CN104674351B - A kind of formiate LiCa (COOH)3Monocrystalline optical material and preparation method thereof - Google Patents
A kind of formiate LiCa (COOH)3Monocrystalline optical material and preparation method thereof Download PDFInfo
- Publication number
- CN104674351B CN104674351B CN201510102062.8A CN201510102062A CN104674351B CN 104674351 B CN104674351 B CN 104674351B CN 201510102062 A CN201510102062 A CN 201510102062A CN 104674351 B CN104674351 B CN 104674351B
- Authority
- CN
- China
- Prior art keywords
- lica
- cooh
- monocrystalline
- beaker
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention discloses a kind of formiate LiCa (COOH)3Monocrystalline optical material and preparation method thereof, it is 4.0 × 4.0 × 1.5~4.5 × 4.5 × 2.5mm by size3LiCa (COOH)3Monocrystalline forms.Described LiCa (COOH)3Monocrystalline is colourless transparent crystal.Described LiCa (COOH)3The chemical formula of single crystal compound is LiCa (COOH)3.In preparation process of the present invention, agents useful for same is commercial product, without cumbersome preparation；It is combined using hydro-thermal method and liquid phase method and obtains large-sized monocrystalline；Process controllability is strong, easy to operate, and obtained product purity is high.The lithium formate calcium monocrystalline optical material of gained of the invention, is expected to be widely used in terms of novel metal organic frame semiconductor, optic communication and optics, while the LiCa (COOH)3The preparation method of monocrystalline is simply, conveniently.
Description
Technical field
The present invention relates to a kind of formiate monocrystal material and preparation method thereof, in particular to a kind of metal organic frame first
Barbiturates LiCa (COOH)3Monocrystalline optical material and preparation method thereof.
Technical background
Metal-organic framework (Metal-Organic Frameworks, MOFs) material is because in catalysis, hydrogen storage and optics member
Part etc. has potential application value and received significant attention, and is 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
The advantages of symmetrical structure etc., people attempt formiate compound being applied to optics, it is desirable to design and be based on
The novel optical material of formiate, it will expand the exploration space of optical material significantly.
In recent years, device for non-linear optical becomes a focus in novel optical investigation of materials field.Nonlinear optics
Material refers to that its optical property depends on the material of incident intensity, and nonlinear optical property is also referred to as the light under strong light action
Property is learned, these properties is primarily due to and is only just showed under the light action that is concerned with by force as laser.Utilize nonlinear optical
Frequency and incident light can be obtained by learning the non-linear process such as frequency multiplication and frequency, difference frequency, optically erasing and the Multiphoton Absorbtion of crystal
The different laser of frequency, so as to reach the purpose of light frequency conversion.This crystalloid is widely used in laser frequency conversion, four ripples mix
Frequently, light beam steering, image amplification, optical information processing, optical storage, optical-fibre communications, underwater communication, laser countermeasure (s) and nuclear fusion etc. are ground
Study carefully field.
Lithium forate crystal is a kind of water white transparency, the good potential nonlinear optical material of optical property.Lithium formate
Preparation method mainly has hydro-thermal method, liquid phase method and double decomposition etc..Hydro-thermal method refers in the pressure vessel of sealing, using water as
Solvent, in 100~400 DEG C of temperature, pressure is more than 0.1MPa until under conditions of tens to hundreds of MPa, makes predecessor (raw material)
React and crystallize.One special physicochemical environment that can not be obtained in atmospheric conditions is provided, makes predecessor anti-
Answer in system and sufficiently dissolved, form atom or molecular growth primitive, be nucleated and crystallize.Hydro-thermal method has reaction speed
It hurry up, product purity height, better crystallinity degree, reunite the advantages that few.At present, the formiate metal synthesized by hydro-thermal method-have machine frame
Frame material is more still, to be extremely restricted based on powder crystallite and small monocrystalline as device application, therefore how preferably
Control the growth of its monocrystalline so that the size of monocrystalline reaches the requirement for being easy to making devices, and widens its industry and apply with non-
Often important meaning.At present, a kind of formiate LiCa (COOH)3Monocrystalline optical material and preparation method thereof is not yet reported that.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, there is provided a kind of formiate LiCa (COOH)3Monocrystalline light
Learn material and preparation method thereof.To obtain new LiCa (COOH)3Material and larger-sized LiCa (COOH)3Monocrystalline, together
When the LiCa (COOH)3The preparation method of monocrystalline is simply, conveniently.
The technical scheme is that：
A kind of formiate LiCa (COOH)3Monocrystalline optical material by size be 2.5 × 2.5 × 1.5~3.0 × 3.0 ×
2.0mm3LiCa (COOH)3Monocrystalline forms.
Described LiCa (COOH)3Monocrystalline is colourless transparent crystal.Described LiCa (COOH)3The chemistry of single crystal compound
Formula is LiCa (COOH)3。
The formiate LiCa (COOH)3Monocrystalline optical material preparation method comprises the steps：
(1) 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) calcium formate, lithium formate, DMF are dissolved in distilled water, stirring makes it fully dissolve；Wherein
The mol ratio of calcium formate and lithium formate is 1: 1, and it is 15L that every mole of calcium formate, which correspondingly distills water consumption, DMF
Volume ratio with distilled water is 1: 6；
(3) mixed solution obtained by step (2) is loaded in reactor, 100~110 DEG C is heated to after sealing and is carried out instead
Should, and 60~72 hours are incubated, then naturally cool to room temperature；
(4) the reacted saturation clear liquid of step (3) is taken out and is fitted into the beaker that step (1) was cleaned with pipette,
Then beaker is put into climatic chamber；30 sections of temperature lowering curves are set, temperature range is 30~21 DEG C, every section of 0.3 DEG C of temperature difference,
Every section of temperature range is incubated 1.5~2 hours, and humidity is 50~60%；
(5) crystal grain of beaker bottom is washed 3 times with absolute ethyl alcohol, LiCa is obtained within 15 minutes in 60 DEG C of vacuum drying
(COOH)3Monocrystal material.
The model HWS-080 models of described climatic chamber.Humidity in the step 4) is by humidifier and constant temperature
Constant humidity cabinet controls.
Beneficial effect：
In preparation process of the present invention, agents useful for same is commercial product, without cumbersome preparation；Utilize hydro-thermal method and liquid phase method phase
With reference to acquisition Novel Formate metalloid-organic frame monocrystalline optical material and larger-sized monocrystalline；Process controllability is strong,
Easy to operate, obtained product purity is high.
The LiCa (COOH) of gained of the invention3Monocrystalline optical material, it is expected in novel metal-organic frame semiconductor, light
It is widely used in terms of communication and optics.
Brief description of the drawings
Fig. 1 is with LiCa produced by the present invention (COOH)3Monocrystalline digital photograph；
Fig. 2 is with LiCa produced by the present invention (COOH)3X-ray diffraction (XRD) spectrogram of monocrystalline；
Fig. 3 (a) is obtained LiCa (COOH)3Monocrystalline XPS is composed entirely；
Fig. 3 (b) is obtained LiCa (COOH)3The Ca2p of monocrystalline XPS spectrum figure；
Fig. 3 (c) is obtained LiCa (COOH)3The Li1s of monocrystalline XPS spectrum figure.
Embodiment
The present invention is further illustrated below in conjunction with example.
The present invention prepares LiCa (COOH)3Monocrystalline optical material is to be combined method using hydro-thermal method and liquid phase method.Burning
The concentrated sulfuric acid, acetone, absolute ethyl alcohol and deionized water are sequentially added in cup, excusing from death cleaning 15 minutes, residual in beaker to remove respectively
The impurity such as remaining metal ion, organic matter, the beaker after cleaning is saved backup.By 2 mmol calcium formates, 2mmol lithium formates, 5mL
DMF (DMF) is dissolved in 30mL distilled water, and stirring makes it fully dissolve；Wherein calcium formate and lithium formate rubs
Your ratio is 1: 1, DMF and the volume ratio of distilled water is 1: 6.The mixed solution is loaded in reactor, is heated to after sealing
100~110 DEG C are reacted, and are incubated 60~72 hours, then naturally cool to room temperature.Reacted saturation clear liquid is used
Pipette is taken out and is fitted into the beaker that step (1) was cleaned, and then beaker is put into climatic chamber；30 sections of coolings of setting
Curve, temperature range are 30~21 DEG C, and every section of 0.3 DEG C of temperature difference, every section of temperature range is incubated 1.5~2 hours, humidity is 50~
60%.The crystal grain of beaker bottom is washed 3 times with absolute ethyl alcohol, water white transparency is obtained within 15 minutes in 60 DEG C of vacuum drying
LiCa(COOH)3Crystal.
Embodiment 1
2mmol calcium formates, 2mmol lithium formates, 5mL DMFs (DMF) are dissolved in 30mL distilled water,
Stirring makes it fully dissolve；Wherein the mol ratio of calcium formate and lithium formate is 1: 1, DMF and the volume ratio of distilled water is 1: 6.Will
The mixed solution loads in reactor, and 105 DEG C are heated to after sealing and is reacted, and is incubated 60 hours, then naturally cold
But to room temperature.Reacted saturation clear liquid is taken out and is fitted into the beaker that step (1) was cleaned with pipette, then by beaker
It is put into climatic chamber；30 sections of temperature lowering curves are set, temperature range is 30~21 DEG C, every section of 0.3 DEG C of temperature difference, every section of humidity province
Between be incubated 2 hours, humidity 50%.The crystal grain of beaker bottom is washed 3 times with absolute ethyl alcohol, in 60 DEG C of vacuum drying
The LiCa (COOH) for obtaining water white transparency in 15 minutes3Crystal.
Gained crystal is observed into (such as Fig. 1) directly under digital camera, it can be found that crystal is in water white transparency, size is
2.5 × 2.5 × 1.5~3.0 × 3.0 × 2.0mm3Crystal.Fig. 2 powder XRD analysis shows product LiCa (COOH)3With crystalline substance
Volume data storehouse CCDC：246991 (Cambridge crystal data centers) are completely corresponding, illustrate the crystal structure and perovskite of products therefrom
[(the CH of structure3)2NH2]Mn(HCOO)3Unanimously.Fig. 2 interior illustration shows that crystal along (012) direction oriented growth, is formed single
It is brilliant.There is no the diffraction maximum for finding calcium formate, lithium formate and other impurity in XRD spectrum, the product for showing synthesis is pure
LiCa(COOH)3Monocrystalline crystal.It can be seen that LiCa (COOH) during Fig. 3 a XPS is composed entirely3Contain Li, Ca, C in monocrystalline, O elements,
The atomic ratio of product is calculated close to 1: 1: 3: 6 through XPS integrating peak areas, and Ca and Li valent state is respectively+2
Valency (Fig. 3 b) and+1 valency (Fig. 3 c), the chemical formula for showing products therefrom are LiCa (COOH)3。
Embodiment 2
Such as embodiment 1,2mmol calcium formates, 2mmol lithium formates, 5mL DMFs (DMF) are dissolved in
In 30mL distilled water, stirring makes it fully dissolve；Wherein the mol ratio of calcium formate and lithium formate is the body of 1: 1, DMF and distilled water
Product is than being 1: 6.The mixed solution is loaded in reactor, 110 DEG C are heated to after sealing and is reacted, and it is small to be incubated 65
When, then naturally cool to room temperature.Reacted saturation clear liquid is taken out and loaded the beaker that step (1) cleaned with pipette
In, then beaker is put into climatic chamber；30 sections of temperature lowering curves are set, temperature range is 30~21 DEG C, every section of temperature difference 0.3
DEG C, every section of temperature range is incubated 1.5 hours, humidity 55%.The crystal grain of beaker bottom is washed 3 times with absolute ethyl alcohol,
The LiCa (COOH) for obtaining water white transparency in 15 minutes is dried in vacuo in 60 DEG C3Crystal.The pattern and structure of product with embodiment 1
It is identical.
Embodiment 3
Such as embodiment 1,2mmol calcium formates, 2mmol lithium formates, 5mL DMFs (DMF) are dissolved in
In 30mL distilled water, stirring makes it fully dissolve；Wherein the mol ratio of calcium formate and lithium formate is the body of 1: 1, DMF and distilled water
Product is than being 1: 6.The mixed solution is loaded in reactor, 110 DEG C are heated to after sealing and is reacted, and it is small to be incubated 65
When, then naturally cool to room temperature.Reacted saturation clear liquid is taken out and loaded the beaker that step (1) cleaned with pipette
In, then beaker is put into climatic chamber；30 sections of temperature lowering curves are set, temperature range is 30~21 DEG C, every section of temperature difference 0.3
DEG C, every section of temperature range is incubated 2 hours, humidity 60%.The crystal grain of beaker bottom is washed 3 times with absolute ethyl alcohol, in
60 DEG C are dried in vacuo the LiCa (COOH) for obtaining water white transparency in 15 minutes3Crystal.The pattern and structure of product with the phase of embodiment 1
Together.
Embodiment 4
Such as embodiment 1,2mmol calcium formates, 2mmol lithium formates, 5mL DMFs (DMF) are dissolved in
In 30mL distilled water, stirring makes it fully dissolve；Wherein the mol ratio of calcium formate and lithium formate is the body of 1: 1, DMF and distilled water
Product is than being 1: 6.The mixed solution is loaded in reactor, 100 DEG C are heated to after sealing and is reacted, and it is small to be incubated 72
When, then naturally cool to room temperature.Reacted saturation clear liquid is taken out and loaded the beaker that step (1) cleaned with pipette
In, then beaker is put into climatic chamber；30 sections of temperature lowering curves are set, temperature range is 30~21 DEG C, every section of temperature difference 0.3
DEG C, every section of temperature range is incubated 1.5 hours, humidity 50%.The crystal grain of beaker bottom is washed 3 times with absolute ethyl alcohol,
The LiCa (COOH) for obtaining water white transparency in 15 minutes is dried in vacuo in 60 DEG C3Crystal.The pattern and structure of product with embodiment 1
It is identical.
Embodiment 5
Such as embodiment 1,2mmol calcium formates, 2mmol lithium formates, 5mL DMFs (DMF) are dissolved in
In 30mL distilled water, stirring makes it fully dissolve；Wherein the mol ratio of calcium formate and lithium formate is the body of 1: 1, DMF and distilled water
Product is than being 1: 6.The mixed solution is loaded in reactor, 100 DEG C are heated to after sealing and is reacted, and it is small to be incubated 65
When, then naturally cool to room temperature.Reacted saturation clear liquid is taken out and loaded the beaker that step (1) cleaned with pipette
In, then beaker is put into climatic chamber；30 sections of temperature lowering curves are set, temperature range is 30~21 DEG C, every section of temperature difference 0.3
DEG C, every section of temperature range is incubated 2 hours, humidity 50%.The crystal grain of beaker bottom is washed 3 times with absolute ethyl alcohol, in
60 DEG C are dried in vacuo the LiCa (COOH) for obtaining water white transparency in 15 minutes3Crystal.The pattern and structure of product with the phase of embodiment 1
Together.
Claims (3)
- A kind of 1. formiate LiCa (COOH)3The preparation method of monocrystalline optical material, it is characterised in that comprise the steps：(1) 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) calcium formate, lithium formate, DMF are dissolved in distilled water, stirring makes it fully dissolve；Wherein formic acid The mol ratio of calcium and lithium formate is 1: 1, and it is 15L that every mole of calcium formate, which correspondingly distills water consumption, and DMF is with steaming The volume ratio of distilled water is 1: 6；(3) mixed solution obtained by step (2) is loaded in reactor, 100~110 DEG C is heated to after sealing and is reacted, And 60~72 hours are incubated, then naturally cool to room temperature；(4) the reacted saturation clear liquid of step (3) is taken out and is fitted into the beaker that step (1) was cleaned with pipette, then Beaker is put into climatic chamber；30 sections of temperature lowering curves are set, temperature range is 30~21 DEG C, every section of 0.3 DEG C, every section of temperature difference Temperature range is incubated 1.5~2 hours, and humidity is 50~60%；(5) crystal grain of beaker bottom is washed 3 times with absolute ethyl alcohol, LiCa is obtained within 15 minutes in 60 DEG C of vacuum drying (COOH)3Monocrystal material；It is 2.5 × 2.5 × 1.5~3.0 × 3.0 × 2.0mm to obtain by size3LiCa (COOH)3Monocrystalline group Into formiate LiCa (COOH)3Monocrystalline optical material, LiCa (COOH)3Monocrystal material is colourless transparent crystal.
- 2. LiCa (COOH) according to claim 13The preparation method of monocrystalline optical material, it is characterised in that described constant temperature The model HWS-080 models of constant humidity cabinet.
- 3. LiCa (COOH) according to claim 13The preparation method of monocrystalline optical material, it is characterised in that the step 4) In humidity controlled by humidifier and climatic chamber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510102062.8A CN104674351B (en) | 2015-03-09 | 2015-03-09 | A kind of formiate LiCa (COOH)3Monocrystalline optical material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510102062.8A CN104674351B (en) | 2015-03-09 | 2015-03-09 | A kind of formiate LiCa (COOH)3Monocrystalline optical material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104674351A CN104674351A (en) | 2015-06-03 |
| CN104674351B true CN104674351B (en) | 2018-03-20 |
Family
ID=53309912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510102062.8A Active CN104674351B (en) | 2015-03-09 | 2015-03-09 | A kind of formiate LiCa (COOH)3Monocrystalline optical material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104674351B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4123062A1 (en) * | 1991-07-12 | 1993-01-14 | Degussa | Calcium formate prepn. with high yield and quality - by reacting calcium hydroxide and methanol, distilling off methanol and crystallising the prod., used as e.g. cement setting accelerator, etc. |
| DE19929346A1 (en) * | 1999-06-26 | 2000-12-28 | Bayer Ag | Dust-free, free-flowing calcium formate production, especially for use as feed additive, by agglomerating microcrystalline material in presence of auxiliary |
-
2015
- 2015-03-09 CN CN201510102062.8A patent/CN104674351B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| Irreversible transformation of chiral to achiral polymorph of K[Co(HCOO)3]:synthesis,structures, and magnetic properties;Zhiming Duan, et al.;《Dalton Trans.》;20110317;第40卷;第4465-4473页 * |
| Perovskite-like Metal Formates with Weak Ferromagnetism and as Precursors to Amorphous Materials;Xin-Yi Wang, et al.;《Inorg. Chem.》;20040626;第43卷(第15期);第4615-4625页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104674351A (en) | 2015-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105384188A (en) | Cesium lead bromide powder preparation method | |
| CN108559503B (en) | Cs (volatile organic Compounds)2AgBiBr6Double perovskite and preparation method thereof | |
| CN107986323B (en) | A kind of CsPb2Br5The preparation method of inorganic perovskite nanometer sheet | |
| CN109411327B (en) | All-inorganic perovskite nanowire CsPbX2Y and preparation method and application thereof | |
| CN104788505B (en) | A kind of DMCoF/DMMnF heterojunction materials of metal organic frame single crystal epitaxial growth and preparation method thereof | |
| CN104674334B (en) | A kind of formiate LiMg (COOH)3Monocrystalline optical material and preparation method thereof | |
| CN109338465B (en) | Perovskite single crystal material and preparation method and application thereof | |
| CN110128134B (en) | Preparation method of lead titanate film with niobium-doped strontium titanate as substrate | |
| CN104674351B (en) | A kind of formiate LiCa (COOH)3Monocrystalline optical material and preparation method thereof | |
| CN110563666B (en) | Preparation method of 2-thiazolidinone | |
| CN104674350B (en) | A kind of multiferroic formiate LiCo (COOH)3Monocrystal material and preparation method thereof | |
| CN104726937B (en) | Calcium formate single crystal optical material and preparation method thereof | |
| CN101494170B (en) | Method for preparing Sm2O3 film by microwave assisted hydrothermal process | |
| CN104651942B (en) | A kind of multiferroic formiate LiMn (COOH)3Monocrystal material and preparation method thereof | |
| CN111005061B (en) | Preparation method of perovskite single crystal | |
| CN104788507B (en) | A kind of mg-doped metal organic frame DMMg0.5Mn0.5F monocrystal materials and preparation method thereof | |
| CN104788506B (en) | A kind of DMMnF/DMCoF heterojunction materials of metal organic frame single crystal epitaxial growth and preparation method thereof | |
| CN106637414A (en) | Metal-organic framework DMMnF/strontium formate heterojunction single crystal optical material and preparation method thereof | |
| CN107226481B (en) | A kind of preparation method of the spherical lanthanium titanate of particle | |
| CN104725434B (en) | A kind of mg-doped metal organic frame DMMg0.5Co0.5F monocrystal materials and preparation method thereof | |
| CN103708534B (en) | A kind of solution method prepares the method for cesium triiodide tin thin film | |
| CN104788476A (en) | Metal-organic framework DMCaF monocrystalline material and preparation method thereof | |
| CN104788475B (en) | A kind of metal organic frame DMMgF monocrystal materials and preparation method thereof | |
| CN104762661A (en) | A copper-doped metal-organic framework DMMnF single crystal material and a preparing method thereof | |
| CN104762662A (en) | A copper-doped metal-organic framework DMCoF single crystal material and a preparing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191113 Address after: No.1, Chuangye building, 1750 Shengli West Road, Yuhui District, Bengbu City, Anhui Province Patentee after: Bengbu xiaoshuren Software Technology Co., Ltd Address before: 322209 Zhejiang County of Pujiang Province Yu Xiang Pu Yang Village No. 54 Patentee before: Zhang Xiangli |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200214 Address after: 410600 Manufacturing Park Road, Maotian Industrial Park, Chengjiao Township, Ningxiang, Changsha, Hunan Province Patentee after: Ningxiang Xinyang Chemical Co.,Ltd. Address before: No.1, Chuangye building, 1750 Shengli West Road, Yuhui District, Bengbu City, Anhui Province Patentee before: Bengbu xiaoshuren Software Technology Co., Ltd |