CN104788506A - Metal-organic framework single crystal epitaxially grown DMMnF/DMCoF heterojunction material and preparation method thereof - Google Patents
Metal-organic framework single crystal epitaxially grown DMMnF/DMCoF heterojunction material and preparation method thereof Download PDFInfo
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- CN104788506A CN104788506A CN201510101695.7A CN201510101695A CN104788506A CN 104788506 A CN104788506 A CN 104788506A CN 201510101695 A CN201510101695 A CN 201510101695A CN 104788506 A CN104788506 A CN 104788506A
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Abstract
The invention discloses a metal-organic framework single crystal epitaxially grown DMMnF/DMCoF heterojunction material and a preparation method thereof. The metal-organic framework single crystal epitaxially grown /DMCoF heterojunction material is a heterojunction composed of a DMCoF single crystal substrate with a size of 1.8*1.8*1.8-2*2*2mm<3> and DMMnF epitaxial single crystals with a size of 2.2*2.2*2.2-2.6*2.6*2.6mm<3> and a thickness of 0.2-0.3mm. In the preparation process of the invention, the used reagents are commercial products and have no need for tedious preparation, hydrothermal method and liquid phase method are combined to obtain the large size single crystals, the process has strong controllability and is easy to operate, and the prepared product has high purity. The DMMnF/DMCoF heterojunction 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 heterojunction material of a kind of metal-organic framework single crystal epitaxial growth and preparation method thereof, specifically refer to a kind of monocrystalline [(CH
3)
2nH
2] Mn (HCOO)
3/ [(CH
3)
2nH
2] Co (HCOO)
3(be abbreviated as DMMnF/DMCoF, DM is [(CH to heterojunction material
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 and DMCoF 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 and DMCoF 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 DMMnF and the DMCoF 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 and DMCoF 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 epitaxy metal-organic framework monocrystalline, wish the size that can be improved monocrystalline by epitaxy metal-organic framework monocrystalline, and obtain some novel heterojunction materials, thus greatly expand the using value of metal-organic framework.At present, a kind of DMMnF/DMCoF heterojunction and preparation method thereof of metal-organic framework single crystal epitaxial growth is not also reported.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide DMMnF/DMCoF heterojunction material of a kind of metal-organic framework single crystal epitaxial growth and preparation method thereof, the preparation method of this DMMnF/DMCoF heterojunction material is simple, convenient simultaneously.
Technical scheme of the present invention is:
A kind of DMMnF/DMCoF heterojunction material of metal-organic framework single crystal epitaxial growth is by being of a size of 1.8 × 1.8 × 1.8 ~ 2 × 2 × 2 mm
3dMCoF single crystalline substrate and be of a size of 2.2 × 2.2 × 2.2 ~ 2.6 × 2.6 × 2.6 mm
3, thickness is the heterojunction of the DMMnF epitaxy single-crystal composition of 0.2 ~ 0.3 mm.
Described DMCoF is rediance cubes monocrystalline, and chemical formula is [(CH
3)
2nH
2] Co (HCOO)
3;described DMMnF is white clear cubes monocrystalline, and chemical formula is [(CH
3)
2nH
2] Mn (HCOO)
3.
The preparation method of the DMMnF/DMCoF heterojunction material of described metal-organic framework single crystal epitaxial growth 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) cobalt chloride, DMF are dissolved in distilled water, stir and make it fully dissolve; Wherein every mole of corresponding distilled water consumption of cobalt chloride is 7.5L, and the volume ratio of DMF and distilled water is 1:1;
(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) step (3) reacted cobalt 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 29 ~ 21 ° of C, every section of temperature difference 0.3 ° of C, and every section of temperature range is incubated 2.5 ~ 3 hours, and humidity is 50 ~ 55%;
(5) by the crystal grain of beaker bottom absolute ethanol washing 3 times, the DMCoF cubic crystal of rediance within 1 hour, is obtained in 60 ° of C vacuum-dryings;
(6) cobalt chloride in step (2) is replaced with Manganous chloride tetrahydrate, implementation step (2) and step (3) obtain the saturated clear liquid of reacted manganese, the DMCoF cubic crystal of the rediance of step (5) gained is put into the saturated clear liquid of manganese, according to the conditioned response of step (4);
(7) epitaxially grown DMMnF/DMCoF heterojunction material is namely obtained according to step (5).
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 metal-organic frame heterojunction material; Process controllability is strong, easy to operate, and obtained product purity is high.
The DMMnF/DMCoF heterojunction material of gained of the present invention, is expected to store in novel metal-organic frame semi-conductor, information and be widely used in optics.
Accompanying drawing explanation
Fig. 1 is DMMnF/DMCoF heterojunction schematic diagram of the present invention;
Fig. 2 is the DMCoF monocrystalline digital photograph obtained with the present invention;
Fig. 3 is the DMMnF/DMCoF heterojunction monocrystalline digital photograph obtained with the present invention;
Fig. 4 is X-ray diffraction (XRD) spectrogram of the DMMnF/DMCoF heterojunction monocrystalline obtained with the present invention;
The DMCoF substrate monocrystal spectrogram that Fig. 5 the present invention obtains, wherein (a) composes entirely with the DMCoF substrate monocrystal XPS that the present invention obtains, and (b) is the XPS spectrum figure of the DMCoF substrate monocrystal Co2p obtained with the present invention;
Fig. 6 is the DMMnF epitaxy single-crystal spectrogram obtained with the present invention, and wherein (a) composes entirely with the DMMnF epitaxy single-crystal XPS that the present invention obtains, and (b) is the XPS spectrum figure of the DMMnF epitaxy single-crystal Mn2p obtained with the present invention.
Embodiment
The present invention is further illustrated below in conjunction with example.
It is adopt hydrothermal method and liquid phase method to combine method that the present invention prepares DMMnF/DMCoF heterojunction monocrystal material.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.2.5 mmol cobalt chloride, 15 mL DMFs (DMF) are dissolved in 15 mL distilled water, stir and make it fully dissolve; Wherein the volume ratio of DMF and distilled water is 1:1.Cobalt chloride solution 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.Saturated for reacted cobalt clear liquid transfer pipet taken out and loads in cleaned beaker, then beaker being put into climatic chamber; Set 30 sections of temperature lowering curves, temperature range is 29 ~ 21 ° of C, every section of temperature difference 0.3 ° of C, and every section of temperature range is incubated 2.5 ~ 3 hours, and humidity is 50 ~ 55%.By the crystal grain of beaker bottom absolute ethanol washing 3 times, within 1 hour, obtain the DMCoF cubic crystal of rediance in 60 ° of C vacuum-dryings.2.5 mmol Manganous chloride tetrahydrates are replaced cobalt chloride, as above the saturated clear liquid of reacted manganese is obtained described in step, the rediance DMCoF cubic crystal obtained in above-mentioned steps is put into this saturated clear liquid, identical reaction conditions is set in climatic chamber, the epitaxially grown white clear DMMnF cubic crystal of final acquisition.
Embodiment 1
2.5 mmol cobalt chloride, 15 mL DMFs (DMF) are dissolved in 15 mL distilled water, stir and make it fully dissolve; Wherein the volume ratio of DMF and distilled water is 1:1.Cobalt chloride solution is loaded in reactor, be heated to 140 ° of C after sealing and react, and be incubated 72 hours, then naturally cool to room temperature.Saturated for reacted cobalt clear liquid transfer pipet taken out and loads in cleaned beaker, then beaker being put into climatic chamber; Set 30 sections of temperature lowering curves, temperature range is 29 ~ 21 ° of C, and every section of temperature difference 0.3 ° 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 1 hour, obtain the DMCoF cubic crystal of rediance in 60 ° of C vacuum-dryings.2.5 mmol Manganous chloride tetrahydrates are replaced cobalt chloride, as above the saturated clear liquid of reacted manganese is obtained described in step, the rediance DMCoF cubic crystal obtained in above-mentioned steps is put into this saturated clear liquid, identical reaction conditions is set in climatic chamber, final acquisition white clear DMMnF cubic crystal.
Gained DMCoF crystal is directly observed (as Fig. 2) under digital camera, can find that crystal is rediance, be of a size of 1.8 × 1.8 × 1.8 ~ 2 × 2 × 2 mm
3cubic crystal.The XRD analysis of Fig. 4 a shows that product is that DMCoF(corresponds to CCDC:246992, crystal data center, Cambridge), and along 012 direction oriented growth, form monocrystalline.Find out from Fig. 3 digital photograph, the white clear DMMnF monocrystalline in the successful epitaxy of DMCoF plane of crystal, is of a size of 2.2 × 2.2 × 2.2 mm
3cubic crystal, the thickness of DMMnF monocrystalline is 0.2 ~ 0.3 mm.The XRD analysis of Fig. 4 b shows that epitaxially grown crystal is that DMMnF(corresponds to CCDC:246991, crystal data center, Cambridge), and along (012) direction oriented growth, form epitaxy single-crystal heterojunction.In XRD spectrum, small diffraction peak is DMCoF substrate monocrystal.Can find out during the XPS of Fig. 5 a composes entirely in substrate monocrystal containing Co, O, N, C element, calculate the atomic ratio of product close to 1:6:1:5 through XPS integrating peak areas, and the valent state of Co is+divalent (Fig. 5 b), shows that the chemical formula of products therefrom is [(CH
3)
2nH
2] Co (HCOO)
3.In like manner, the XPS of DMMnF entirely composes and shows that the chemical formula of gained epitaxy single-crystal is [(CH with Mn2p collection of illustrative plates (Fig. 6)
3)
2nH
2] Mn (HCOO)
3.
Embodiment 2
As embodiment 1,2.5 mmol cobalt chloride, 15 mL DMFs (DMF) are dissolved in 15 mL distilled water, stir and make it fully dissolve; Wherein the volume ratio of DMF and distilled water is 1:1.Cobalt chloride solution is loaded in reactor, be heated to 135 ° of C after sealing and react, and be incubated 65 hours, then naturally cool to room temperature.Saturated for reacted cobalt clear liquid transfer pipet taken out and loads in cleaned beaker, then beaker being put into climatic chamber; Set 30 sections of temperature lowering curves, temperature range is 29 ~ 21 ° of C, and every section of temperature difference 0.3 ° of C, every section of temperature range is incubated 3 hours, and humidity is 50%.By the crystal grain of beaker bottom absolute ethanol washing 3 times, within 1 hour, obtain the DMCoF cubic crystal of rediance in 60 ° of C vacuum-dryings.2.5 mmol Manganous chloride tetrahydrates are replaced cobalt chloride, as above the saturated clear liquid of reacted manganese is obtained described in step, the rediance DMCoF cubic crystal obtained in above-mentioned steps is put into this saturated clear liquid, identical reaction conditions is set in climatic chamber, final acquisition DMMnF/DMCoF heterojunction monocrystalline.The pattern of product is all identical with embodiment 1 with structure.
Embodiment 3
As embodiment 1,2.5 mmol cobalt chloride, 15 mL DMFs (DMF) are dissolved in 15 mL distilled water, stir and make it fully dissolve; Wherein the volume ratio of DMF and distilled water is 1:1.Cobalt chloride solution is loaded in reactor, be heated to 145 ° of C after sealing and react, and be incubated 60 hours, then naturally cool to room temperature.Saturated for reacted cobalt clear liquid transfer pipet taken out and loads in cleaned beaker, then beaker being put into climatic chamber; Set 30 sections of temperature lowering curves, temperature range is 29 ~ 21 ° of C, and every section of temperature difference 0.3 ° of C, every section of temperature range is incubated 2 hours, and humidity is 52%.By the crystal grain of beaker bottom absolute ethanol washing 3 times, within 1 hour, obtain the DMCoF cubic crystal of rediance in 60 ° of C vacuum-dryings.2.5 mmol Manganous chloride tetrahydrates are replaced cobalt chloride, as above the saturated clear liquid of reacted manganese is obtained described in step, the rediance DMCoF cubic crystal obtained in above-mentioned steps is put into this saturated clear liquid, identical reaction conditions is set in climatic chamber, final acquisition DMMnF/DMCoF heterojunction monocrystalline.The pattern of product is all identical with embodiment 1 with structure.
Embodiment 4
As embodiment 1,2.5 mmol cobalt chloride, 15 mL DMFs (DMF) are dissolved in 15 mL distilled water, stir and make it fully dissolve; Wherein the volume ratio of DMF and distilled water is 1:1.Cobalt chloride solution is loaded in reactor, be heated to 140 ° of C after sealing and react, and be incubated 65 hours, then naturally cool to room temperature.Saturated for reacted cobalt clear liquid transfer pipet taken out and loads in cleaned beaker, then beaker being put into climatic chamber; Set 30 sections of temperature lowering curves, temperature range is 29 ~ 21 ° of C, and every section of temperature difference 0.3 ° of C, every section of temperature range is incubated 2 hours, and humidity is 55%.By the crystal grain of beaker bottom absolute ethanol washing 3 times, within 1 hour, obtain the DMCoF cubic crystal of rediance in 60 ° of C vacuum-dryings.2.5 mmol Manganous chloride tetrahydrates are replaced cobalt chloride, as above the saturated clear liquid of reacted manganese is obtained described in step, the rediance DMCoF cubic crystal obtained in above-mentioned steps is put into this saturated clear liquid, identical reaction conditions is set in climatic chamber, final acquisition DMMnF/DMCoF heterojunction monocrystalline.The pattern of product is all identical with embodiment 1 with structure.
Embodiment 5
As embodiment 1,2.5 mmol cobalt chloride, 15 mL DMFs (DMF) are dissolved in 15 mL distilled water, stir and make it fully dissolve; Wherein the volume ratio of DMF and distilled water is 1:1.Cobalt chloride solution is loaded in reactor, be heated to 140 ° of C after sealing and react, and be incubated 70 hours, then naturally cool to room temperature.Saturated for reacted cobalt clear liquid transfer pipet taken out and loads in cleaned beaker, then beaker being put into climatic chamber; Set 30 sections of temperature lowering curves, temperature range is 29 ~ 21 ° of C, and every section of temperature difference 0.3 ° of C, every section of temperature range is incubated 2.5 hours, and humidity is 55%, total coreaction 80 hours.By the crystal grain of beaker bottom absolute ethanol washing 3 times, within 1 hour, obtain the DMCoF cubic crystal of rediance in 60 ° of C vacuum-dryings.2.5 mmol Manganous chloride tetrahydrates are replaced cobalt chloride, as above the saturated clear liquid of reacted manganese is obtained described in step, the rediance DMCoF cubic crystal obtained in above-mentioned steps is put into this saturated clear liquid, identical reaction conditions is set in climatic chamber, final acquisition DMMnF/DMCoF heterojunction monocrystalline.The pattern of product is all identical with embodiment 1 with structure.
Claims (4)
1. a DMMnF/DMCoF heterojunction material for metal-organic framework single crystal epitaxial growth, is characterized in that, is by being of a size of 1.8 × 1.8 × 1.8 ~ 2 × 2 × 2 mm
3dMCoF single crystalline substrate and be of a size of 2.2 × 2.2 × 2.2 ~ 2.6 × 2.6 × 2.6 mm
3, thickness is the heterojunction of the DMMnF epitaxy single-crystal composition of 0.2 ~ 0.3 mm.
2. the DMMnF/DMCoF heterojunction material of metal-organic framework single crystal epitaxial growth according to claim 1, it is characterized in that described DMCoF is rediance cubes monocrystalline, chemical formula is [(CH
3)
2nH
2] Co (HCOO)
3;described DMMnF is white clear cubes monocrystalline, and chemical formula is [(CH
3)
2nH
2] Mn (HCOO)
3.
3. a preparation method for the DMMnF/DMCoF heterojunction material of metal-organic framework single crystal epitaxial growth as claimed in claim 1, is characterized in that, comprise 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) cobalt chloride, DMF are dissolved in distilled water, stir and make it fully dissolve; Wherein every mole of corresponding distilled water consumption of cobalt chloride is 7.5L, and the volume ratio of DMF and distilled water is 1:1;
(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) step (3) reacted cobalt 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 29 ~ 21 ° of C, every section of temperature difference 0.3 ° of C, and every section of temperature range is incubated 2.5 ~ 3 hours, and humidity is 50 ~ 55%;
(5) by the crystal grain of beaker bottom absolute ethanol washing 3 times, the DMCoF cubic crystal of rediance within 1 hour, is obtained in 60 ° of C vacuum-dryings;
(6) cobalt chloride in step (2) is replaced with Manganous chloride tetrahydrate, implementation step (2) and step (3) obtain the saturated clear liquid of reacted manganese, the DMCoF cubic crystal of the rediance of step (5) gained is put into the saturated clear liquid of manganese, according to the conditioned response of step (4);
(7) epitaxially grown DMMnF/DMCoF heterojunction material is namely obtained according to step (5).
4. DMMnF/DMCoF heterojunction material preparation method according to claim 3, is characterized in that the humidity in described step (4) is controlled by humidifier and climatic chamber.
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| CN106637414A (en) * | 2016-12-15 | 2017-05-10 | 浙江理工大学 | Metal-organic framework DMMnF/strontium formate heterojunction single crystal optical material and preparation method thereof |
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| CN102414255A (en) * | 2009-02-27 | 2012-04-11 | 环球油品公司 | Block coordination copolymers |
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| CN106637414A (en) * | 2016-12-15 | 2017-05-10 | 浙江理工大学 | Metal-organic framework DMMnF/strontium formate heterojunction single crystal optical material and preparation method thereof |
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