CN110980791A - P type delafossite structure CuScO2Crystalline material, method for the production thereof and use thereof - Google Patents
P type delafossite structure CuScO2Crystalline material, method for the production thereof and use thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J35/33—
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
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- H10K30/81—Electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/549—Organic PV cells
Abstract
The invention discloses a p-type delafossite structure CuScO2Crystalline material and a method for its preparation and use, the method comprising: step 1, preparation of a reaction precursor: with Cu2+Source reactant and Sc3+Taking a source reactant as a raw material, taking deionized water as a reaction solution, adding a reducing agent and a mineralizer, and fully stirring until the reducing agent and the mineralizer are completely dissolved to prepare a reaction precursor; step 2, carrying out hydrothermal reaction on the reaction precursor at 210-240 ℃ for 12-48 hours, carrying out centrifugal cleaning treatment on the reaction product to obtain a precipitate, and drying the precipitate to obtain the catalystP-type delafossite structure CuScO2A crystalline material. The invention prepares gram-grade CuScO by using a hydrothermal method through single reaction2The crystal material does not need to adjust the pH value of a precursor reactant; in addition, the invention explores and researches CuScO for the first time2The catalyst material is applied to the oxygen evolution of electrolyzed water, and shows good oxygen evolution activity and stability of the electrolyzed water under the alkaline condition.
Description
Technical Field
The invention relates to the technical field of synthesis and preparation of nano materials, in particular to a p-type delafossite structure CuScO2Crystalline material, a method for the preparation thereof and use thereof.
Background
Transparent Conductive Oxide (TCO) materials are widely used in the fields of flat panel displays, solar photovoltaic cells, Transparent electrodes of touch screens, special function window coatings, other thin film photoelectric devices and the like with the characteristics of high conductivity, good optical transparency and the like. However, TCO materials currently in widespread research and use are essentially n-type semiconductors, such as SnO2、In2O3And ZnO, etc. If the p-type transparent conductive material with excellent performance can be prepared, active devices such as transparent p-n junctions, transparent FETs and the like can be manufactured, and even a transparent circuit can be realized. Therefore, the research and development of the novel p-type TCO material with excellent performance and stable process can expand the application field of the transparent conductive material, improve the scientific research and social and economic values of the material, and have important theoretical and practical significance.
Delafossite structural metal oxide (ABO)2A ═ Cu, Ag, etc., B ═ Al, Ga, Sc, In, etc.) are an important class of p-type transparent conductive oxide materials. CuAlO was first reported on Nature in 1997 by professor Hosono, university of Tokyo, Japan, in 19972P-type conductivity of the film, room temperature conductivity of 9.5 × 10-2s·cm-1. Acceptor CuAlO2Inspiring of the design philosophy of the chemical valence band, series ABO2Structural materials have become a major research concern for researchers. ABO of delafossite structure2Has a hexagonal layered crystal structure due to BO6Different stacking of co-octahedra leads to delafossite structural oxide ABO2There are two crystal forms, 2H and 3R. As a typical p-type semiconductor material, the series ABO2Materials are widely reported to be applied to the fields of photoelectric devices such as transparent conductive oxides, solar cell devices, photo/electro-catalysts and the like. CuScO2Has larger optical band gap width, and the band gap value is about 3.3-4.2eV due to CuScO2The Cu-Cu bond in the alloy has short length, is beneficial to the insertion of excessive O element, and is hopefulHas high p-type conductivity. The document reports that CuScO is obtained after heat treatment at 450 DEG C2The conductivity of the film at room temperature is as high as 30S/cm. Theoretical calculations show that: CuScO of 3R crystal form2Cell parameters ofThe valence band consists primarily of the 3d and 2p states of O for Cu, while the conduction band consists primarily of the 3d state for Sc. The copper vacancy and oxygen interstitial defect is CuScO due to its lower energy of formation2Leading to CuScO2Has p-type conductivity. Thus, CuScO2The material has larger optical band gap width and higher conductivity, and has good application prospect in the field of photoelectric devices. At present, CuScO is treated at home and abroad2The research reports of the materials are less, and the research reports are mostly concentrated on CuScO2Film material aspect, relating to CuScO2Very few reports of crystal powder material preparation and performance studies are reported.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a p-type delafossite structure CuScO2The invention discloses a crystal material, a preparation method and application thereof, and gram-grade CuScO is prepared by single reaction of a hydrothermal method2The crystal material has the advantages of simple preparation process without adjusting the pH value of a precursor reactant, easy control of process parameters and good experimental repeatability; in addition, the invention explores and researches CuScO for the first time2The catalyst material is applied to the oxygen evolution of electrolyzed water, and shows good oxygen evolution activity and stability of the electrolyzed water under the alkaline condition.
The invention is realized by the following steps:
one purpose of the invention is to provide a p-type delafossite structure CuScO2A method of preparing a crystalline material, the method comprising:
step 1, preparation of a reaction precursor: with Cu2+Source reactant and Sc3+Taking a source reactant as a raw material, taking deionized water as a reaction solution, adding a reducing agent and a mineralizer, and fully stirring until the reducing agent and the mineralizer are completely dissolved to prepare a reaction precursor;
Preferably, the Cu2+Source reactant and Sc3+The source reactant comprises Cu (NO)3)2And Sc (NO)3)3Or other compounds containing Sc3+And Cu2+The compound of (1).
Preferably, the Cu2+Source reactant and Sc3+The molar ratio of the source reactants is 1.0-1.5: 1.
preferably, the mineralizer is NaOH, and the mineralizer and the Cu2+The molar weight of the source reactant is 6-10: 1.
preferably, the reducing agent is one of ethylene glycol, polyethylene glycol, glucose, ascorbic acid and hydrazine hydrate. The ratio of the volume of the reducing agent to the total volume of the reaction solution is 0.15-1 ml: 65-75 ml.
Preferably, the hydrothermal reaction is carried out in a hydrothermal reaction kettle, and the filling rate of a reaction solution in the hydrothermal reaction kettle is 65-75%.
Preferably, the centrifugal cleaning treatment in step 2 comprises the following specific steps: adding deionized water and NH with the dilute mass fraction of 1-10%3·H2And O, carrying out centrifugal cleaning on the reaction products by absolute ethyl alcohol according to any sequence. The drying step in the step 2 is as follows: drying the mixture for 4 to 12 hours in a vacuum drying oven at 60 ℃.
The second purpose of the invention is to provide the p-type delafossite structure CuScO prepared by the method2A crystalline material.
The invention also aims to provide the p-type delafossite structure CuScO2Use of a crystalline material in a photovoltaic functional device of a transparent conductive oxide. In particular to a novel semiconductor material applied to various photoelectric functional devices, such as solar cells, electrolyzed water, photo-electrolyzed water or photocatalytic devices.
Specifically, the conductive matrix supports CuScO2The method for preparing the crystal material comprises the following steps:firstly, weighing a certain amount of CuScO2Ultrasonically dispersing the powder in a mixed solution of water-isopropanol-Nafion (the volume ratio is 25: 24: 1), and then using a pipette to remove a corresponding volume of CuScO2The suspension is dropped on the surface of a conductive substrate (such as a glassy carbon electrode, a metal mesh, a foil and a carbon-based carrier, such as carbon paper, carbon cloth) to adjust the loading amount (CuScO)2In amounts of 0.15, 0.30 and 0.45mg/cm2) And after the conductive matrix is naturally dried, baking the conductive matrix at 120 ℃ for 0.5 hour for later use.
The fourth purpose of the invention is to provide the p-type delafossite structure CuScO2The crystal material is used as a catalyst material for efficient electrolytic water oxygen evolution.
Specifically, CuScO is added2The powder is dispersed in the mixed solution of water-isopropanol-Nafion by ultrasonic to prepare CuScO2Suspending liquid, and then preparing Ni @ CuScO with different loading amounts2And the electrode is used for carrying out electrolytic water performance test by utilizing the electrochemical workstation. The test method for oxygen evolution by electrolyzing water comprises the following steps: the electrochemical workstation is used for testing by adopting a three-electrode system, and the working electrode is a nickel mesh loaded CuScO2(Ni@CuScO2) And a blank nickel screen, wherein the electrolyte is 1M KOH aqueous solution. The activity of oxygen evolution of electrolyzed water is tested by cyclic voltammetry scanning, and the stability of the reaction of oxygen evolution of the electrolyzed water is tested by a constant current potential method.
Compared with the prior art, the invention has the following advantages and effects:
1. the invention provides a p-type delafossite structure CuScO2The crystal material is prepared into the p-type delafossite structure CuScO with the size of about 2 mu m by utilizing a one-step reaction method by utilizing a low-temperature hydrothermal reaction and regulating and controlling hydrothermal reaction process parameters including reaction precursor components, reaction temperature, reaction time and the like2A crystalline material; the method avoids the accurate control of the pH value of the reaction precursor, and has the advantages of simple preparation process, easy control of process parameters, good experimental repeatability and high single-time yield up to about 2.0 g; the used reaction raw materials have wide sources and low prices and are low in large-scale production cost.
2. The invention provides a p-type delafossite structure CuScO2Two uses of the crystalline material:
(1) p-type delafossite structure CuScO2The crystal material can be used as a novel semiconductor material to be applied to various photoelectric functional devices such as solar cells, electrolyzed water, photo-electrolyzed water or photocatalysis.
(2) For the first time to CuScO2The electrolytic water oxygen evolution activity of the crystal material is tested to confirm that the CuScO2The crystal material has higher electrocatalytic oxygen evolution activity and good working stability under alkaline conditions, and specifically comprises the following components in percentage by weight:
when the loading amount is 0.30mg/cm2,Ni@CuScO2Shows the best electrocatalytic oxygen evolution activity (no IR correction, fig. 3) and good stability (no IR correction, fig. 4). Ni @ CuScO2Generate current of 10mAcm-2Requires an over-potential η10477mV, after 18 hours of continuous work, the overpotential increases by about 20 mV. Indicating CuScO2The crystal material is expected to be used as a high-efficiency electrolytic water oxygen evolution catalyst material.
Drawings
FIG. 1 is a CuScO prepared in example 12An X-ray diffraction pattern of the crystalline material;
FIG. 2 is a CuScO prepared in example 12Scanning electron microscope images of the crystal materials;
FIG. 3 shows (1MKOH) Ni @ CuScO under basic conditions as tested in Experimental example 22Electrocatalytic oxygen evolution activity results of (a);
FIG. 4 shows (1M KOH) Ni @ CuScO under basic conditions as tested in Experimental example 22The stability of the electrocatalytic oxygen evolution reaction.
Detailed Description
Example 1
The embodiment provides a delafossite structure CuScO catalyst for oxygen evolution by electrolysis of water2The crystal material and the preparation method thereof comprise the following steps:
firstly preparing a reaction precursor (or called a hydrothermal reaction precursor): adding Cu (NO)3)2And Sc (NO)3)3According to a molar ratio of 1: 1, adding the mixture into the reaction solution, stirring the mixture for 10 to 15 minutes in a magnetic stirrer, and adding the mixture into the reaction solutionCu(NO3)2And (3) taking NaOH with the molar number of 10 times as the mineralizer, finally adding 0.5ml of ethylene glycol, and continuously stirring for 10-15 minutes until the ethylene glycol is completely dissolved to obtain a reaction precursor.
The reaction precursor is transferred to a hydrothermal reaction kettle (generally made of polytetrafluoroethylene), the resistivity of deionized water is 18.24M omega cm (25 ℃), and the filling rate is about 70%. And sealing the kettle body, and then placing the kettle body in a program temperature control oven to perform hydrothermal reaction, wherein the reaction temperature is set to be 240 ℃, and the reaction time is set to be 24 hours.
After the reaction is finished, the kettle body is naturally cooled to room temperature, and the kettle body is opened to take out a reaction product (to obtain a precipitate). The reaction product (resulting precipitate) was treated sequentially with deionized water and dilute NH3·H2Centrifugally cleaning for 3 times by using O (mass fraction of 5%), deionized water, absolute ethyl alcohol and the like, and finally drying in a vacuum oven at the temperature of 60 ℃ for 12 hours to obtain the p-type delafossite structure CuScO2A crystalline material.
Example 2
The embodiment provides a delafossite structure CuScO catalyst for oxygen evolution by electrolysis of water2The crystal material and the preparation method thereof comprise the following steps:
firstly preparing a reaction precursor (or called a hydrothermal reaction precursor): adding Cu (NO)3)2And Sc (NO)3)3According to a molar ratio of 1.5: 1, adding the mixture into the reaction solution, stirring the mixture for 10 to 15 minutes in a magnetic stirrer to dissolve the mixture, and then adding Cu (NO)3)2And (3) taking NaOH with the molar number of 10 times as the mineralizer, finally adding 1.0ml of ethylene glycol, and continuously stirring for 10-15 minutes until the ethylene glycol is completely dissolved to obtain a reaction precursor.
The reaction precursor was transferred to a hydrothermal reaction kettle (typically polytetrafluoroethylene) with a deionized water resistivity of 18.24M Ω · cm (25 ℃), and a fill rate of about 65%. And sealing the kettle body, and then placing the kettle body in a program temperature control oven to perform hydrothermal reaction, wherein the reaction temperature is set to be 240 ℃, and the reaction time is set to be 48 hours.
After the reaction is finished, the kettle body is naturally cooled to room temperature, and the kettle body is opened to take out a reaction product (to obtain a precipitate). The reaction product (resulting precipitate) was treated sequentially with deionized water and dilute NH3·H2Centrifugally cleaning for 3 times by using O (mass fraction of 10%), deionized water, absolute ethyl alcohol and the like, and finally drying in a vacuum oven at the temperature of 60 ℃ for 4 hours to obtain the p-type delafossite structure CuScO2A crystalline material.
Example 3
The embodiment provides a delafossite structure CuScO catalyst for oxygen evolution by electrolysis of water2The crystal material and the preparation method thereof comprise the following steps:
firstly preparing a reaction precursor (or called a hydrothermal reaction precursor): adding Cu (NO)3)2And Sc (NO)3)3According to a molar ratio of 1.25: 1, adding the mixture into the reaction solution, stirring the mixture for 10 to 15 minutes in a magnetic stirrer to dissolve the mixture, and then adding Cu (NO)3)2NaOH with the molar number of 6 times is used as a mineralizer, and finally 1.0ml of ethylene glycol is added, and the mixture is continuously stirred for 10-15 minutes until the mixture is completely dissolved, so that a reaction precursor is obtained.
The reaction precursor was transferred to a hydrothermal reaction kettle (typically polytetrafluoroethylene) with a deionized water resistivity of 18.24M Ω · cm (25 ℃), and a fill rate of about 75%. And sealing the kettle body, and then placing the kettle body in a program temperature control oven to perform hydrothermal reaction, wherein the reaction temperature is set to be 210 ℃, and the reaction time is set to be 12 hours.
After the reaction is finished, the kettle body is naturally cooled to room temperature, and the kettle body is opened to take out a reaction product (to obtain a precipitate). The reaction product (resulting precipitate) was treated sequentially with deionized water and dilute NH3·H2Centrifugally cleaning for 3 times by using O (mass fraction of 1%), deionized water, absolute ethyl alcohol and the like, and finally drying in a vacuum oven at the temperature of 60 ℃ for 12 hours to obtain the p-type delafossite structure CuScO2A crystalline material.
Example 4
The embodiment provides a delafossite structure CuScO catalyst for oxygen evolution by electrolysis of water2The crystal material and the preparation method thereof comprise the following steps:
firstly preparing a reaction precursor (or called a hydrothermal reaction precursor): adding Cu (NO)3)2And Sc (NO)3)3According to a molar ratio of 1.25: 1, adding the mixture into the reaction solution, stirring the mixture for 10 to 15 minutes in a magnetic stirrer to dissolve the mixture, and then adding Cu (NO)3)2And (3) taking NaOH with the mole number of 15 times as a mineralizer, finally adding 0.15ml of ethylene glycol, and continuously stirring for 10-15 minutes until the ethylene glycol is completely dissolved to obtain a reaction precursor.
The reaction precursor is transferred to a hydrothermal reaction kettle (generally made of polytetrafluoroethylene), the resistivity of deionized water is 18.24M omega cm (25 ℃), and the filling rate is about 70%. And sealing the kettle body, and then placing the kettle body in a program temperature control oven to perform hydrothermal reaction, wherein the reaction temperature is set to be 220 ℃, and the reaction time is set to be 24 hours.
After the reaction is finished, the kettle body is naturally cooled to room temperature, and the kettle body is opened to take out a reaction product (to obtain a precipitate). The reaction product (resulting precipitate) was treated sequentially with deionized water and dilute NH3·H2Centrifugally cleaning for 3 times by using O (mass fraction of 5%), deionized water, absolute ethyl alcohol and the like, and finally drying in a vacuum oven at the temperature of 60 ℃ for 8 hours to obtain the p-type delafossite structure CuScO2A crystalline material.
Experimental example 1P-type delafossite structure CuScO2Characterization of crystalline materials
FIG. 1 is a reaction product p-type delafossite structure CuScO prepared in example 12An X-ray diffraction pattern of the crystalline material; the abscissa of the graph is the diffraction angle and the ordinate is the relative intensity. As can be seen from FIG. 1, when 0.5ml of ethylene glycol was added at a reaction temperature of 240 ℃ for 24 hours, CuScO was produced2The number of the crystal material corresponding to the standard diffraction pattern is #40-1038, and the crystal material is CuScO with a delafossite structure2The crystalline material is a main crystalline phase. It should be noted that the p-type delafossite structure CuScO prepared in examples 2 to 4 was obtained2The X-ray diffraction pattern of figure 1 can also be obtained for crystalline materials.
FIG. 2 shows the p-type delafossite structure CuScO prepared in example 12Scanning electron microscope image of crystal material. As can be seen from the figure, the prepared CuScO2The size of the crystal is about 2 mu m, and the micro-morphology of the crystal conforms to the hexagonal sheet shape of the typical delafossite structure crystal material.
Experimental example 2
1. The p-type delafossite CuScO prepared in examples 1 to 4 has a structure2The oxygen evolution activity of the crystal material in water electrolysis is tested. Mixing CuScO2The particles are loaded with CuScO on the surface of a working electrode or the surface of conductive glass (FTO) by using a thin film deposition technology (such as a dropping coating method, a thermal spraying decomposition method and the like)2Crystalline material for use as an electrolytic hydration agent material. For example, 15mg of CuScO is weighed2The powder was ultrasonically dispersed in 1ml of a mixed solution of water-isopropyl alcohol-Nafion (volume ratio 25: 24: 1), and 20. mu.l of CuScO was pipetted using a pipette2The suspension is dripped on the surface of a nickel screen to prepare CuScO2The loading amount of (A) was 0.30mg/cm2Ni @ CuScO of2The electrode is baked for 0.5 hour at 120 ℃ after the nickel screen is naturally dried, and can be used as a catalyst electrode material in a light/electrolytic water oxygen evolution experiment. The electrochemical workstation is used for testing by adopting a three-electrode system, and the working electrode is a nickel mesh loaded CuScO2(Ni@CuScO2) And a blank nickel screen control sample, and the electrolyte is 1M KOH aqueous solution. Testing the oxygen evolution activity of electrolyzed water by cyclic voltammetry scanning (voltage scanning window: 1.0V-2.0V vs. RHE, reversible hydrogen electrode potential, scanning speed 5mV/s), and constant current potential method (10 mAcm)-2And 20mAcm-2) The stability of the electrolytic water oxygen evolution reaction is tested.
2. The electrocatalytic oxygen evolution activity results are shown in FIG. 3, and the cyclic voltammetry scanning curve shows that the CuScO is loaded2Crystals 0.30mg/cm2Then, Ni @ CuScO2The electrocatalytic oxygen evolution activity is obviously improved, and the generated current is 10mAcm-2Requires an over-potential η10530mV (Ni) down to η10=477mV(Ni@CuScO2)。
Ni @ CuScO (1M KOH) under alkaline condition2The stability results of the electrocatalytic oxygen evolution reaction of (1) are shown in FIG. 4, where a blank nickel mesh electrode was used at constant current (10 mAcm)-2And 20mAcm-2) After 18 hours of operation, the overpotential increased by about 50 mV. And Ni @ CuScO2(0.30mg/cm2) After the electrode is operated for 18 hours under constant current, the overpotential of the electrode increases by about 20mV, which indicates that CuScO2The crystal material has good stability of electrolytic water oxygen evolution reaction.
Experimental example 3
The p-type delafossite structure CuS prepared in examples 1 to 4 abovecO2Other uses of the crystal material mainly refer to the use as an electrode material in photoelectric functional devices of semiconductor oxides. Mixing CuScO2The particles are prepared into CuScO on the surface of conductive glass (FTO) by using a film deposition technology (such as a screen printing method, a thermal spraying decomposition method and the like)2Thin film materials are used as electrode materials for solar cells (dye/quantum dot sensitized, perovskite solar cells, etc.). For example, CuScO is added in proportion2Crystal material (1.0g), ethyl cellulose (5.0g), terpineol (6.0g), absolute ethyl alcohol (30.0g) and the like, and CuScO with different solid contents is obtained after ultrasonic dispersion, rotary evaporation and other treatments2Brushing a film on the surface of the conductive glass by using a screen printing method, removing organic matters by heat treatment and sintering to finally obtain CuScO2And (3) electrode film materials.
The invention is not to be considered as limited to the particular embodiments shown, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. P type delafossite structure CuScO2A method for preparing a crystalline material, the method comprising:
step 1, preparation of a reaction precursor: with Cu2+Source reactant and Sc3+Taking a source reactant as a raw material, taking deionized water as a reaction solution, adding a reducing agent and a mineralizer, and fully stirring until the reducing agent and the mineralizer are completely dissolved to prepare a reaction precursor;
step 2, carrying out hydrothermal reaction on the reaction precursor at 210-240 ℃ for 12-48 hours, then carrying out centrifugal cleaning treatment on the reaction product to obtain a precipitate, and drying the precipitate to obtain the p-type delafossite structure CuScO2A crystalline material.
2. The p-type delafossite-structured CuScO of claim 12A method for producing a crystalline material, characterized in that the Cu2+Source reactant and Sc3+The source reactant comprises Cu (NO)3)2And Sc (NO)3)3Or other compounds containing Sc3+And Cu2+The compound of (1).
3. The p-type delafossite-structured CuScO of claim 22A method for producing a crystalline material, characterized in that the Cu2+Source reactant and Sc3+The molar ratio of the source reactants is 1.0-1.5: 1.
4. the p-type delafossite-structured CuScO of claim 12The preparation method of the crystal material is characterized in that the mineralizer is NaOH, and the mineralizer and the Cu2+The molar weight of the source reactant is 6-10: 1.
5. the p-type delafossite-structured CuScO of claim 12The preparation method of the crystal material is characterized in that the reducing agent is one of ethylene glycol, polyethylene glycol, glucose, ascorbic acid and hydrazine hydrate.
6. The p-type delafossite-structured CuScO of claim 12The preparation method of the crystal material is characterized in that the hydrothermal reaction is carried out in a hydrothermal reaction kettle, and the filling rate of a reaction solution in the hydrothermal reaction kettle is 65-75%.
7. The p-type delafossite-structured CuScO of claim 12The preparation method of the crystal material is characterized in that the centrifugal cleaning treatment in the step 2 comprises the following specific steps: adding deionized water and NH with the dilute mass fraction of 1-10%3·H2O, carrying out centrifugal cleaning on reaction products by absolute ethyl alcohol according to any sequence; the drying step in the step 2 is as follows: drying the mixture for 4 to 12 hours in a vacuum drying oven at 60 ℃.
8. P-type delafossite structure CuScO prepared by the method of any one of claims 1 to 72A crystalline material.
9. The method of claim 8P-type delafossite structure CuScO2Use of a crystalline material in a photovoltaic functional device of a transparent conductive oxide.
10. The p-type delafossite structure CuScO of claim 82The crystal material is used as a catalyst material for efficient electrolytic water oxygen evolution.
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