CN110970630B - CuO nanosheet and top-down preparation method and application thereof - Google Patents

CuO nanosheet and top-down preparation method and application thereof Download PDF

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CN110970630B
CN110970630B CN201911155860.1A CN201911155860A CN110970630B CN 110970630 B CN110970630 B CN 110970630B CN 201911155860 A CN201911155860 A CN 201911155860A CN 110970630 B CN110970630 B CN 110970630B
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cuo
sodium hydroxide
copper
ammonium persulfate
solution
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CN110970630A (en
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陈光需
赵伟伟
杜瑞安
李正健
宾宇良
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Guangdong Zhida Yinowei Technology Co ltd
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South China University of Technology SCUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a CuO nanosheet and a preparation method and application thereof. The CuO nanosheet is prepared by a top-down method, namely, the CuO with the nanostructure is prepared from a copper material with a larger size by technologies such as ultrasonic etching and the like, and the specific operation method comprises the following steps: removing oil, pickling and washing a copper raw material, adding the copper raw material into a mixed solution of ammonium persulfate and sodium hydroxide, carrying out ultrasonic treatment and filtration, carrying out centrifugal separation on filtrate, taking precipitate, washing and drying to obtain a precursor; and grinding the precursor into powder, heating and roasting to obtain the CuO nanosheet. The preparation method provided by the invention has the advantages of simple process, low cost, uniform appearance of the obtained product, good repeatability and high electrocatalysis performance. The CuO nano-sheet is used as a catalyst for electrocatalytic reduction of carbon dioxide, and is reduced under-0.97 volt by taking a reversible hydrogen electrode as a standard to obtain C 2+ The faradaic efficiency of the product is over 60%, showing high C of CuO electrocatalyst in carbon dioxide reduction 2+ And (4) product selectivity.

Description

CuO nanosheet and top-down preparation method and application thereof
Technical Field
The invention belongs to the field of nanotechnology and the field of electrocatalysis, and particularly relates to a CuO nanosheet and a top-down preparation method and application thereof.
Background
At present, with the large-scale exploitation and use of fossil fuels such as petroleum, natural gas and the like, two global problems of energy crisis and environmental pollution are becoming more serious. The emission of excessive carbon dioxide in the atmosphere causes a series of global problems, such as greenhouse effect, rise of sea level, drought of land and the like. Facing a plurality of energy environmental problems, if carbon dioxide can be converted into living resources required by people, the method is an effective solution. Electrocatalytic carbon dioxide reduction technology, as a novel energy conversion technology, can convert carbon dioxide into high-value fuels such as ethylene, ethanol, propanol and the like by using electric energy converted from renewable energy sources to realize recycling of carbon dioxide, and has attracted wide attention in recent years (Seh, z.w. et al.
With the goal of practical application of electrocatalytic carbon dioxide reduction technology, there has been a great deal of research into the design and development of novel copper electrocatalysts, however, on the one hand, the use of CO 2 RR selectively converts carbon dioxide to high energy density C such as ethylene, ethanol and the like 2+ The conversion of the product is relatively low; on the other hand, the traditional preparation method of the nano copper-based catalyst is complex, has small yield and is not beneficial to large-scale preparation, so that how to improve the activity, selectivity and yield of the copper catalyst still faces huge challenges (Zhang, l., zhao, z. -J).& Gong, J. Nanostructured Materials for Heterogeneous Electrocatalytic CO 2 Reduction and the outer Related Reaction mechanisms, angew. Chem. Int. Ed. 56, 11326-11353 (2017). Therefore, based on the above discussion, it would be a main objective to promote the realization of carbon dioxide resource to explore a method for preparing a large amount of copper-based catalyst with high selectivity and high catalytic activity.
Disclosure of Invention
The invention aims to provide a method for preparing CuO nanosheets from top to bottom and application thereof, aiming at the problems of complex preparation method, low yield and the like in the prior art. The CuO nanosheet provided by the invention can be applied to a catalyst for electrochemical reduction reaction, and the catalyst is high in catalytic activity and good in stability.
The invention adopts a top-down method nano material preparation technology to prepare a large amount of copper-based catalyst, and is a simple and effective preparation technology.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a preparation method of a CuO nano sheet from top to bottom, which comprises the following steps:
(1) Removing oil, pickling and washing a copper raw material, adding the copper raw material into a mixed solution of ammonium persulfate and sodium hydroxide, carrying out ultrasonic treatment, filtering to obtain a filtrate, centrifuging the filtrate to obtain a precipitate, carrying out centrifugal washing for multiple times, and drying to obtain a precursor;
(2) And (2) grinding the precursor in the step (1) into powder, and then heating for roasting treatment to obtain the CuO nanosheet.
Further, the copper raw material in the step (1) is one of copper foil, copper pipe, copper powder, foam copper and the like.
Further, the oil removing treatment of the step (1) comprises: soaking the copper raw material in an acetone solution for ultrasonic treatment, wherein the ultrasonic treatment time is 0.1-5h, and the ultrasonic frequency of the ultrasonic treatment is 20-40 kHZ.
Preferably, in the oil removing treatment in the step (1), the time of ultrasonic treatment is 1h.
Further, in the step (1), the acid washing treatment is carried out by using a nitric acid solution, and the concentration of the nitric acid solution is 0.5mol/L-1mol/L.
Preferably, in the acid washing treatment in the step (1), the concentration of the nitric acid solution is 0.5mol/L.
Further, the mixed solution of ammonium persulfate and sodium hydroxide in the step (1) is a solution formed by uniformly mixing a sodium persulfate solution and a sodium hydroxide solution; in the mixed solution of ammonium persulfate and sodium hydroxide, the concentration of the ammonium persulfate is 0.1-0.15 mol/L, and the concentration of the sodium hydroxide is 2.5-3.0 mol/L.
Preferably, in the mixed solution of ammonium persulfate and sodium hydroxide in the step (1), the molar ratio of ammonium persulfate to sodium hydroxide is 1.
Further, the mass-to-volume ratio of the copper raw material to the mixed solution of ammonium persulfate and sodium hydroxide in the step (1) is 1.0 g/mL-1.5g/mL.
Further, the ultrasonic frequency of the ultrasonic treatment in the step (1) is 20-40 kHZ; the ultrasonic treatment time is 0.5 h-2h; the drying temperature is 60-80 ℃ and the drying time is 4 h-8 h.
Preferably, the ultrasonic frequency of the ultrasonic treatment in the step (1) is 20kHZ.
Preferably, the time of the ultrasonic treatment in the step (1) is 1h.
Furthermore, the aperture size of a filter screen used for filtering is 10 meshes.
Further, the temperature of the roasting treatment in the step (2) is 200-300 ℃, and the time of the roasting treatment is 2-4h.
The invention provides a CuO nano sheet prepared by the top-down method.
The CuO nanosheet provided by the invention can be applied to preparation of an electrochemical reduction reaction electrode. Preferably, in the electrochemical reduction reaction, the substance electrochemically reduced is carbon dioxide.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The preparation method of the CuO nanosheet provided by the invention is a top-down method, has the characteristics of simple process, low cost and the like, and the obtained product has uniform appearance and good repeatability;
(2) The CuO nanosheet provided by the invention has high electro-catalytic performance, the CuO suspension is dripped on a glassy carbon electrode by taking a reversible hydrogen electrode as a standard, and the prepared copper nanosheet aggregate electrode material is reduced to C by carbon dioxide under the condition of negative 0.97 volt 2+ In which the faradaic efficiency of ethylene exceeds 41%, the faradaic efficiency of ethanol exceeds 15%, and the faradaic efficiency of n-propanol exceeds 4%, exhibits high C for CuO nanoplatelets in carbon dioxide reduction 2+ And (4) selectivity.
Drawings
FIG. 1 is an XRD pattern of CuO nanosheet prepared in example 1;
fig. 2 is an SEM image of CuO nanoplates prepared in example 1;
fig. 3 is a TEM image of CuO nanoplates prepared in example 1;
FIG. 4 is an SEM image of CuONSs prepared in example 8;
FIG. 5 is a TEM image of CuONSs prepared in example 8;
FIG. 6 is a graph of Faraday efficiencies of CuONSs prepared in example 8 for electrochemically reducing carbon dioxide to different products in potassium bicarbonate solution;
FIG. 7 is a graph of the electrochemical reduction of CuONSs prepared in example 8 to C in potassium bicarbonate solution 2 H 4 Stability test chart (2).
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically detailed, are all those that can be realized or understood by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
A preparation method of CuO nano sheet from top to bottom comprises the following steps:
(1) Shearing 0.25 g copper foil into small pieces, soaking in an acetone solution for 30 min for ultrasonic surface degreasing treatment, wherein the ultrasonic frequency is 20kHZ, taking out, soaking and washing in a nitric acid solution (the concentration of the nitric acid solution is 0.5 mol/L) for 3 times, taking out, washing with deionized water, adding into a mixed solution of ammonium persulfate and sodium hydroxide with the volume of 50 mL, wherein the concentration of the ammonium persulfate is 0.134 mol/L and the concentration of the sodium hydroxide is 2.66mol/L in the mixed solution of the ammonium persulfate and the sodium hydroxide, performing ultrasonic treatment, the ultrasonic frequency is 20kHZ and the ultrasonic treatment time is 1h, filtering to obtain a filtrate, filtering to obtain a filter screen, centrifuging for 3min at the rotation speed of 7000rpm, taking a precipitate, then respectively washing the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying to obtain a precursor, the drying temperature is 80 ℃, and the drying time is 6h;
(2) Grinding the precursor in the step (1) into powder, then transferring the powder into a muffle furnace to be heated for roasting treatment, wherein the roasting treatment temperature is 200 ℃, and the roasting treatment time is 2h, so as to obtain the CuO nanosheet.
The XRD pattern of the CuO catalyst prepared in example 1 is shown in fig. 1, and it can be seen from fig. 1 that the XRD peak of the prepared CuO completely corresponds to that of the standard PDF card, indicating that the finally prepared product is CuO. SEM and TEM images of CuO nanoplates prepared in example 1 are shown in fig. 2 and 3, respectively, and it can be seen from fig. 2 and 3 that CuO particles are uniformly dispersed, assembled into nanoplates from countless nanobelts, and then self-assembled into flower-like particles, and the overall particle size is about 800 nm.
Example 2
A preparation method of CuO nano sheet from top to bottom comprises the following steps:
(1) Cutting 0.25 g copper foil into small pieces, soaking in an acetone solution for 30 min for surface degreasing treatment, wherein the ultrasonic frequency is 20kHZ, taking out, soaking and washing in a nitric acid solution (the concentration of the nitric acid solution is 0.5 mol/L) for 3 times, taking out, washing with deionized water, adding into a mixed solution of ammonium persulfate and sodium hydroxide with the volume of 50 mL, wherein the concentration of the ammonium persulfate is 0.1mol/L and the concentration of the sodium hydroxide is 2.5mol/L in the mixed solution of the ammonium persulfate and the sodium hydroxide, performing ultrasonic treatment, the ultrasonic frequency of the ultrasonic treatment is 20kHZ and the ultrasonic treatment time is 0.5h, filtering to obtain a filtrate, wherein the pore size of a filter screen used for filtering is 10 meshes, centrifuging for 3min at the rotation speed of 7000rpm, taking a precipitate, then respectively washing the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying to obtain a precursor, the drying temperature is 60 ℃, and the drying time is 4h;
(2) Grinding the precursor in the step (1) into powder, then transferring the powder into a muffle furnace to be heated for roasting treatment, wherein the roasting treatment temperature is 200 ℃, and the roasting treatment time is 2h, so as to obtain the CuO nanosheet.
Example 3
A preparation method of a CuO nano sheet from top to bottom comprises the following steps:
(1) Cutting 0.25 g copper foil into small pieces, soaking in an acetone solution for 30 min by ultrasonic treatment for surface degreasing treatment, wherein the ultrasonic frequency is 30 kHZ, taking out, soaking and washing in a nitric acid solution (the nitric acid concentration is 0.75 mol/L) for 3 times, taking out, washing with deionized water, adding into a mixed solution of ammonium persulfate and sodium hydroxide with the volume of 50 mL, wherein the ammonium persulfate concentration is 0.125 mol/L and the sodium hydroxide concentration is 2.75mol/L in the mixed solution of the ammonium persulfate and the sodium hydroxide, performing ultrasonic treatment, the ultrasonic frequency is 30 kHZ and the ultrasonic treatment time is 1h, filtering to obtain a filtrate, filtering to obtain a filter screen, centrifuging for 3min at the rotation speed of 7000rpm, taking a precipitate, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and drying to obtain a precursor, wherein the drying temperature is 70 ℃, and the drying time is 4h;
(2) Grinding the precursor in the step (1) into powder, then transferring the powder into a muffle furnace to be heated for roasting treatment, wherein the roasting treatment temperature is 250 ℃, and the roasting treatment time is 3h, so as to obtain the CuO nanosheet.
Example 4
A preparation method of CuO nano sheet from top to bottom comprises the following steps:
(1) Cutting 0.25 g copper foil into small pieces, soaking in an acetone solution for 30 min to carry out surface degreasing treatment, wherein the ultrasonic frequency is 40kHZ, taking out, soaking and washing in a nitric acid solution (the nitric acid concentration is 1 mol/L) for 3 times, taking out, washing with deionized water, adding into a mixed solution of ammonium persulfate and sodium hydroxide with the volume of 50 mL, wherein the ammonium persulfate concentration is 0.15mol/L and the sodium hydroxide concentration is 3mol/L in the mixed solution of the ammonium persulfate and the sodium hydroxide, carrying out ultrasonic treatment, the ultrasonic frequency of the ultrasonic treatment is 40kHZ, the ultrasonic treatment time is 2h, filtering to obtain a filtrate, filtering to use a filter screen with the pore size of 10 meshes, centrifuging for 3min at the rotation speed of 7000rpm, taking a precipitate, then respectively washing the precipitate with deionized water and absolute ethyl alcohol for 3 times, and drying to obtain the precipitate, wherein the drying temperature is 80 ℃, and the drying time is 4h;
(2) Grinding the precursor in the step (1) into powder, and then transferring the powder into a muffle furnace to be heated for roasting treatment, wherein the roasting treatment temperature is 300 ℃, and the roasting treatment time is 4h, so as to obtain the CuO nanosheet.
Example 5
A preparation method of CuO nano sheet from top to bottom comprises the following steps:
(1) Shearing 0.25 g copper pipe into small pieces, soaking in an acetone solution for 30 min to carry out surface degreasing treatment, wherein the ultrasonic frequency is 20kHZ, taking out, soaking and washing in a nitric acid solution (the nitric acid concentration is 0.5 mol/L) for 3 times, taking out, washing with deionized water, adding into a mixed solution of ammonium persulfate and sodium hydroxide with the volume of 50 mL, wherein the ammonium persulfate concentration is 0.134 mol/L and the sodium hydroxide concentration is 2.66mol/L in the mixed solution of the ammonium persulfate and the sodium hydroxide, carrying out ultrasonic treatment, wherein the ultrasonic frequency is 20kHZ and the ultrasonic treatment time is 1h, filtering to obtain a filtrate, filtering to obtain a filter screen, centrifuging for 3min at the rotation speed of 7000rpm, taking a precipitate, respectively washing the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying to obtain a precursor, wherein the drying temperature is 80 ℃ and the drying time is 6h;
(2) Grinding the precursor in the step (1) into powder, then transferring the powder into a muffle furnace to be heated for roasting treatment, wherein the roasting treatment temperature is 200 ℃, and the roasting treatment time is 2h, so as to obtain the CuO nanosheet.
Example 6
A preparation method of CuO nano sheet from top to bottom comprises the following steps:
(1) Cutting 0.25 g foam copper into small blocks, soaking in an acetone solution for 30 min for surface degreasing treatment, wherein the frequency of ultrasonic is 20kHZ, taking out, transferring into a nitric acid solution (the concentration of nitric acid is 0.5 mol/L), soaking and washing for 3 times, taking out, washing with deionized water, adding into a mixed solution of ammonium persulfate and sodium hydroxide with the volume of 50 mL, wherein the concentration of ammonium persulfate is 0.134 mol/L and the concentration of sodium hydroxide is 2.66mol/L in the mixed solution of ammonium persulfate and sodium hydroxide, carrying out ultrasonic treatment, wherein the ultrasonic frequency of ultrasonic treatment is 20kHZ and the ultrasonic treatment time is 1h, filtering to obtain a filtrate, wherein the pore size of a filter screen used for filtering is 10 meshes, centrifuging for 3min at the rotating speed of 7000rpm, taking a precipitate, then respectively washing the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying to obtain a precursor, wherein the drying temperature is 80 ℃, and the drying time is 6h;
(2) Grinding the precursor in the step (1) into powder, then transferring the powder into a muffle furnace to be heated for roasting treatment, wherein the roasting treatment temperature is 200 ℃, and the roasting treatment time is 2h, so as to obtain the CuO nanosheet.
Example 7
A preparation method of a CuO nano sheet from top to bottom comprises the following steps:
(1) 0.25 g copper powder is placed in 30 mL deionized water to be washed, taken out and dried, then added into a mixed solution of ammonium persulfate and sodium hydroxide with the volume of 50 mL, the concentration of the ammonium persulfate is 0.134 mol/L and the concentration of the sodium hydroxide is 2.66mol/L in the mixed solution of the ammonium persulfate and the sodium hydroxide, ultrasonic treatment is carried out, the ultrasonic frequency of the ultrasonic treatment is 20kHZ, the ultrasonic treatment time is 1h, the centrifugal treatment is carried out for 3min under the condition that the rotating speed is 7000rpm, precipitates are taken out, then the precipitates are respectively washed for 3 times by deionized water and absolute ethyl alcohol, a precursor is obtained by drying, the drying temperature is 80 ℃, and the drying time is 6h;
(2) Grinding the precursor in the step (1) into powder, then transferring the powder into a muffle furnace to be heated for roasting treatment, wherein the roasting treatment temperature is 200 ℃, and the roasting treatment time is 2h, so as to obtain the CuO nanosheet.
Example 8
In order to investigate the electrocatalytic properties of the CuO nanoplates prepared, the CuO nanoplates prepared in the examples were subjected to an electrocatalytic carbon dioxide reduction experiment. Example 8 the CuO nanoplate prepared in example 2 was selected for an electrocatalytic carbon dioxide reduction experiment. Before an electrocatalytic carbon dioxide reduction experiment is performed, the CuO nanosheet prepared in example 2 needs to be subjected to a pre-reduction treatment.
The pre-reduction treatment comprises the following steps:
(1) Preparing a working electrode: mixing 20mg of CuO nanosheet prepared in example 2, 1.85mL of absolute ethyl alcohol and 5wt% of nafion solution, uniformly dispersing by ultrasonic for 1h to obtain a dispersion liquid, uniformly dispersing 10 mu L of the dispersion liquid on a glassy carbon electrode with the diameter of 10 mm, and naturally airing to obtain a working electrode; on the working electrode, the loading amount of the CuO nano sheet prepared in example 2 is 0.52 mg/cm 2 ；
(2) Adopting a transparent sealed three-electrode H-shaped cell system as a reaction device, wherein an electrolyte solution is a potassium bicarbonate solution, the concentration of the potassium bicarbonate solution is 0.5mol/L, a working electrode is the working electrode prepared in the step (1), a counter electrode is a platinum sheet electrode, and a reference electrode is a saturated calomel electrode;
(3) And (3) using the three-electrode H-type battery system in the step (2) as a reaction device to be communicated with a power supply, keeping the voltage of the working electrode at minus 0.23V (Vs RHE) until the current is stable, and reducing the CuO nanosheet on the surface of the glassy carbon electrode from brown to dark red when the current is stable, thereby completing the pre-reduction treatment and obtaining the pre-reduced CuO nanosheet. And marking the CuO nanosheets subjected to the pre-reduction treatment as CuONSs.
The CuONSs were observed under a scanning electron microscope and a transmission electron microscope, and the results are shown in FIG. 4 and FIG. 5, respectively. As can be seen from FIGS. 4 and 5, after pre-reduction, the overall morphology of the CuONSs catalyst remains uniform, and a large number of mesopores of 20 nm appear on the surface. After the CuO nano-sheet prepared by other embodiments is subjected to pre-reduction treatment, the overall appearance of the CuO nano-sheet is kept uniform, and a large number of mesopores are generated on the surface.
Example 9
The CuONSs prepared in example 8 above were used to perform an electrocatalytic reduction experiment on carbon dioxide under the following reaction conditions: the concentration of the potassium bicarbonate solution is 0.5mol/L (electrolyte solution), carbon dioxide gas is continuously introduced into the solution at the speed of 20 mL/min to saturate the solution before the test, then the Faraday efficiency and the current density test are carried out at normal temperature and normal pressure, and the Faraday efficiency of the CuONSs under different potentials is measured by adopting a timing current curve technology. The remaining reaction conditions were the same as the pre-reduction conditions described above. The test results are as follows.
FIG. 6 is a graph of Faraday efficiencies of the CuONSs described in example 9 when electrochemically reducing carbon dioxide in potassium bicarbonate solution to yield different products. As can be seen from FIG. 6, the prepared CuONSs catalyst has the Faraday efficiency of 41% of ethylene at minus 0.97 volt, the Faraday efficiency of carbon dioxide reduction exceeds 60%, the Faraday efficiency of hydrogen evolution reaction is lower than 20%, and the hydrogen evolution selectivity of side reaction is effectively inhibited.
FIG. 7 is a graph of the electrochemical reduction of CuONSs in potassium bicarbonate solution to C for the CuONSs in example 9 2 H 4 Stability test chart. As can be seen from FIG. 7, the prepared CuONSs can maintain the activity and stability for more than 5 hours at minus 0.97 volts.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.

Claims (4)

1. An application of CuO nanosheets in electrocatalytic carbon dioxide reduction is characterized in that the preparation method of CuO nanosheets mainly comprises the following steps:
(1) Removing oil, pickling and washing a copper raw material, adding the copper raw material into a mixed solution of ammonium persulfate and sodium hydroxide, carrying out ultrasonic treatment, filtering to obtain a filtrate, centrifuging the filtrate to obtain a precipitate, washing and drying to obtain a precursor; the ultrasonic treatment time is 0.1-5h; the mass volume ratio of the copper raw material to the mixed solution of ammonium persulfate and sodium hydroxide is (0.01-2): 1g/mL; the mixed solution of ammonium persulfate and sodium hydroxide is a solution formed by uniformly mixing a sodium persulfate solution and a sodium hydroxide solution; in the mixed solution of ammonium persulfate and sodium hydroxide, the concentration of the ammonium persulfate is 0.1-0.15 mol/L, and the concentration of the sodium hydroxide is 2.5-3.0 mol/L; the ultrasonic frequency of the ultrasonic treatment is 20-40 kHZ; the ultrasonic treatment time is 0.1h-5h; the drying temperature is 60-80 ℃, and the drying time is 1-8 h; the aperture size of the screen or the filter screen used for filtering is 10 meshes;
(2) Grinding the precursor in the step (1) into powder, and then heating for roasting treatment to obtain the CuO nanosheet; the temperature of the roasting treatment is 200-300 ℃, and the time of the roasting treatment is 2-4h.
2. The application of the CuO nanosheet in electrocatalytic carbon dioxide reduction according to claim 1, wherein the copper raw material in step (1) is one or more of copper foil, copper tube, copper powder and copper foam.
3. Use of CuO nanoplates in electrocatalytic carbon dioxide reduction according to claim 1, wherein the degreasing of step (1) comprises: soaking the copper raw material in an acetone solution for ultrasonic treatment, wherein the ultrasonic treatment time is 0.1-5h, and the ultrasonic frequency of the ultrasonic treatment is 20-40 kHZ.
4. The application of CuO nano sheet in electrocatalytic carbon dioxide reduction according to claim 1, wherein in the step (1), the acid washing treatment is performed by using a nitric acid solution, and the concentration of the nitric acid solution is 0.1mol/L-1mol/L.
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