CN107098401B - A kind of delafossite structure CuCoO2Crystalline material and its low temperature preparation method - Google Patents
A kind of delafossite structure CuCoO2Crystalline material and its low temperature preparation method Download PDFInfo
- Publication number
- CN107098401B CN107098401B CN201710407330.6A CN201710407330A CN107098401B CN 107098401 B CN107098401 B CN 107098401B CN 201710407330 A CN201710407330 A CN 201710407330A CN 107098401 B CN107098401 B CN 107098401B
- Authority
- CN
- China
- Prior art keywords
- cucoo
- reaction
- compound
- crystalline material
- delafossite structure
- 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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to delafossite structure crystalline materials to be synthetically prepared field, is synthetically prepared CuCoO at a lower temperature in particular with hydro-thermal method2Crystalline material.A kind of delafossite structure CuCoO2The low temperature preparation method of crystalline material, it is characterised in that：It is reacted using low-temperature hydrothermal, fill factor of the regulation including reaction solution in precursors component, reaction temperature and hydrothermal reaction kettle, at 100~120 DEG C, with Co (NO3)2·6H2O and Cu (NO3)2·3H2O is after reactant reaction 12~36 hours, and by reaction product after eccentric cleaning processing and drying, obtain 1~4 micron of size obtains delafossite structure CuCoO2Crystalline material.The present invention is synthetically prepared CuCoO with other2The method of crystalline material is compared, ultralow temperature, high yield, low cost, low pollution.
Description
Technical field
The present invention relates to delafossite structure crystalline materials to be synthetically prepared field, at a lower temperature in particular with hydro-thermal method
It is synthetically prepared CuCoO2Crystalline material.
Background technique
1997, the Kawazoe of Tokyo polytechnical university is taught reported that being based on valence band chemistry repairs for the first time on Nature
(Chemical modulation of Valence band, abbreviation CMVB) theory is adornd, pulse laser is utilized to deposit (Pulse
Laser Deposition, abbreviation PLD) technology, it prepares with the delafossite knot for being suitble to a large amount of how sub- holes to exist and transport
Structure (ABO2) intrinsically p-type electrically conducting transparent CuAlO2Film, the conductivity of film is 0.95s/cm at room temperature.This achievement pushes
P-type delafossite structure transparent conductive oxide (Transparent conductive oxide, abbreviation TCO) material it is swift and violent
Development, brings hope to prepare p-n junction diode and the transparent semiconductor device of all-transparent.It is theoretical based on valence band chemical modification
Design preparation CuAlO2The inspiration of film, a large amount of ABO with delafossite structure2(A=Cu or Ag；B=Al, Ga, In, Sc, Y,
Cr, Co or La etc.) material, lanthanum copper oxysulfide (LaCuOS and LaCuOSe etc.) and SrCu2O2Equal materials become the weight of p-type TCO
Point perpetual object.In recent years, application study of the transparent conductive oxide film in various fields rapidly develops, and new TCO is thin
Membrane material is commonplace.Meanwhile it is relevant theoretical as band theory, doping theory and crystal structure theory have also obtained further
It is perfect.The research and development of p-type TCO material are implemented as possibility for make all-transparent p-n junction, with p-n junction are basic for realizing
The meaning of the practical application of the photoelectric device of structure is very great, has also caused the investigation of materials that numerous values must be explored at the same time
The appearance of project.
2010, M.Beekman et al. passed through CuCl and LiCoO2Between simple ion exchange solid-state reaction, 590
After reacting 48 hours at DEG C, polycrystalline delafossite oxide CuCoO is prepared for the first time2Material.CuCoO2Crystal is a kind of novel p
Type transparent conductive oxide material, belongs to R-3m space group.The CuCoO of 3R crystal form2Cell parameter Currently, generally CuCoO can be prepared by ion-exchange reactions or high temperature solid state reaction2Crystalline material.Example
Such as 2013, Ruttanapun C et al. synthesized delafossite structure at 1005 DEG C of high temperature, using conventional solid reaction method
CuCoO2Crystalline material.But CuCoO is not synthesized about hydro-thermal method2The correlative study of crystalline material is reported.Therefore, water is utilized
Thermal method prepares CuCoO2Material be it is very novel, for explore prepare p-type CuCoO2Nanocrystalline material and its device, which are applied, to be had
Highly important research significance.
Up to the present, copper-based delafossite material, including high temperature solid-state method, collosol and gel can be prepared there are many method
Method, pulsed laser deposition, sputtering method, chemical vapour deposition technique, hydro-thermal method etc..In the method that these prepare target product,
Hydro-thermal method is a kind of relatively green simple preparation method, crystalline oxides can be directly obtained from aqueous medium, it is considered to be ring
Border is polluted less, cost is relatively low, is easy to a kind of commercialized method with stronger competitiveness.With traditional solid phase high-temperature sintering process
Prepare delafossite structure CuCoO2Crystalline material compares, hydro-thermal method reactant is placed under special environment (closed, low temperature,
High pressure etc.) synthetic reaction occurs, two complicated experimental implementations of high-temperature calcination and ball milling are avoided, also prevention introduces impurity and makes
At fault of construction.Meanwhile by adjusting hydrothermal reaction condition, such as reactant presoma component, reaction time, temperature, pressure
And solution ph etc., it is easy to get to high purity, crystal form is good, pattern and size tunable delafossite CuCoO2Material.
Currently, the research report about the copper-based delafossite material of hydrothermal reaction at low temperature synthesis series focuses mostly in CuAlO2,
CuGaO2, CuCrO2And CuFeO2On, it does not find temporarily any using hydrothermal reaction at low temperature synthesis delafossite structure CuCoO2Material
Research report.Therefore, it is badly in need of stepping up to carry out the copper-based delafossite CuCoO of hydro-thermal method synthesis2The basic research of semiconductor material, system
Hydro-thermal preparation process is optimized and revised, its hydrothermal growth mechanism is inquired into, regulates and controls its characteristic of semiconductor comprehensively, it is various novel to be suitable for
In photoelectric functional device.
Summary of the invention
The technical problem to be solved by the present invention is to：A kind of delafossite structure CuCoO is provided2Crystalline material and its low temperature system
Preparation Method, this method can low-temperature hydrothermal synthesize CuCoO2Crystalline material.
The present invention solves its technical problem, and the following technical solution is employed：A kind of delafossite structure CuCoO2Crystalline material,
It is characterized in that it is obtained by following steps：
1) precursors are prepared：By containing Cu2+Compound, contain Co2+Compound in Cu2+、Co2+Molar ratio 1：1,
It chooses and contains Cu2+Compound and contain Co2+Compound；
At room temperature, Cu will be contained2+Compound and contain Co2+Compound be added in pure water, it is abundant in magnetic stirring apparatus
After stirring and dissolving, obtain containing Cu2+With contain Co2+Aqueous solution, Cu2+And Co2+Concentration be respectively 4.33-4.92Wt%, 5.17-
5.87Wt%；It adds containing Cu2+Or contain Co2+Compound 4~8 times of moles NaOH as mineralizer, be stirred well to
After dissolution completely, precursors are obtained, for use；
2) then precursors are transferred in hydrothermal reaction kettle, filling rate is 65~75%, at 100~120 DEG C
Reaction 12~36 hours；After reaction product is handled, dried through multiple eccentric cleaning, delafossite structure CuCoO is obtained2Crystal
Material.
A kind of above-mentioned delafossite structure CuCoO2The low temperature preparation method of crystalline material, it is characterised in that including walking as follows
Suddenly：
1) precursors are prepared：By containing Cu2+Compound, contain Co2+Compound in Cu2+、Co2+Molar ratio 1：1,
It chooses and contains Cu2+Compound and contain Co2+Compound；
At room temperature, Cu will be contained2+Compound and contain Co2+Compound be added in pure water, it is abundant in magnetic stirring apparatus
After stirring and dissolving, obtain containing Cu2+With contain Co2+Aqueous solution, Cu2+And Co2+Concentration be respectively 4.33-4.92Wt%, 5.17-
5.87Wt%；It adds containing Cu2+Or contain Co2+Compound 4~8 times of moles NaOH as mineralizer, be stirred well to
After dissolution completely, precursors are obtained, for use；
2) then precursors are transferred in hydrothermal reaction kettle, filling rate is 65~75%, at 100~120 DEG C
React 12~36 hours (keeping the temperature 12~36 hours at a temperature of 100~120 DEG C of baking oven after sealing to be reacted)；Wait react knot
Reaction kettle natural cooling after beam takes out reaction product, reaction product is handled through eccentric cleaning, and drying (dry in baking oven) obtains
To delafossite structure CuCoO2Crystalline material.
Described contains Cu2+Compound be Cu (NO3)2·3H2O。
Described contains Co2+Compound be Co (NO3)2·6H2O。
The filling rate of the precursors (i.e. reaction solution), refers to precursors in adjusting hydrothermal reaction kettle of the present invention
The filling rate of (i.e. reaction solution) can be 65~75%.
The method of eccentric cleaning processing is：Successively use pure water, ammonium hydroxide (concentration 50-90Wt%), pure water, anhydrous
The secondary ordered pair reaction product of ethyl alcohol carries out eccentric cleaning for several times.Or successively use ammonium hydroxide (concentration 50-90Wt%), pure water, nothing
The secondary ordered pair reaction product of water-ethanol carries out eccentric cleaning for several times.Can also according to pure water, ammonium hydroxide (concentration 50-90Wt%),
The order of dehydrated alcohol is adjusted.
The stoving process is：By eccentric cleaning treated sediment in 60 DEG C of dryings in electric drying oven with forced convection
24~48 hours.
The CuCoO of above method preparation provided by the invention2Crystalline material, purposes are：In transparent conductive oxide
Application in photoelectric functional device.
The photoelectric functional device of the transparent conductive oxide can be photoelectrochemical cell or dye sensitization of solar
Battery.
The present invention utilizes hydro-thermal reaction, prepares CuCoO by single step reaction method under lower temperature (100~120 DEG C)2
Crystalline material.A kind of CuCoO is developed for the first time2Crystalline material compared with low temperature, high yield, the fast preparation method of low cost, for
Promote delafossite structure p-type semiconductor material and its application development in field of photoelectric devices, all has highly important science
Value.
Compared with prior art, the present invention its remarkable result mainly has：CuCoO is synthesized using hydro-thermal method for the first time2Crystal material
Material has been filled up both at home and abroad about being synthetically prepared out delafossite structure CuCoO under ultralow temperature hydrothermal condition2The research of semiconductor material
Blank.
The present invention compared with prior art, mainly there is following advantage：
(1) this method preparation process is simple, and experimental repeatability is good, and single yield is high.
(2) the reaction raw material sources that this method uses are extensive, and all products are inorganic matter, and environmental pollution is small, at low cost.
(3) when reaction temperature is 100~120 DEG C, the delafossite structure that crystalline size is about 1~4 μm can be obtained
CuCoO2Material.
(4) it is reacted using low-temperature hydrothermal, can quickly prepare CuCoO2Crystalline material.
Detailed description of the invention
Fig. 1 is reaction product X ray diffracting spectrum prepared in the embodiment of the present invention 1,2,3,4,5：Horizontal seat in figure
It is designated as angle of diffraction, ordinate is relative intensity.From figure 1 it appears that when reaction temperature is 100~120 DEG C, it can be with
Prepare CuCoO2Material.XRD diffraction maximum is 3R delafossite structure CuCoO2Characteristic peak, corresponding standard diffraction map number
For #21-0256.
Fig. 2 is reaction product X ray diffracting spectrum prepared in the embodiment of the present invention 1,2,3,4,5：Horizontal seat in figure
It is designated as angle of diffraction, ordinate is relative intensity.From figure 2 it can be seen that can be made when the reaction time is 12~36h
Standby CuCoO out2Material.The peak crystallization of apparent 3R phase copper cobalt oxide, XRD spectrum and CuCoO is presented in the XRD diffraction maximum of reaction product2
PDF card match, corresponding standard diffraction map number is #21-0256.
Fig. 3 is reaction product CuCoO prepared in the embodiment of the present invention 22The scanning electron microscope (SEM) photograph of crystalline material.Anti-
It is 24 hours, when reaction temperature is 100 DEG C between seasonable, it is micro- to reaction product observation shooting using field emission scanning electron microscope
See pattern photo.As can be seen that prepared CuCoO from Fig. 3, Fig. 42Crystalline size is about 1~4 μm, and microscopic appearance is more
For hexagonal layer structure, meet typical delafossite material crystal structure.
Fig. 4 is the enlarged drawing of Fig. 3.
Specific embodiment
Chemicals used in hydro-thermal reaction presoma of the present invention mainly includes Cu (NO3)2·3H2O、 Co
(NO3)2·6H2O, NaOH, dehydrated alcohol, pure water, NH3·H2O.Precursors are prepared first, and it is anti-to be then transferred into hydro-thermal
It answers in kettle, heat preservation a period of time is reacted under baking oven specific temperature after sealing.To reaction kettle natural cooling after reaction,
Reaction product is taken out, obtains CuCoO after the processing of multiple eccentric cleaning is dried in an oven2Crystalline material.
Below with reference to examples and drawings, the present invention is further illustrated, but is not limited to the following content.
Embodiment 1：
At room temperature, according to Co2+：Cu2+Molar ratio is 1：1 weighs Co (NO3)2·6H2O and Cu (NO3)2·3H2After O, add
Enter into pure water, Cu2+And Co2+Concentration be respectively 4.33-4.92Wt%, 5.17-5.87Wt%, through magnetic stirrer
30~60 minutes；Until completely dissolved, added mineralizer effect contains Cu2+Or contain Co2+Compound 4 times of moles
NaOH, continue stirring 30~60 minutes, until be completely dissolved, form hydro-thermal reaction presoma, obtain precursors.It will be above-mentioned
Precursors are transferred in hydrothermal reaction kettle (generally polytetrafluoroethylene (PTFE)), control reaction solution (i.e. precursors) filling
Rate about 70%.Sealing autoclave body is placed in temperature programmed control case and carries out hydro-thermal reaction, sets reaction temperature as 100 DEG C, the reaction time
It is 24~36 hours.
After reaction, it to autoclave body cooled to room temperature, opens autoclave body and takes out reaction product.Successively use pure water, ammonia
Water (concentration 50-90Wt%), pure water, dehydrated alcohol eccentric cleaning for several times, finally in an oven 60 DEG C keep the temperature 24~48 hours
It is dry, the delafossite structure CuCoO of available 1~4 μm of size2Crystalline material.
Embodiment 2：
At room temperature according to Co2+：Cu2+Molar ratio is 1：1 weighs Co (NO3)2·6H2O and Cu (NO3)2·3H2After O, add
Enter into pure water, Cu2+And Co2+Concentration be respectively 4.33-4.92Wt%, 5.17-5.87Wt%, through magnetic stirrer
30~60 minutes, until completely dissolved, added mineralizer effect contained Cu2+Or contain Co2+Compound 5 times of moles
NaOH, continue stirring 30~60 minutes, until be completely dissolved, form hydro-thermal reaction presoma, obtain precursors.It will be above-mentioned
Precursors are transferred in hydrothermal reaction kettle (generally polytetrafluoroethylene (PTFE)), control reaction solution filling rate about 70%.Seal pot
Body, which is placed in temperature programmed control case, carries out hydro-thermal reaction, sets reaction temperature as 100 DEG C, the reaction time is 12~36 hours.
After reaction, it to autoclave body cooled to room temperature, opens autoclave body and takes out reaction product.Successively use pure water, ammonia
Water (concentration 50-90Wt%), pure water, dehydrated alcohol eccentric cleaning for several times, finally in an oven 60 DEG C keep the temperature 24~48 hours
It is dry, the delafossite structure CuCoO of available 1~4 μm of size2Crystalline material.
Embodiment 3：
At room temperature according to Co2+：Cu2+Molar ratio is 1：1 weighs Co (NO3)2·6H2O and Cu (NO3)2·3H2After O, add
Enter into pure water, Cu2+And Co2+Concentration be respectively 4.33-4.92Wt%, 5.17-5.87Wt%, through magnetic stirrer
30~60 minutes, until completely dissolved, added mineralizer effect contained Cu2+Or contain Co2+Compound 6 times of moles
NaOH), continue stirring 30~60 minutes, until be completely dissolved, form hydro-thermal reaction presoma, obtain precursors.
Above-mentioned precursors are transferred in hydrothermal reaction kettle (generally polytetrafluoroethylene (PTFE)), reaction solution filling rate is controlled
About 70%.Sealing autoclave body is placed in temperature programmed control case and carries out hydro-thermal reaction, sets reaction temperature as 100~120 DEG C, when reaction
Between be 24 hours.
After reaction, it to autoclave body cooled to room temperature, opens autoclave body and takes out reaction product.Successively use pure water, ammonia
Water (concentration 50-90Wt%), pure water, dehydrated alcohol eccentric cleaning for several times, finally in an oven 60 DEG C keep the temperature 24~48 hours
It is dry, the delafossite structure CuCoO of available 1~4 μm of size2Crystalline material.
Embodiment 4：
At room temperature according to Co2+：Cu2+Molar ratio is 1：1 weighs Co (NO3)2·6H2O and Cu (NO3)2·3H2After O, add
Enter into pure water, Cu2+And Co2+Concentration be respectively 4.33-4.92Wt%, 5.17-5.87Wt%, through magnetic stirrer
30~60 minutes, until completely dissolved, added mineralizer effect contained Cu2+Or contain Co2+Compound 8 times of moles
NaOH, continue stirring 30~60 minutes, until be completely dissolved, form hydro-thermal reaction presoma, obtain precursors.
Above-mentioned precursors are transferred in hydrothermal reaction kettle (generally polytetrafluoroethylene (PTFE)), reaction solution filling rate is controlled
About 75%.Sealing autoclave body is placed in temperature programmed control case and carries out hydro-thermal reaction, sets reaction temperature as 100~120 DEG C, when reaction
Between be 24 hours.
After reaction, it to autoclave body cooled to room temperature, opens autoclave body and takes out reaction product.Successively use pure water, ammonia
Water (concentration 50-90Wt%), pure water, dehydrated alcohol eccentric cleaning for several times, finally in an oven 60 DEG C keep the temperature 24~48 hours
It is dry, the delafossite structure CuCoO of available 1~4 μm of size2Crystalline material.
Embodiment 5：
At room temperature according to Co2+：Cu2+Molar ratio is 1：1 weighs Co (NO3)2·6H2O and Cu (NO3)2·3H2After O, add
Enter into pure water, Cu2+And Co2+Concentration be respectively 4.33-4.92Wt%, 5.17-5.87Wt%, through magnetic stirrer
30~60 minutes, until completely dissolved, added mineralizer effect contained Cu2+Or contain Co2+Compound 5 times of moles
NaOH, continue stirring 30~60 minutes, until be completely dissolved, form hydro-thermal reaction presoma, obtain precursors.
Above-mentioned precursors are transferred in hydrothermal reaction kettle (generally polytetrafluoroethylene (PTFE)), reaction solution filling rate is controlled
About 65~75%.Sealing autoclave body is placed in temperature programmed control case and carries out hydro-thermal reaction, sets reaction temperature as 100 DEG C, when reaction
Between be 24 hours.
After reaction, it to autoclave body cooled to room temperature, opens autoclave body and takes out reaction product.Successively use pure water, ammonia
Water (concentration 50-90Wt%), pure water, dehydrated alcohol eccentric cleaning for several times, finally in an oven 60 DEG C keep the temperature 24~48 hours
It is dry, the delafossite structure CuCoO of available 1~4 μm of size2Crystalline material.
Embodiment 6 (application)：
Delafossite structure CuCoO prepared by above-described embodiment 1-42The purposes of crystalline material, is primarily referred to as transparent
It is used in the photoelectric functional device of conductive oxide as electrode material.
By CuCoO2Particle uses film deposition techniques (such as silk screen print method, scraper method), in electro-conductive glass (FTO) table
CuCoO is prepared on face2Thin-film material is used as electrode material in sensitization solar battery or photoelectrochemical cell.For example, according to
Certain proportion adds CuCoO2Crystal obtains the CuCoO of different solid contents2Slurry, then using silk screen print method in electro-conductive glass
Surface brush film finally obtains CuCoO after thermally treated sintering removes organic matter2Electrode film material.
Claims (5)
1. a kind of delafossite structure CuCoO2The low temperature preparation method of crystalline material, it is characterised in that include the following steps：1) it prepares
Precursors：By containing Cu2+Compound, contain Co2+Compound in Cu2+、Co2+Molar ratio 1：1, it chooses and contains Cu2+Change
It closes object and contains Co2+Compound；At room temperature, Cu will be contained2+Compound and contain Co2+Compound be added in pure water, in magnetic
After dissolution is sufficiently stirred in power blender, obtain containing Cu2+With contain Co2+Aqueous solution, Cu2+And Co2+Concentration be respectively 4.33-
4.92Wt%, 5.17-5.87Wt%；It adds containing Cu2+Or contain Co2+Compound 4~8 times of moles NaOH as mine
Agent obtains precursors, for use after being stirred well to dissolution completely；2) it is anti-and then by precursors to be transferred to hydro-thermal
It answers in kettle, filling rate is 65~75%, is reacted 12~36 hours at 100~120 DEG C；It is naturally cold to reaction kettle after reaction
But, reaction product is taken out, reaction product is handled through eccentric cleaning, dries, obtains delafossite structure CuCoO2Crystalline material.
2. a kind of delafossite structure CuCoO according to claim 12The low temperature preparation method of crystalline material, feature exist
In described contains Cu2+Compound be Cu (NO3)2·3H2O。
3. a kind of delafossite structure CuCoO according to claim 12The low temperature preparation method of crystalline material, feature exist
In described contains Co2+Compound be Co (NO3)2·6H2O。
4. a kind of delafossite structure CuCoO according to claim 12The low temperature preparation method of crystalline material, feature exist
In the method for the eccentric cleaning processing is：Successively using pure water, ammonium hydroxide, pure water, dehydrated alcohol secondary ordered pair reaction product into
Row eccentric cleaning is for several times；Or eccentric cleaning is successively carried out for several times using the secondary ordered pair reaction product of ammonium hydroxide, pure water, dehydrated alcohol；
The ammonia concn is 50-90Wt%.
5. a kind of delafossite structure CuCoO according to claim 12The low temperature preparation method of crystalline material, feature exist
In the stoving process is：By eccentric cleaning treated sediment in electric drying oven with forced convection in 60 DEG C dry 24~
48 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710407330.6A CN107098401B (en) | 2017-06-02 | 2017-06-02 | A kind of delafossite structure CuCoO2Crystalline material and its low temperature preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710407330.6A CN107098401B (en) | 2017-06-02 | 2017-06-02 | A kind of delafossite structure CuCoO2Crystalline material and its low temperature preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107098401A CN107098401A (en) | 2017-08-29 |
| CN107098401B true CN107098401B (en) | 2018-11-30 |
Family
ID=59659109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710407330.6A Active CN107098401B (en) | 2017-06-02 | 2017-06-02 | A kind of delafossite structure CuCoO2Crystalline material and its low temperature preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107098401B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109748327B (en) * | 2019-02-25 | 2020-08-04 | 武汉理工大学 | Low-temperature preparation of CuCoO based on MOFs material2Method for producing nanocrystalline material |
| CN110980791B (en) * | 2019-12-05 | 2021-05-11 | 武汉理工大学 | P type delafossite structure CuScO2Crystalline material, method for the production thereof and use thereof |
| CN113401931B (en) * | 2021-06-03 | 2022-08-09 | 山东省科学院能源研究所 | CuAlO with delafossite structure 2 Preparation method of (1) |
| CN114160065B (en) * | 2021-11-17 | 2024-02-13 | 昆明理工大学 | Preparation method of crystalline phase controllable delafossite AgFeO2 powder material |
| CN115305572B (en) * | 2022-07-06 | 2023-07-21 | 信阳师范学院 | Monocrystalline material GaCuPO 5 Is prepared from monocrystalline material GaCuPO 5 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880081A (en) * | 2014-03-28 | 2014-06-25 | 武汉理工大学 | Preparation method for delafossite-structure AgCrO2 nanocrystalline material |
| CN104058461A (en) * | 2014-07-04 | 2014-09-24 | 武汉理工大学 | Low-temperature preparation method for CuFeO2 crystal material of delafossite structure |
-
2017
- 2017-06-02 CN CN201710407330.6A patent/CN107098401B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880081A (en) * | 2014-03-28 | 2014-06-25 | 武汉理工大学 | Preparation method for delafossite-structure AgCrO2 nanocrystalline material |
| CN104058461A (en) * | 2014-07-04 | 2014-09-24 | 武汉理工大学 | Low-temperature preparation method for CuFeO2 crystal material of delafossite structure |
Non-Patent Citations (1)
| Title |
|---|
| Characterization of delafossite-type CuCoO2 prepared by ion exchange;M. Beekman等;《Journal of Alloys and Compounds》;20090930;第489卷;第336-338页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107098401A (en) | 2017-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107098401B (en) | A kind of delafossite structure CuCoO2Crystalline material and its low temperature preparation method | |
| CN104058461B (en) | A kind of delafossite structure CuFeO2The low temperature preparation method of crystalline material | |
| Su et al. | Growth of large CH3NH3PbX3 (X= I, Br) single crystals in solution | |
| CN109748327A (en) | One kind preparing CuCoO based on MOFs material at low temperature2The method of nanocrystalline material | |
| CN103880081B (en) | A kind of delafossite structure AgCrO 2the preparation method of nanocrystalline material | |
| Choi et al. | Hydrothermal synthesis and photocatalytic properties of CuGaO2/ZnO hexagonal platelet hybrids | |
| CN102897722B (en) | Alpha-In2Se3 nano-grade flower-ball solvothermal synthesizing method | |
| CN112694125A (en) | Black molybdenum trioxide nanosheet, and preparation method and application thereof | |
| Ursu et al. | Effect of Al doping on performance of CuGaO 2 p-type dye-sensitized solar cells | |
| Vallejo et al. | Synthesis and characterization of nanoparticles of CZTSe by microwave-assited chemical synthesis | |
| CN113716601A (en) | Hydroxyl cadmium chloride crystal and preparation method thereof | |
| CN103887501A (en) | Method for preparing copper selenide lithium ion battery electrode material | |
| Phumying et al. | Optical properties of β-Ga2O3 nanorods synthesized by a simple and cost-effective method using egg white solution | |
| JP6143047B2 (en) | Wavelength conversion device and manufacturing method thereof | |
| KR101509332B1 (en) | Preparation of copper selenide compound controlling particle size and composition | |
| CN107170583A (en) | A kind of method and its application that the aluminium-doped zinc oxide for dye-sensitized solar cell anode is prepared based on hydrotalcite | |
| Li et al. | Synthesis of TiO2-SrTiO3 hetero-structured nanorod arrays and their photoelectrical performance in all-solid-state dye-sensitized solar cells | |
| CN101838011B (en) | Preparation method of CuAlO2 microcrystal | |
| CN101734712A (en) | Method for preparing high-quality copper indium sulfide by employing single-source molecular precursor | |
| CN103466688A (en) | Method for preparing ZnS nanosheet | |
| Chandrasekaran | Synthesis of ZnO Nano Particles via Simple Solution Route for DSSC's Using Synthetic and Natural Dyes | |
| CN103613115A (en) | Method for synthesizing ZnO/ZnSe (zinc oxide/zinc selenide) coaxial nano structure through gas-phase anion exchange | |
| CN103601157B (en) | A kind of method that ethanediamine auxiliary polyhydric alcohol based sols synthesis Cu-In-Al-Se is nanocrystalline | |
| CN109516494B (en) | Method for synthesizing stannous sulfide by low-temperature liquid phase | |
| CN103265060A (en) | Preparation method of monodisperse hexagonal-phase sodium yttrium fluoride mesoscopic crystal particles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |