CN107098401A - 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
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Abstract
The present invention relates to the synthetically prepared field of delafossite structure crystalline material, in particular with hydro-thermal method synthetically prepared CuCoO at a lower temperature2Crystalline material.A kind of delafossite structure CuCoO2The low temperature preparation method of crystalline material, it is characterised in that:Reacted using low-temperature hydrothermal, regulation and control include the fill factor of 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 reactant reaction after 12~36 hours, after reaction product is handled and dried through eccentric cleaning, and obtain 1~4 micron of size obtains delafossite structure CuCoO2Crystalline material.The present invention and other synthetically prepared CuCoO2The method of crystalline material is compared, ultralow temperature, high yield, low cost, low stain.
Description
Technical field
The present invention relates to the synthetically prepared field of delafossite structure crystalline material, in particular with hydro-thermal method at a lower temperature
Synthetically prepared CuCoO2Crystalline material.
Background technology
1997, the Kawazoe professors of Tokyo polytechnical university on Nature based on valence band chemistry repaiied first by report
(Chemical modulation of Valence band, abbreviation CMVB) theory is adornd, pulsed laser deposition (Pulse is utilized
Laser Deposition, abbreviation PLD) technology, prepare the delafossite knot for existing and transporting with suitable a large amount of how sub- holes
Structure (ABO2) intrinsically p-type electrically conducting transparent CuAlO2Film, the electrical conductivity of film is 0.95s/cm at room temperature.This achievement is promoted
P-type delafossite structure transparent conductive oxide (Transparent conductive oxide, abbreviation TCO) material it is swift and violent
Development, hope is brought for the p-n junction diode and transparent semiconductor device that prepare all-transparent.It is theoretical based on valence band chemical modification
Design prepares 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 SrCu2O2Turn into p-type TCO weight Deng material
Point perpetual object.In recent years, application study of the transparent conductive oxide film in various fields is developed rapidly, and new TCO is thin
Membrane material is of common occurrence.Meanwhile, related is theoretical as band theory, doping theory and crystal structure theory have also been obtained further
It is perfect.The research and development of p-type TCO materials are implemented as possibility by make all-transparent p-n junction, are basic for realizing using p-n junction
The meaning of the practical application of the photoelectric device of structure is very great, the investigation of materials at the same time also having triggered numerous values to explore
The appearance of problem.
2010, M.Beekman et al. passed through CuCl and LiCoO2Between simple ion exchange solid-state reaction, 590
After being reacted 48 hours at DEG C, polycrystalline delafossite oxide CuCoO is prepared first2Material.CuCoO2Crystal is a kind of new p
Type transparent conductive oxide material, belongs to R-3m space groups.The CuCoO of 3R crystal formations2Cell parameter At present, CuCoO typically 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 do not synthesize CuCoO on hydro-thermal method2The correlative study report of crystalline material.Therefore, water is utilized
Hot method prepares CuCoO2Material is very novel, and p-type CuCoO is prepared for exploring2Nanocrystalline material and its device, which are applied, to be had
Highly important Research Significance.
Up to the present, a variety of methods prepare copper-based delafossite material, including high temperature solid-state method, collosol and gel
Method, pulsed laser deposition, sputtering method, chemical vapour deposition technique, hydro-thermal method etc..In these prepare the method for target product,
Hydro-thermal method is a kind of simple preparation method of green relatively, crystalline oxides directly can be obtained from aqueous medium, it is considered to be ring
Border is polluted less, cost is relatively low, be 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.) occur synthetic reaction, it is to avoid and high-temperature calcination and ball milling two complicated experimental implementations, also prevention introduces impurity and made
Into 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 the delafossite CuCoO of purity height, good crystal formation, pattern and size tunable2Material.
At present, the research report for synthesizing serial copper-based delafossite material on hydrothermal reaction at low temperature focuses mostly in CuAlO2,
CuGaO2, CuCrO2And CuFeO2On, do not find any use hydrothermal reaction at low temperature synthesis delafossite structure CuCoO temporarily2Material is ground
Study carefully 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 semi-conducting material, system is excellent
Change adjustment hydro-thermal preparation technology, inquire into its hydrothermal growth mechanism, its characteristic of semiconductor is regulated and controled comprehensively, with suitable for various new light
In Electricity Functional device.
The content of the invention
The technical problems to be solved by the invention are: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 uses following technical scheme: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, containing Co2+Compound in Cu2+、Co2+Mol ratio 1:1,
Choose and contain Cu2+Compound and containing Co2+Compound;
At room temperature, Cu will be contained2+Compound and containing Co2+Compound be added in pure water, it is abundant in magnetic stirring apparatus
After stirring and dissolving, obtain containing Cu2+With containing Co2+The aqueous solution, Cu2+And Co2+Concentration be respectively 4.33-4.92Wt%, 5.17-
5.87Wt%;Add containing Cu2+Or containing Co2+Compound 4~8 times of moles NaOH as mineralizer, be stirred well to
After dissolving completely, precursors are obtained, it is stand-by;
2) and then by precursors it is transferred in hydrothermal reaction kettle, filling rate is 65~75%, at 100~120 DEG C
Reaction 12~36 hours;After reaction product is handled through multiple eccentric cleaning, drying, delafossite structure CuCoO is obtained2Crystal material
Material.
A kind of above-mentioned delafossite structure CuCoO2The low temperature preparation method of crystalline material, it is characterised in that including following step
Suddenly:
1) precursors are prepared:By containing Cu2+Compound, containing Co2+Compound in Cu2+、Co2+Mol ratio 1:1,
Choose and contain Cu2+Compound and containing Co2+Compound;
At room temperature, Cu will be contained2+Compound and containing Co2+Compound be added in pure water, it is abundant in magnetic stirring apparatus
After stirring and dissolving, obtain containing Cu2+With containing Co2+The aqueous solution, Cu2+And Co2+Concentration be respectively 4.33-4.92Wt%, 5.17-
5.87Wt%;Add containing Cu2+Or containing Co2+Compound 4~8 times of moles NaOH as mineralizer, be stirred well to
After dissolving completely, precursors are obtained, it is stand-by;
2) and then by precursors it is transferred in hydrothermal reaction kettle, filling rate is 65~75%, at 100~120 DEG C
Reaction 12~36 hours (be incubated and reacted at a temperature of 100~120 DEG C of baking oven after sealing for 12~36 hours);Question response terminates
Reactor natural cooling, takes out reaction product, reaction product is handled through eccentric cleaning afterwards, and drying (is dried) in baking oven, is obtained
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 reactor of the present invention
The filling rate of (i.e. reaction solution) can be 65~75%.
The method of eccentric cleaning processing is:Use pure water successively, it is ammoniacal liquor (concentration is 50-90Wt%), pure water, anhydrous
The secondary ordered pair reaction product of ethanol carries out eccentric cleaning for several times.Or ammoniacal liquor (concentration is 50-90Wt%), pure water, nothing are used successively
The secondary ordered pair reaction product of water-ethanol carries out eccentric cleaning for several times.Can also according to pure water, ammoniacal liquor (concentration is 50-90Wt%),
The order of absolute ethyl alcohol is adjusted.
Described stoving process is:Sediment after eccentric cleaning is handled is in electric drying oven with forced convection in 60 DEG C of dryings
24~48 hours.
CuCoO prepared by the above method that the present invention is provided2Crystalline material, its purposes is:In transparent conductive oxide
Application in photoelectric functional device.
The photoelectric functional device of described transparent conductive oxide can be photoelectrochemical cell or dye sensitization of solar
Battery.
The present invention utilizes hydro-thermal reaction, and CuCoO is prepared by single step reaction method under lower temperature (100~120 DEG C)2
Crystalline material.A kind of CuCoO is developed first2Crystalline material compared with low temperature, high yield, low cost fast preparation method, for
Promote delafossite structure p-type semiconductor material and its application development in field of photoelectric devices, be respectively provided with highly important science
Value.
Compared with prior art, its remarkable result mainly has the present invention:CuCoO is synthesized using hydro-thermal method first2Crystal material
Material, filled up both at home and abroad under ultralow temperature hydrothermal condition it is synthetically prepared go out delafossite structure CuCoO2The research of semi-conducting material
Blank.
The present invention compared with prior art, mainly there is following advantage:
(1) this method preparation technology is simple, and experimental repeatability is good, and single yield is high.
(2) extensively, all products are inorganic matter to the reaction raw material sources that this method is used, and environmental pollution is small, and cost is low.
(3) when reaction temperature is 100~120 DEG C, it can obtain the delafossite structure that crystalline size is about 1~4 μm
CuCoO2Material.
(4) reacted using low-temperature hydrothermal, can quickly prepare CuCoO2Crystalline material.
Brief description of the drawings
Fig. 1 is reaction product X ray diffracting spectrum prepared in the embodiment of the present invention 1,2,3,4,5:It is horizontal in figure to sit
Angle of diffraction is designated as, ordinate is relative intensity.From figure 1 it appears that when reaction temperature is 100~120 DEG C, can be with
Prepare CuCoO2Material.XRD diffraction maximums are 3R delafossite structures CuCoO2Characteristic peak, correspondence standard diffraction collection of illustrative plates numbering
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:It is horizontal in figure to sit
Angle of diffraction is designated as, ordinate is relative intensity.From figure 2 it can be seen that when the reaction time is 12~36h, can make
It is standby go out CuCoO2Material.The peak crystallization of obvious 3R phases copper cobalt oxide, XRD spectrum and CuCoO is presented in the XRD diffraction maximums of reaction product2
PDF cards match, correspondence standard diffraction collection of illustrative plates numbering 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 between seasonable, when reaction temperature is 100 DEG C, micro- is shot to reaction product observation 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 Fig. 3 enlarged drawing.
Embodiment
Chemicals used in hydro-thermal reaction presoma of the present invention, mainly including Cu (NO3)2·3H2O、Co
(NO3)2·6H2O, NaOH, absolute ethyl alcohol, pure water, NH3·H2O.Precursors are prepared first, are then transferred into hydro-thermal anti-
Answer in kettle, insulation a period of time is reacted under baking oven specified temp after sealing.Question response terminates rear reactor natural cooling,
Reaction product is taken out, is handled through multiple eccentric cleaning and obtains CuCoO after drying in an oven2Crystalline material.
With reference to embodiment and accompanying drawing, the present invention is further illustrated, but is not limited to the following content.
Embodiment 1:
At room temperature, according to Co2+:Cu2+Mol ratio is 1:1 weighs Co (NO3)2·6H2O and Cu (NO3)2·3H2After O, plus
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 containing Co2+Compound 4 times of moles
NaOH, continue to stir 30~60 minutes, to being completely dissolved, form hydro-thermal reaction presoma, obtain precursors.Will be above-mentioned
Precursors are transferred in hydrothermal reaction kettle (generally polytetrafluoroethylene (PTFE)), control reaction solution (i.e. precursors) filling rate
About 70%.It is placed in temperature programmed control case after sealing kettle and carries out hydro-thermal reaction, set reaction temperature as 100 DEG C, the reaction time is
24~36 hours.
After reaction terminates, treat that kettle naturally cools to room temperature, open kettle and take out reaction product.Pure water, ammonia are used successively
Water (concentration is 50-90Wt%), pure water, absolute ethyl alcohol eccentric cleaning for several times, finally in an oven 60 DEG C be incubated 24~48 hours
Dry, the delafossite structure CuCoO of 1~4 μm of size can be obtained2Crystalline material.
Embodiment 2:
At room temperature according to Co2+:Cu2+Mol ratio is 1:1 weighs Co (NO3)2·6H2O and Cu (NO3)2·3H2After O, plus
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 containing Co2+Compound 5 times of moles
NaOH, continue to stir 30~60 minutes, to being completely dissolved, form hydro-thermal reaction presoma, obtain precursors.Will be above-mentioned
Precursors are transferred in hydrothermal reaction kettle (generally polytetrafluoroethylene (PTFE)), control reaction solution filling rate about 70%.Seal pot
It is placed in after body in temperature programmed control case and carries out hydro-thermal reaction, set reaction temperature as 100 DEG C, the reaction time is 12~36 hours.
After reaction terminates, treat that kettle naturally cools to room temperature, open kettle and take out reaction product.Pure water, ammonia are used successively
Water (concentration is 50-90Wt%), pure water, absolute ethyl alcohol eccentric cleaning for several times, finally in an oven 60 DEG C be incubated 24~48 hours
Dry, the delafossite structure CuCoO of 1~4 μm of size can be obtained2Crystalline material.
Embodiment 3:
At room temperature according to Co2+:Cu2+Mol ratio is 1:1 weighs Co (NO3)2·6H2O and Cu (NO3)2·3H2After O, plus
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 containing Co2+Compound 6 times of moles
NaOH), continue to stir 30~60 minutes, to being 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%.It is placed in after sealing kettle in temperature programmed control case and carries out hydro-thermal reaction, reaction temperature is set as 100~120 DEG C, during reaction
Between be 24 hours.
After reaction terminates, treat that kettle naturally cools to room temperature, open kettle and take out reaction product.Pure water, ammonia are used successively
Water (concentration is 50-90Wt%), pure water, absolute ethyl alcohol eccentric cleaning for several times, finally in an oven 60 DEG C be incubated 24~48 hours
Dry, the delafossite structure CuCoO of 1~4 μm of size can be obtained2Crystalline material.
Embodiment 4:
At room temperature according to Co2+:Cu2+Mol ratio is 1:1 weighs Co (NO3)2·6H2O and Cu (NO3)2·3H2After O, plus
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 containing Co2+Compound 8 times of moles
NaOH, continue to stir 30~60 minutes, to being 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%.It is placed in after sealing kettle in temperature programmed control case and carries out hydro-thermal reaction, reaction temperature is set as 100~120 DEG C, during reaction
Between be 24 hours.
After reaction terminates, treat that kettle naturally cools to room temperature, open kettle and take out reaction product.Pure water, ammonia are used successively
Water (concentration is 50-90Wt%), pure water, absolute ethyl alcohol eccentric cleaning for several times, finally in an oven 60 DEG C be incubated 24~48 hours
Dry, the delafossite structure CuCoO of 1~4 μm of size can be obtained2Crystalline material.
Embodiment 5:
At room temperature according to Co2+:Cu2+Mol ratio is 1:1 weighs Co (NO3)2·6H2O and Cu (NO3)2·3H2After O, plus
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 containing Co2+Compound 5 times of moles
NaOH, continue to stir 30~60 minutes, to being 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%.It is placed in after sealing kettle in temperature programmed control case and carries out hydro-thermal reaction, reaction temperature is set as 100 DEG C, during reaction
Between be 24 hours.
After reaction terminates, treat that kettle naturally cools to room temperature, open kettle and take out reaction product.Pure water, ammonia are used successively
Water (concentration is 50-90Wt%), pure water, absolute ethyl alcohol eccentric cleaning for several times, finally in an oven 60 DEG C be incubated 24~48 hours
Dry, the delafossite structure CuCoO of 1~4 μm of size can be obtained2Crystalline material.
Embodiment 6 (application):
Delafossite structure CuCoO prepared by above-described embodiment 1-42The purposes of crystalline material, is primarily referred to as transparent
Used in the photoelectric functional device of conductive oxide as electrode material.
By CuCoO2Particle uses film deposition techniques (such as silk screen print method, doctor blade method), in electro-conductive glass (FTO) table
CuCoO is prepared on face2Thin-film material, 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
After surface brush film, thermally treated sintering organics removal, CuCoO is finally obtained2Electrode film material.
Claims (6)
1. a kind of delafossite structure CuCoO2Crystalline material, it is characterised in that it is obtained by following steps:
1) precursors are prepared:By containing Cu2+Compound, containing Co2+Compound in Cu2+、Co2+Mol ratio 1:1, choose
Containing Cu2+Compound and containing Co2+Compound;
At room temperature, Cu will be contained2+Compound and containing Co2+Compound be added in pure water, be sufficiently stirred in magnetic stirring apparatus
After dissolving, obtain containing Cu2+With containing Co2+The aqueous solution, Cu2+And Co2+Concentration be respectively 4.33-4.92Wt%, 5.17-
5.87Wt%;Add containing Cu2+Or containing Co2+Compound 4~8 times of moles NaOH as mineralizer, be stirred well to
After dissolving completely, precursors are obtained, it is stand-by;
2) and then by precursors it is transferred in hydrothermal reaction kettle, filling rate is 65~75%, is reacted at 100~120 DEG C
12~36 hours;After reaction product is handled through multiple eccentric cleaning, drying, delafossite structure CuCoO is obtained2Crystalline material.
2. a kind of delafossite structure CuCoO2The low temperature preparation method of crystalline material, it is characterised in that comprise the following steps:
1) precursors are prepared:By containing Cu2+Compound, containing Co2+Compound in Cu2+、Co2+Mol ratio 1:1, choose
Containing Cu2+Compound and containing Co2+Compound;
At room temperature, Cu will be contained2+Compound and containing Co2+Compound be added in pure water, be sufficiently stirred in magnetic stirring apparatus
After dissolving, obtain containing Cu2+With containing Co2+The aqueous solution, Cu2+And Co2+Concentration be respectively 4.33-4.92Wt%, 5.17-
5.87Wt%;Add containing Cu2+Or containing Co2+Compound 4~8 times of moles NaOH as mineralizer, be stirred well to
After dissolving completely, precursors are obtained, it is stand-by;
2) and then by precursors it is transferred in hydrothermal reaction kettle, filling rate is 65~75%, is reacted at 100~120 DEG C
12~36 hours;Question response terminates rear reactor natural cooling, takes out reaction product, reaction product is handled through eccentric cleaning,
Drying, obtains delafossite structure CuCoO2Crystalline material.
3. a kind of delafossite structure CuCoO according to claim 22The low temperature preparation method of crystalline material, its feature exists
In described contains Cu2+Compound be Cu (NO3)2·3H2O。
4. a kind of delafossite structure CuCoO according to claim 22The low temperature preparation method of crystalline material, its feature exists
In described contains Co2+Compound be Co (NO3)2·6H2O。
5. a kind of delafossite structure CuCoO according to claim 22The low temperature preparation method of crystalline material, its feature exists
In the method for the eccentric cleaning processing is:Pure water, ammoniacal liquor (concentration is 50-90Wt%), pure water, absolute ethyl alcohol are used successively
Secondary ordered pair reaction product carry out eccentric cleaning for several times;Or ammoniacal liquor (concentration is 50-90Wt%), pure water, anhydrous second are used successively
The secondary ordered pair reaction product of alcohol carries out eccentric cleaning for several times;Or according to pure water, ammoniacal liquor (concentration is 50-90Wt%), absolute ethyl alcohol
Order be adjusted.
6. a kind of delafossite structure CuCoO according to claim 22The low temperature preparation method of crystalline material, its feature exists
In described stoving process is:Sediment after eccentric cleaning is handled dries 24 in electric drying oven with forced convection in 60 DEG C~
48 hours.
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CN109748327A (en) * | 2019-02-25 | 2019-05-14 | 武汉理工大学 | One kind preparing CuCoO based on MOFs material at low temperature2The method of nanocrystalline material |
CN110980791A (en) * | 2019-12-05 | 2020-04-10 | 武汉理工大学 | P type delafossite structure CuScO2Crystalline material, method for the production thereof and use thereof |
CN113401931A (en) * | 2021-06-03 | 2021-09-17 | 山东省科学院能源研究所 | CuAlO with delafossite structure2Preparation method of (1) |
CN114160065A (en) * | 2021-11-17 | 2022-03-11 | 昆明理工大学 | Preparation method of delafossite AgFeO2 powder material with controllable crystal phase |
CN115305572A (en) * | 2022-07-06 | 2022-11-08 | 信阳师范学院 | Single crystal material GaCuPO 5 Preparation method of (1) and single crystal material GaCuPO 5 |
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M. BEEKMAN等: "Characterization of delafossite-type CuCoO2 prepared by ion exchange", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
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CN110980791A (en) * | 2019-12-05 | 2020-04-10 | 武汉理工大学 | P type delafossite structure CuScO2Crystalline material, method for the production thereof and use thereof |
CN113401931A (en) * | 2021-06-03 | 2021-09-17 | 山东省科学院能源研究所 | CuAlO with delafossite structure2Preparation method of (1) |
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) |
CN114160065A (en) * | 2021-11-17 | 2022-03-11 | 昆明理工大学 | Preparation method of delafossite AgFeO2 powder material with controllable crystal phase |
CN114160065B (en) * | 2021-11-17 | 2024-02-13 | 昆明理工大学 | Preparation method of crystalline phase controllable delafossite AgFeO2 powder material |
CN115305572A (en) * | 2022-07-06 | 2022-11-08 | 信阳师范学院 | Single crystal material GaCuPO 5 Preparation method of (1) and single crystal material GaCuPO 5 |
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 |
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