CN109748327B - Low-temperature preparation of CuCoO based on MOFs material2Method for producing nanocrystalline material - Google Patents

Low-temperature preparation of CuCoO based on MOFs material2Method for producing nanocrystalline material Download PDF

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CN109748327B
CN109748327B CN201910138897.7A CN201910138897A CN109748327B CN 109748327 B CN109748327 B CN 109748327B CN 201910138897 A CN201910138897 A CN 201910138897A CN 109748327 B CN109748327 B CN 109748327B
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熊德华
李宏
杜子娟
钱津辰
张天阳
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Wuhan University of Technology WUT
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Abstract

The invention relates to a method for preparing nano CuCoO by synthesis at a lower temperature by using a hydrothermal method2A method of crystallizing a material. MOFs material-based CuCoO for preparing delafossite structure at low temperature2The method for preparing the nanocrystalline material is characterized by comprising the following steps of: preparing a reaction precursor by taking a Metal Organic Framework (MOFs) material as an initial reactant, putting the reaction precursor into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 100-140 ℃ for 24-48 hours, carrying out centrifugal cleaning treatment on a reaction product to obtain a precipitate, and drying the precipitate to obtain the CuCoO with a delafossite structure of 50-200 nm size2A nanocrystalline material. The method has the characteristics of simple operation, easy control of process parameters, no pollution, high yield, low temperature and high speed; can be widely used in various novel photoelectric functional devices.

Description

Low-temperature preparation of CuCoO based on MOFs material2Method for producing nanocrystalline material
Technical Field
The invention relates to the field of synthesis and preparation of MOFs (Metal Organic Frameworks) materials and nano materials, in particular to a method for synthesizing and preparing nano-scale delafossite structure CuCoO by using a hydrothermal method at a lower reaction temperature2A method of crystallizing a material.
Background
Delafossite type oxide (ABO)2A ═ Cu, Ag, etc., B ═ Al, Ga, Cr, Co, L a, etc.) are important transition metal oxide materials, cusalo was first reported in Nature in 1997 by professor of Hosono, university of tokyo, japan2The p-type conductivity of the film is 9.5 × 10 at room temperature-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 moietyConductor material, 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.
CuCoO2The material is a novel, cheap and environment-friendly ABO2A material. In the 3R cuprite phase CuCoO2In which Cu has an intimate shell d10 structure, an O-Cu-O layer having a dumbbell-like linear structure, and CoO6And the common-edge octahedron layers are stacked alternately. CuCoO of 3R crystal form2Cell parameters of
Figure BDA0001977901400000011
Because the hybridization of the copper 3d orbital and the oxygen 2p orbital leads to the localization of oxygen atoms at the valence band edge, and the hexagonal close-packed copper layer is the main conductive layer, the material has larger optical band gap width and higher conductivity, and has good application prospect in the field of photoelectric devices. At present, CuCoO is treated at home and abroad2The research reports of the material are less, and CuCoO can be prepared by ion exchange reaction or high-temperature solid-phase reaction2A crystalline material. However, too long a reaction time or too high a reaction temperature may result in CuCoO2The material has a large crystal size and a low reaction efficiency, for example, in 2010, M.Beekman et al, by CuCl and L iCoO2The reaction is carried out for 48 hours at 590 ℃ to prepare the polycrystalline delafossite oxide CuCoO2A material. 2013, Ruttanapun et al synthesized CuCoO with delafossite structure by a conventional solid-phase reaction method at a high temperature of 1005 DEG C2A crystalline material. Compared with the traditional ion exchange reaction method or high-temperature sintering method, the hydrothermal method has the advantages that the reactants are placed in a special environment (closed, high-pressure and the like) to perform synthesis reaction, two complex experimental operations of high-temperature calcination and ball milling are avoided, the product synthesis efficiency can be greatly improved, and the method is widely applied to the field of synthesis of nano-structure crystal materials. The applicant subject group is that CuCoO with the size of 2 microns is firstly synthesized and prepared by using a low-temperature hydrothermal method in 2017 at the reaction temperature of 100 DEG C2Crystal material and research on the oxygen evolution activity of the electrolyzed water. But due to CuCoO2Size of crystalline materialLarger, smaller specific surface area results in less active sites, and the activity of the electrolyzed water still needs to be improved. Furthermore, due to the nanoscale p-type semiconductor ABO2The synthesis and preparation of materials are very difficult, ABO2The shortage of the nanocrystalline material seriously restricts the application research of photoelectric devices of the series of materials. Currently, only CuGaO is available2、CuCrO2、CuAlO2、CuMnO2、AgCrO2The related reports of several nanocrystalline materials have not found about the synthesis of nano CuCoO by a hydrothermal method2Research on crystalline materials is reported. Therefore, there is an urgent need to explore, develop and utilize a new material synthesis method to effectively control the crystal micro-morphology and size thereof to prepare high-quality CuCoO2A nanocrystalline material. Therefore, the hydrothermal method for preparing CuCoO is studied2The nanocrystalline material is very novel and is useful for exploring the preparation of p-type ABO2The nanocrystalline material and the device application thereof have very important research significance.
Disclosure of Invention
The invention aims to provide a method for preparing CuCoO with a delafossite structure at low temperature2The method for preparing the nanocrystalline material has the characteristics of low temperature and high speed.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: method for preparing CuCoO with nanoscale delafossite structure at low temperature2A method of crystallizing a material, comprising the steps of: preparing a reaction precursor (or called hydrothermal reaction precursor, namely preparing the reaction precursor by taking a MOFs material containing Cu or Co as an initial reactant), putting the reaction precursor into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24-48 hours at 100-140 ℃, carrying out centrifugal cleaning on the reaction product to obtain a precipitate, and drying the precipitate to obtain CuCoO with a delafossite structure2Crystalline material (CuCoO with crystal size of about 50-200 nm)2A crystalline material.
According to the technical scheme, the preparation method of the reaction precursor comprises the following steps: adding a Co source reactant and a Cu source reactant into a mixed solution of deionized water and absolute ethyl alcohol according to the mass ratio of 1: 1-1.3, wherein the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 0.4-3.0, fully stirring and dissolving in a magnetic stirrer (stirring for 10-15 minutes), adding NaOH which is 10-50 times of the mass of the Co source reactant or the Cu source reactant, serving as a mineralizer, and fully stirring until the materials are completely dissolved to obtain a reaction precursor.
Specifically, the preparation method of the reaction precursor comprises one of the following three steps (the volume ratio of deionized water to absolute ethyl alcohol is 1: 0.4-3.0):
1) adding a Co MOFs material and a Cu-based compound into a mixed solution of deionized water and absolute ethyl alcohol according to the mass ratio of 1: 1-1.3, stirring and dissolving, then adding a Co MOFs material or NaOH with the mass 10-50 times that of the Cu-based compound as a mineralizer, and stirring until the materials are completely dissolved to obtain a reaction precursor;
2) adding a Co-based compound and a Cu MOFs material into a mixed solution of deionized water and absolute ethyl alcohol according to a mass ratio of 1: 1-1.3, stirring and dissolving, then adding NaOH which is 10-50 times of the mass of the Co-based compound or the Cu MOFs material as a mineralizer, and stirring until the materials are completely dissolved to obtain a reaction precursor;
3) adding Co MOFs material and Cu MOFs material into a mixed solution of deionized water and absolute ethyl alcohol according to the mass ratio of 1: 1-1.3, stirring and dissolving, adding Co MOFs material or NaOH which is 10-50 times of the mass of Cu MOFs material as a mineralizer, and stirring until the materials are completely dissolved to obtain a reaction precursor.
According to the technical scheme, the Cu source reactant is Cu-containing2+Compound of { e.g. Cu (NO)3)2、CuSO4Aqueous solutions }, or Cu-containing MOFs materials.
According to the technical scheme, the Co reactant is Co-containing2+Compound of { such as Co (NO)3)2、CoSO4Aqueous solutions }, or MOFs materials containing Co.
According to the technical scheme, in the hydrothermal reaction, a reaction solution in a hydrothermal reaction kettle is a mixed solution of deionized water and absolute ethyl alcohol, and the composition of the mixed solution is as follows: the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 0.4-3.0, the resistivity of the deionized water is 18.24M omega cm (25 ℃), and the filling rate is 60-75%.
According to the technical scheme, theThe centrifugal cleaning treatment method comprises the following steps: sequentially adopting deionized water and dilute NH3·H2And carrying out centrifugal cleaning on the reaction product by using O (mass fraction of 1-10%) and absolute ethyl alcohol in sequence. Wherein the cleaning sequence of the centrifugal cleaning liquid can be adjusted (deionized water and dilute NH can also be adopted)3·H2Centrifugal washing with O, deionized water, absolute ethanol, etc.).
According to the technical scheme, the centrifugal cleaning treatment method comprises the following steps: according to dilute NH3·H2And performing centrifugal cleaning on O (mass fraction of 1-10%), deionized water and absolute ethyl alcohol in sequence.
According to the technical scheme, the drying comprises the following steps: and drying the precipitate after the centrifugal cleaning treatment in a vacuum drying oven at 60 ℃ for 4-12 hours.
The CuCoO with the structure of preparing delafossite at low temperature2The application of the nanocrystalline material is characterized in that: the material is applied to various photoelectric functional devices as a novel semiconductor working electrode material.
According to the technical scheme, the photoelectric functional device is applied as follows: in solar cells, electrolytic water, photo-electrolytic water, or photocatalytic devices, etc.
The method utilizes low-temperature hydrothermal reaction, regulates and controls the components of a reaction precursor, the reaction temperature and the filling rate parameter of a reaction liquid in a hydrothermal reaction kettle, and prepares the nano-scale CuCoO by a one-step reaction method at a lower temperature (100-140 ℃) for the first time2A crystalline material. Introducing Cu or Co source by taking MOFs material as reactant to develop CuCoO2The rapid preparation method of the crystal material with low temperature, high yield and low cost has very important academic value for promoting the p-type semiconductor material with the delafossite structure and the application development of the p-type semiconductor material in the field of photoelectric devices.
Compared with the prior art, the invention has the beneficial effects that:
first utilizes a low-temperature hydrothermal method to prepare nano-CuCoO2The crystal material fills up the CuCoO with the structure of preparing the delafossite through synthesis at home and abroad2The research of the nanocrystalline material is blank, and p-type ABO is expected to be promoted2Semiconductor material and its use in lightApplications in the field of electrical devices are evolving. Also has the following characteristics:
(1) the method has the advantages of simple preparation process, easily controlled process parameters, good experimental repeatability and high single-time yield.
(2) The method has the advantages of wide source of raw materials, low price and low production cost.
(3) When the reaction temperature is 100-140 ℃, CuCoO can be prepared2A crystalline material (see figure 1). As the reaction temperature was decreased from 140 ℃ to 100 ℃, the nanocrystal size decreased from-150 nm (fig. 2) to-50 nm (fig. 3).
(4) XPS for CuCoO2The valence state information of the surface element of the crystal material is tested and analyzed (as shown in figure 4), and the test result shows that Cu in the compound is Cu+Co is Co3+Belonging to the group of delafossite (A)IBⅢO2) Structural materials, consistent with literature reports.
Drawings
FIG. 1 is an X-ray diffraction pattern of the reaction product prepared in examples 1, 2, 3 and 4; the abscissa of the graph is the diffraction angle and the ordinate is the relative intensity. As can be seen from the figure, CuCoO can be prepared at the reaction temperature of 100-140 DEG C2The crystal material is numbered as #21-0256 corresponding to a standard diffraction pattern and is a delafossite structure CuCoO2The crystalline material is a main crystalline phase.
FIG. 2 is a CuCoO prepared in example 22Scanning electron microscope image of crystal material. And observing and taking a micro-morphology picture of the reaction product by using a field emission scanning electron microscope at the reaction temperature of 140 ℃. As can be seen from the figure, the prepared CuCoO2The size of the crystal of the material is about 100-200 nm, and the microscopic morphology of the crystal material conforms to that of a typical delafossite structure crystal material.
FIG. 3 is a CuCoO prepared in example 42Scanning electron microscope image of crystal material. And observing and shooting a micro-morphology picture of a reaction product by using a field emission scanning electron microscope when the reaction temperature is 100 ℃. As can be seen from the figure, the prepared CuCoO2The crystal size of the material is about 50-80 nm.
FIG. 4 is a drawing of example 1Prepared CuCoO2The crystal material is analyzed by X-ray photoelectron spectroscopy (XPS), wherein a is shown as Cu 2p 3/2 and Cu 2p 1/2, which are two characteristic lines of Cu 2p, corresponding to 933.0eV and 952.7eV, respectively, and other ABO2Material CuAlO2、CuFeO2The spectral line positions of the middle Cu 2p are similar, which shows that the spectral line positions are Cu+. In addition, it can be seen from the graph b that the two characteristic lines Co 2p 3/2 and Co 2p 1/2 of Co 2p correspond to 780.3eV and 795.4eV, respectively, and Co 2p 1/22O3The characteristic spectral line positions of the medium Co 2p are close, which shows that the medium Co 2p is Co3+。
Detailed Description
The invention utilizes hydrothermal reaction to prepare nano CuCoO2The chemicals used for the crystalline material mainly comprise Co (NO)3)2Methanol, 2-methylimidazole, isophthalic acid, Cu (NO)3)2NaOH, absolute ethanol, NH3·H2O and deionized water, etc.
For example, the preparation of MOFs crystal material containing Cu (Cu-BTC): Cu-BTC containing Cu is prepared by a hydrothermal synthesis method (which is a method reported in the existing literature), and Cu-BTC powder can be obtained after centrifugal cleaning and drying.
For example, preparation of Co-containing MOFs crystalline material (ZIF-67): ZIF-67 containing Co (a method reported in the existing literature) is prepared by a room temperature aging method, and ZIF-67 powder can be obtained after centrifugal cleaning and drying.
The present invention will be further described with reference to the following examples and drawings, but is not limited to the following.
Example 1:
CuCoO for preparing nanoscale delafossite structure at low temperature2A method of crystallizing a material comprising the steps of:
firstly preparing a reaction precursor (or called a hydrothermal reaction precursor): co MOFs crystal material (ZIF-67) and Cu (NO)3)2Adding the mixture into a reaction solution (the reaction solution is a mixed solution of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:2.5) according to the mass ratio of 1:1, stirring the mixture in a magnetic stirrer for 10 to 15 minutes to dissolve the mixture, and then adding ZIF-67 with the mass of 10 to 10And taking NaOH as a mineralizer, and continuously stirring for 10-15 minutes until the NaOH is completely dissolved to obtain a reaction precursor.
The reaction precursor is transferred into a hydrothermal reaction kettle (generally made of polytetrafluoroethylene), a reaction solution is controlled (a reaction solution in the hydrothermal reaction kettle is a mixed solution of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:2.5), the resistivity of the 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 140 ℃, 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 O (mass fraction of 1%), deionized water, absolute ethyl alcohol and the like for 2 times, and finally drying in a vacuum oven at 60 ℃ for 12 hours to obtain CuCoO with the size of 100-200 nm2A nanocrystalline material.
Example 2:
CuCoO for preparing nanoscale delafossite structure at low temperature2A method of crystallizing a material comprising the steps of:
firstly preparing a reaction precursor (or called a hydrothermal reaction precursor): ZIF-67 and Cu (NO)3)2Adding the mixture into a reaction solution (the reaction solution is a mixed solution of deionized water and absolute ethyl alcohol, and the volume ratio of the deionized water to the absolute ethyl alcohol is 1:2.5) according to the mass ratio of 1:1.2, fully stirring and dissolving the mixture in a magnetic stirrer for 10-15 minutes, adding NaOH 50 times the mass of ZIF-67 serving as a mineralizer, and continuously stirring the mixture for 10-15 minutes until the mixture is completely dissolved to obtain a reaction precursor.
The reaction precursor is transferred into a hydrothermal reaction kettle (generally made of polytetrafluoroethylene), the reaction liquid is controlled (the reaction liquid in the hydrothermal reaction kettle is a mixed solution of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:2.5), the resistivity of the deionized water is 18.24M omega cm (25 ℃), and the filling rate is 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 140 ℃, 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 3 times with O (mass fraction of 3%), deionized water, absolute ethyl alcohol and the like, and finally drying in a vacuum oven at 60 ℃ for 8 hours to obtain CuCoO with the size of 100-200 nm2A nanocrystalline material.
Example 3:
CuCoO for preparing nanoscale delafossite structure at low temperature2A method of crystallizing a material comprising the steps of:
firstly preparing a reaction precursor (or called a hydrothermal reaction precursor): mixing Co-based MOF materials ZIF-67 and Cu (NO)3)2Adding the mixture into a reaction solution (the reaction solution is a mixed solution of deionized water and absolute ethyl alcohol, and the volume ratio of the deionized water to the absolute ethyl alcohol is 1:2.5) according to the mass ratio of 1:1.2, fully stirring the mixture in a magnetic stirrer for 10 to 15 minutes to dissolve the mixture, and then adding Cu (NO)3)2And (3) taking NaOH with the mass being 10 times of that of the mineralizer, and continuously stirring for 10-15 minutes until the NaOH is completely dissolved to obtain a reaction precursor.
The reaction precursor is transferred into a hydrothermal reaction kettle (generally made of polytetrafluoroethylene), the reaction liquid is controlled (the reaction liquid in the hydrothermal reaction kettle is a mixed solution of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:2.5), the resistivity of the deionized water is 18.24M omega cm (25 ℃), and the filling rate is about 60%. 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 120 ℃, and the reaction time is set to be 24 hours.
After the reaction is finished, opening the kettle body to take out a reaction product after the kettle body is naturally cooled to room temperature. The reaction product (resulting precipitate) was treated sequentially with deionized water and dilute NH3·H2Centrifugally cleaning for 3 times O (mass fraction of 5%), deionized water, absolute ethyl alcohol and the like, and finally drying in a vacuum oven at 60 ℃ for 8 hours to obtain CuCoO with the size of 80-200 nm2A nanocrystalline material.
Example 4:
CuCoO for preparing nanoscale delafossite structure at low temperature2A method of crystallizing a material comprising the steps of:
firstly preparing a reaction precursor (or called a hydrothermal reaction precursor): ZIF-67 and Cu (NO)3)2Adding the mixture into a reaction solution (the reaction solution is a mixed solution of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:2.5) according to the mass ratio of 1:1.3, fully stirring the mixture in a magnetic stirrer for 10 to 15 minutes to dissolve the mixture, and then adding Cu (NO)3)2And (3) taking NaOH with the mass being 50 times of that of the mineralizer, and continuously stirring for 10-15 minutes until the NaOH is completely dissolved to obtain a reaction precursor.
The reaction precursor is transferred into a hydrothermal reaction kettle (generally made of polytetrafluoroethylene), and a reaction solution (the reaction solution in the hydrothermal reaction kettle is a mixed solution of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:2.5) is controlled, wherein the filling rate of the deionized water is about 75% at 18.24M omega cm (25 ℃). 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 100 ℃, and the reaction time is set to be 24-48 hours.
After the reaction is finished, opening the kettle body to take out a reaction product after the kettle body is naturally cooled to room temperature. The reaction product (resulting precipitate) was treated sequentially with deionized water and dilute NH3·H2Centrifugally cleaning for 3 times O (mass fraction of 10%), deionized water, absolute ethyl alcohol and the like, and finally drying in a vacuum oven at 60 ℃ for 8 hours to obtain CuCoO with the size of 50-80 nm2A nanocrystalline material.
Example 5:
CuCoO for preparing nanoscale delafossite structure at low temperature2A method of crystallizing a material comprising the steps of:
firstly preparing a reaction precursor (or called a hydrothermal reaction precursor): ZIF-67 and Cu (NO)3)2Adding the mixture into a reaction solution (the reaction solution is a mixed solution of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:0.4) according to the mass ratio of 1:1.2, stirring the mixture in a magnetic stirrer for 10 to 15 minutes to dissolve the mixture, and then adding Cu (NO)3)2And (3) using NaOH with the mass being 30 times of that of the mineralizer, and continuously stirring for 10-15 minutes until the NaOH is completely dissolved to obtain a reaction precursor.
The reaction precursor is transferred into a hydrothermal reaction kettle (generally made of polytetrafluoroethylene), and a reaction solution (the reaction solution in the hydrothermal reaction kettle is a mixed solution of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:0.4), the resistivity of the deionized water is 18.24M omega cm (25 ℃), and the filling rate is 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 100 ℃, and the reaction time is set to be 48 hours.
After the reaction is finished, opening the kettle body to take out a reaction product after the kettle body is naturally cooled to room temperature. The reaction product (resulting precipitate) was treated sequentially with deionized water and dilute NH3·H2Centrifugally cleaning O (mass fraction of 5%), deionized water, absolute ethyl alcohol and the like for 4 times, and finally drying in a vacuum oven at 60 ℃ for 12 hours to obtain CuCoO2A nanocrystalline material.
Example 6:
CuCoO for preparing nanoscale delafossite structure at low temperature2A method of crystallizing a material comprising the steps of:
firstly preparing a reaction precursor (or called a hydrothermal reaction precursor): mixing Co (NO)3)2And adding an MOFs crystal material (Cu-BTC) of Cu into a reaction solution (the reaction solution is a mixed solution of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:1) according to the mass ratio of 1:1.2, stirring the mixture for 10-15 minutes in a magnetic stirrer for dissolving, then adding NaOH which is 10 times of the mass of the Cu-BTC as a mineralizer, and continuously stirring the mixture for 10-15 minutes until the mixture is completely dissolved to obtain a reaction precursor.
The reaction precursor is transferred into a hydrothermal reaction kettle (generally made of polytetrafluoroethylene), and a reaction solution (the reaction solution in the hydrothermal reaction kettle is a mixed solution of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:1), the resistivity of the 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 140 ℃, and the reaction time is set to be 24 hours.
After the reaction is finished, opening the kettle body to take out a reaction product after the kettle body is naturally cooled to room temperature. The reaction product (resulting precipitate) is in turnUsing deionized water, dilute NH3·H2Centrifugally cleaning O (mass fraction of 5%), deionized water, absolute ethyl alcohol and the like for 4 times, and finally drying in a vacuum oven at 60 ℃ for 12 hours to obtain CuCoO2A nanocrystalline material.
Example 7:
CuCoO for preparing nanoscale delafossite structure at low temperature2A method of crystallizing a material comprising the steps of:
firstly preparing a reaction precursor (or called a hydrothermal reaction precursor): adding Co MOFs crystal material (ZIF-67) and Cu MOFs crystal material (Cu-BTC) into a reaction solution (the reaction solution is a mixed solution of deionized water and absolute ethyl alcohol, and the volume ratio of the deionized water to the absolute ethyl alcohol is 1:3.0) according to the mass ratio of 1:1.2, stirring for 10-15 minutes in a magnetic stirrer to dissolve, adding NaOH which is 10 times the mass of the Cu-BTC to serve as a mineralizer, and continuously stirring for 10-15 minutes until the NaOH is completely dissolved to obtain a reaction precursor.
The reaction precursor is transferred into a hydrothermal reaction kettle (generally made of polytetrafluoroethylene), the reaction liquid is controlled (the reaction liquid in the hydrothermal reaction kettle is a mixed solution of deionized water and absolute ethyl alcohol, the volume ratio of the deionized water to the absolute ethyl alcohol is 1:3.0), the resistivity of the 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 140 ℃, and the reaction time is set to be 24 hours.
After the reaction is finished, opening the kettle body to take out a reaction product after the kettle body is naturally cooled to room temperature. The reaction product (obtained precipitate) is sequentially centrifugally cleaned for 4 times by deionized water, absolute ethyl alcohol and the like, and finally dried in a vacuum oven at the temperature of 60 ℃ for 12 hours to obtain CuCoO2A nanocrystalline material.
Example 8:
CuCoO of delafossite structure prepared in examples 1 to 7 above2The application of the nanocrystalline material mainly refers to the application of the nanocrystalline material as an electrode material in a photoelectric functional device of a semiconductor oxide. Mixing CuCoO2The particles are prepared into CuCoO 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 materialThe material is used as an electrode material of a solar cell (dye/quantum dot sensitization, perovskite solar cell and the like). For example, CuCoO is added in proportion2Carrying out ultrasonic dispersion, rotary evaporation and other treatments on nanocrystalline (1.0g), ethyl cellulose (5.0g), terpineol (6.0g), absolute ethyl alcohol (30.0g) and the like to obtain CuCoO with different solid contents2Brushing 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 the CuCoO2And (3) electrode film materials.
Example 9:
CuCoO of delafossite structure prepared in examples 1 to 7 above2The application of the nanocrystalline material mainly refers to the application of the nanocrystalline material as an electrode material in a photoelectric functional device of a semiconductor oxide. Mixing CuCoO2The particles are loaded with CuCoO 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)2Nanocrystalline materials are used as electrode catalyst materials in photoelectrochemical cells. For example, CuCoO is added in proportion2Nanocrystal (2.0 g), Nafion (10.0g), isopropanol (12.0g), H2O (50.0g) and the like, and CuCoO with a certain concentration is prepared by ultrasonic dispersion2The volume of the nano-crystal suspension is adjusted to prepare CuCoO with different loading capacity2The working electrode material can be used as a catalyst electrode material in a light/electrolytic water hydrogen evolution and oxygen evolution experiment.
It is obvious that those skilled in the art can apply the delafossite structure CuCoO of the present invention2Various modifications and variations can be made in the hydrothermal preparation of nanocrystalline materials and nanocrystalline materials thereof without departing from the spirit and scope of the invention. For example, one or more of MOFs containing Cu or Co and derivatives thereof are used as reactants, and a Cu source or a Co source is introduced to perform a hydrothermal reaction. Thus, if such modifications and variations of the present invention fall within the technical scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (6)

1. CuCoO with structure for preparing delafossite at low temperature2Of nanocrystalline materialsThe method is characterized by comprising the following steps: preparing a reaction precursor by taking MOFs materials as Cu or Co source initial reactants, putting the reaction precursor into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24-48 hours at 100-140 ℃, carrying out centrifugal cleaning treatment on the reaction product to obtain a precipitate, and drying the precipitate to obtain CuCoO with a delafossite structure2A crystalline material;
the preparation method of the reaction precursor comprises the following steps: adding a Co source reactant and a Cu source reactant into a mixed solution of deionized water and absolute ethyl alcohol according to the mass ratio of 1: 1-1.3, wherein the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 0.4-3, fully stirring and dissolving in a magnetic stirrer, adding NaOH which is 10-50 times of the mass of the Co source reactant or the Cu source reactant and is used as a mineralizer, and fully stirring until the materials are completely dissolved to obtain a reaction precursor.
2. The low-temperature preparation of delafossite structure CuCoO according to claim 12The method for preparing the nanocrystalline material is characterized by comprising the following steps: the Cu source reactant is Cu-containing2+Or a MOFs material containing Cu.
3. The low-temperature preparation of delafossite structure CuCoO according to claim 12The method for preparing the nanocrystalline material is characterized by comprising the following steps: the Co reactant is Co-containing2+Or a Co-containing MOFs material.
4. The low-temperature preparation of delafossite structure CuCoO according to claim 12The method for preparing the nanocrystalline material is characterized by comprising the following steps: the centrifugal cleaning treatment method comprises the following steps: according to the sequence of deionized water and dilute NH3·H2And O, carrying out centrifugal cleaning on the reaction products by absolute ethyl alcohol in sequence.
5. The low-temperature preparation of delafossite structure CuCoO according to claim 12The method for preparing the nanocrystalline material is characterized by comprising the following steps: the centrifugal cleaning treatment method comprises the following steps: according to dilute NH3·H2And performing centrifugal cleaning on O, deionized water and absolute ethyl alcohol in sequence.
6. The low-temperature preparation of delafossite structure CuCoO according to claim 12The method for preparing the nanocrystalline material is characterized by comprising the following steps: the drying comprises the following steps: and drying the precipitate after the centrifugal cleaning treatment in a vacuum drying oven at 60 ℃ for 4-12 hours.
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