pipet is taken out and loads in cleaned beaker, then beaker is put into climatic chamber; Set 30 sections of temperature lowering curves, temperature range is 28 ~ 22 ° of C, and every section of temperature difference 0.5 ° of C, every section of temperature range is incubated 2.5 hours, and humidity is 45%.By the crystal grain of beaker bottom absolute ethanol washing 3 times, within 10 minutes, obtain the DM of white translucent in 60 ° of C vacuum-dryings
0.5li
0.5mnF cubic crystal.The pattern of product is all identical with embodiment 1 with structure.
Embodiment 4
As embodiment 1, lithium formate and Manganous chloride tetrahydrate are taken 2.5 mmol according to the mol ratio of 1:2, be dissolved in 15 mL distilled water with 15 mL DMFs (DMF), stir and make it fully dissolve; Wherein the volume ratio of DMF and distilled water is 1:1.This mixing solutions is loaded in reactor, is heated to 145 ° of C after sealing and reacts, and be incubated 65 hours, then naturally cool to room temperature.Reacted saturated clear liquid transfer pipet is taken out and loads in cleaned beaker, then beaker is put into climatic chamber; Set 30 sections of temperature lowering curves, temperature range is 28 ~ 22 ° of C, and every section of temperature difference 0.5 ° of C, every section of temperature range is incubated 2.5 hours, and humidity is 55%.By the crystal grain of beaker bottom absolute ethanol washing 3 times, within 10 minutes, obtain the DM of white translucent in 60 ° of C vacuum-dryings
0.5li
0.5mnF cubic crystal.The pattern of product is all identical with embodiment 1 with structure.
Embodiment 5
As embodiment 1, lithium formate and Manganous chloride tetrahydrate are taken 2.5 mmol according to the mol ratio of 1:2, be dissolved in 15 mL distilled water with 15 mL DMFs (DMF), stir and make it fully dissolve; Wherein the volume ratio of DMF and distilled water is 1:1.This mixing solutions is loaded in reactor, is heated to 145 ° of C after sealing and reacts, and be incubated 70 hours, then naturally cool to room temperature.Reacted saturated clear liquid transfer pipet is taken out and loads in cleaned beaker, then beaker is put into climatic chamber; Set 30 sections of temperature lowering curves, temperature range is 28 ~ 22 ° of C, and every section of temperature difference 0.5 ° of C, every section of temperature range is incubated 3 hours, and humidity is 45%.By the crystal grain of beaker bottom absolute ethanol washing 3 times, within 10 minutes, obtain the DM of white translucent in 60 ° of C vacuum-dryings
0.5li
0.5mnF cubic crystal.The pattern of product is all identical with embodiment 1 with structure.
Claims (5)
1. a lithium doping metal-organic framework DM
0.5li
0.5mnF monocrystal material, is characterized in that, is by being of a size of 1.5 × 1.5 × 1.5 ~ 2.0 × 2.0 × 2.0 mm
3, and diformazan ammonia radical ion DM in compound
+ 1with lithium ion Li
+ 1molar percentage be the DM of 1:1
0.5li
0.5mnF monocrystalline forms.
2. a kind of lithium doping metal-organic framework DM according to claim 1
0.5li
0.5mnF monocrystal material, is characterized in that described DM
0.5li
0.5mnF monocrystalline is white translucent crystal, and chemical formula is [(CH
3)
2nH
2]
0.5li
0.5mn (HCOO)
3.
3. a lithium doping metal-organic framework DM as claimed in claim 1
0.5li
0.5the preparation method of MnF monocrystal material, is characterized in that, comprises the steps:
(1) in beaker, add the vitriol oil, acetone, dehydrated alcohol and deionized water successively, respectively ultrasonic cleaning 15 minutes, to remove residual metal ions and organism in beaker, the beaker after cleaning is saved backup;
(2) lithium formate and Manganous chloride tetrahydrate are taken mixing according to the mol ratio of 1:2, be dissolved in distilled water with DMF, stir and make it fully dissolve; Wherein the volume ratio of DMF and distilled water is 1:1, and needed for every mole of lithium formate and Manganous chloride tetrahydrate mixture, distilled water consumption is 6mL;
(3) step (2) gained mixing solutions is loaded in reactor, be heated to 135 ~ 145 ° of C after sealing and react, and be incubated 60 ~ 72 hours, then naturally cool to room temperature;
(4) reacted for step (3) saturated clear liquid transfer pipet taken out and load in the cleaned beaker of step (1), then beaker being put into climatic chamber; Set 30 sections of temperature lowering curves, temperature range is 28 ~ 22 ° of C, every section of temperature difference 0.5 ° of C, and every section of temperature range is incubated 2.5 ~ 3 hours, and humidity is 45 ~ 55%;
(5) by the crystal grain of beaker bottom absolute ethanol washing 3 times, lithium doping metal-organic framework DM within 10 minutes, is obtained in 60 ° of C vacuum-dryings
0.5li
0.5mnF monocrystal material.
4. lithium doping metal-organic framework DM according to claim 3
0.5li
0.5the preparation method of MnF monocrystal material, is characterized in that the model of described climatic chamber is WHS-70B model.
5. lithium doping metal-organic framework DM according to claim 3
0.5li
0.5the preparation method of MnF monocrystal material, is characterized in that the humidity in described step (4) is controlled by humidifier and climatic chamber.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962037A (en) * | 2012-11-01 | 2013-03-13 | 中国科学院大连化学物理研究所 | Metal-organic framework material for methane adsorption separation and preparation method thereof |
-
2015
- 2015-03-09 CN CN201510101595.4A patent/CN104788497A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962037A (en) * | 2012-11-01 | 2013-03-13 | 中国科学院大连化学物理研究所 | Metal-organic framework material for methane adsorption separation and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| PRASHANT JAIN等: "Multiferroic behavior associated with an order-disorder hydrogen bonding transition in metal-organic frameworks (MOFs) with the perovskite ABX3 architecture", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| PRASHANT JAIN等: "Order-disorder antiferroelectric phase transition in a hybrid inorganic-organic framework with the perovskite architecture", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| 孙阳: "高温单相多铁性材料与强磁电耦合效应", 《物理》 * |
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Application publication date: 20150722 |