CN110970630A - CuO nanosheet and top-down preparation method and application thereof - Google Patents
CuO nanosheet and top-down preparation method and application thereof Download PDFInfo
- Publication number
- CN110970630A CN110970630A CN201911155860.1A CN201911155860A CN110970630A CN 110970630 A CN110970630 A CN 110970630A CN 201911155860 A CN201911155860 A CN 201911155860A CN 110970630 A CN110970630 A CN 110970630A
- Authority
- CN
- China
- Prior art keywords
- cuo
- copper
- sodium hydroxide
- treatment
- ammonium persulfate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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. Adding the CuO toThe rice flakes are used as a catalyst for electrocatalytic reduction of carbon dioxide, and are reduced under-0.97 volt to obtain C by taking a reversible hydrogen electrode as a standard2+The faradaic efficiency of the product is over 60%, showing high C of CuO electrocatalyst in carbon dioxide reduction2+And (4) product selectivity.
Description
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 extensive attention in recent years (Seh, z.w. et al.
Around 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 CO2RR selectively converts carbon dioxide to high energy density C such as ethylene, ethanol and the like2+The conversion of the product is relatively low; on the other hand, the traditional preparation method of the copper-based nano-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 forHeterogeneous Electrocatalytic CO2Reduction and their Related reactions 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 to perform 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 1 h.
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-1 mol/L.
Preferably, in the acid washing treatment in the step (1), the concentration of the nitric acid solution is 0.5 mol/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 1:20-1: 10.
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-1.5 g/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-2 h; the drying temperature is 60-80 ℃, and the drying time is 4-8 h.
Preferably, the ultrasonic frequency of the ultrasonic treatment in the step (1) is 20 kHZ.
Preferably, the time of the ultrasonic treatment in the step (1) is 1 h.
Further, the aperture size of the 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 2-4 h.
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 higher 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 minus 0.97 volt2+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 reduction2+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 nanosheets 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 solution2H4Stability test chart of (1).
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 described in detail, are all realizable or understandable 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) cutting 0.25 g of copper foil into small pieces, soaking the small pieces in an acetone solution for ultrasonic treatment for 30 min to remove oil on the surface, taking out the copper foil, soaking and washing the copper foil in a nitric acid solution (the concentration of the nitric acid solution is 0.5 mol/L) for 3 times, taking out, washing the copper foil with deionized water, adding the copper foil 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 of the ultrasonic treatment is 20kHZ, the ultrasonic treatment time is 1h, filtering to obtain a filtrate, centrifuging the copper foil at the rotating speed of 7000rpm for 3min to obtain precipitates, then respectively washing the precipitates with the 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 6 hours;
(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, and are formed by assembling nanoplates from countless nanobelts and then self-assembling them into flower-like particles, and the entire 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 of copper foil into small pieces, soaking the small pieces in an acetone solution for ultrasonic treatment for 30 min to remove oil on the surface, taking out the copper foil, soaking and washing the copper foil in a nitric acid solution (the concentration of the nitric acid solution is 0.5 mol/L) for 3 times, taking out, washing the copper foil with deionized water, adding the copper foil into a mixed solution of ammonium persulfate and sodium hydroxide with the volume of 50 mL, filtering the mixed solution of the ammonium persulfate and the sodium hydroxide, taking out filtrate, filtering the filtrate, centrifuging the filtrate for 3min at the rotating speed of 7000rpm, taking out precipitates, washing the precipitates with deionized water and absolute ethyl alcohol for 3 times respectively, drying to obtain a precursor, wherein the drying temperature is 60 ℃, and the drying time is 4 h;
(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 CuO nano sheet from top to bottom comprises the following steps:
(1) cutting 0.25 g of copper foil into small pieces, soaking in an acetone solution for ultrasonic treatment for 30 min to remove oil on the surface, taking out the copper foil, soaking and washing the copper foil in a nitric acid solution (the concentration of the nitric acid is 0.75 mol/L) for 3 times, taking out, washing the copper foil with deionized water, adding the copper foil into a mixed solution of ammonium persulfate and sodium hydroxide with the volume of 50 mL, wherein the concentration of the ammonium persulfate is 0.125 mol/L and the concentration of the sodium hydroxide is 2.75mol/L, performing ultrasonic treatment, the ultrasonic frequency of the ultrasonic treatment is 30 kHZ, the time of the ultrasonic treatment is 1h, filtering to obtain a filtrate, the aperture 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 with the deionized water and absolute ethyl alcohol for 3 times, and drying to obtain a precursor, the drying temperature is 70 ℃, and the drying time is 4 hours;
(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 of copper foil into small pieces, soaking the small pieces in an acetone solution for 30 min by ultrasonic treatment for surface degreasing treatment, wherein the ultrasonic frequency is 40kHZ, taking out, transferring the small pieces into a nitric acid solution (the nitric acid concentration is 1 mol/L), soaking and washing for 3 times, taking out, washing with deionized water, adding the obtained product into a mixed solution of ammonium persulfate and sodium hydroxide with the volume of 50 mL, wherein in the mixed solution of the ammonium persulfate and the sodium hydroxide, the ammonium persulfate concentration is 0.15mol/L, the sodium hydroxide concentration is 3mol/L, carrying out ultrasonic treatment, the ultrasonic frequency of the ultrasonic treatment is 40kHZ, the ultrasonic treatment time is 2h, filtering to obtain a filtrate, the aperture size of a filter screen used for filtering is 10 meshes, centrifuging for 3min at the rotating speed of 7000rpm, taking precipitates, then washing the precipitates with deionized water and absolute ethyl alcohol for 3 times respectively, drying to obtain a precursor, wherein the drying temperature is 80 ℃, and the drying time is 4 hours;
(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 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) cutting 0.25 g of copper pipe into small pieces, soaking in an acetone solution for ultrasonic treatment for 30 min to remove oil on the surface, taking out the copper pipe, soaking and washing the copper pipe in a nitric acid solution (the concentration of the nitric acid is 0.5 mol/L) for 3 times, taking out, washing the copper pipe with deionized water, adding the copper pipe 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 of the ultrasonic treatment is 20kHZ, the time of the ultrasonic treatment is 1h, filtering to obtain filtrate, the aperture size of a filter screen used for filtering is 10 meshes, centrifuging for 3min at the rotating speed of 7000rpm, taking precipitates, then respectively washing the precipitates with the 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 6 hours;
(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 of foam copper into small pieces, soaking the small pieces in an acetone solution for ultrasonic treatment for 30 min to remove oil on the surface, taking out the small pieces, soaking and washing the small pieces in a nitric acid solution (the concentration of the nitric acid is 0.5 mol/L) for 3 times, taking out, washing the small pieces with deionized water, adding the small pieces into a mixed solution of ammonium persulfate and sodium hydroxide with the volume of 50 mL, filtering the mixed solution of the ammonium persulfate and the sodium hydroxide with the concentration of 0.134 mol/L and the concentration of the sodium hydroxide of 2.66mol/L to obtain filtrate, performing ultrasonic treatment with the ultrasonic frequency of 20kHZ and the ultrasonic treatment time of 1h, filtering the filtrate, centrifuging the filtrate for 3min at the rotating speed of 7000rpm to obtain precipitates, then respectively washing the precipitates with the 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 6 hours;
(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 CuO nano sheet from top to bottom comprises the following steps:
(1) washing 0.25 g of copper powder in 30 mL of deionized water, taking out and drying, then adding the copper powder into a mixed solution of ammonium persulfate and sodium hydroxide with the volume of 50 mL, wherein in the mixed solution of the ammonium persulfate and the sodium hydroxide, the concentration of the ammonium persulfate is 0.134 mol/L, the concentration of the sodium hydroxide is 2.66mol/L, carrying out ultrasonic treatment, the ultrasonic frequency of the ultrasonic treatment is 20kHZ, the time of the ultrasonic treatment is 1h, centrifuging for 3min under the condition that the rotating speed is 7000rpm, taking a precipitate, then washing the precipitate for 3 times respectively by using the deionized water and absolute ethyl alcohol, and drying to obtain a precursor, wherein the drying temperature is 80 ℃ and the drying time is 6 h;
(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 performance of the prepared CuO nanosheets, the CuO nanosheets 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; the supported amount of the CuO nanosheet prepared in example 2 on the working electrode was 0.52 mg/cm2；
(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 when the current is stable, reducing the CuO nanosheet on the surface of the glassy carbon electrode from brown to dark red to finish the pre-reduction treatment to obtain the CuO nanosheet after the pre-reduction treatment. 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 fig. 4 and 5, after pre-reduction, the overall morphology of the CuONSs catalyst remains uniform, and a large number of 20 nm mesopores 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 testing, then the Faraday efficiency and current density tests 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 carbon dioxide as C in example 92H4Stability 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 (10)
1. A preparation method of CuO nano sheet from top to bottom is characterized by mainly comprising 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;
(2) and (2) grinding the precursor in the step (1) into powder, and then heating to perform roasting treatment to obtain the CuO nanosheet.
2. The top-down preparation method of CuO nanosheets as claimed in 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. A top-down preparation method of CuO nanoplate according to claim 1, wherein the oil removal treatment 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. A top-down preparation method of CuO nanosheets according to claim 1, wherein in step (1), the acid washing treatment is performed using a nitric acid solution having a concentration of 0.1mol/L to 1 mol/L.
5. The CuO nanosheet top-down preparation method according to claim 1, wherein the mixed solution of ammonium persulfate and sodium hydroxide in 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 ammonium persulfate is 0.1-5 mol/L, and the concentration of sodium hydroxide is 1-15 mol/L.
6. The CuO nanosheet top-down preparation method according to claim 1, wherein the mass-to-volume ratio of the copper raw material to the mixed solution of ammonium persulfate and sodium hydroxide in step (1) is 0.01-2: 1 g/mL.
7. A top-down preparation method of CuO nanoplate according to claim 1, wherein the ultrasonic frequency of the ultrasonic treatment of step (1) is 20kHZ to 40 kHZ; the ultrasonic treatment time is 0.1-5 h; 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.
8. The top-down preparation method of CuO nanosheets as recited in claim 1, wherein the baking treatment in step (2) is carried out at a temperature of 100 ℃ to 500 ℃ for a period of 2 to 4 hours.
9. CuO nanoplatelets prepared by a top-down preparation method according to any of claims 1 to 8.
10. Use of the CuO nanoplatelets of claim 9 as an electrocatalyst for electrochemical reduction reactions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911155860.1A CN110970630B (en) | 2019-11-22 | 2019-11-22 | CuO nanosheet and top-down preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911155860.1A CN110970630B (en) | 2019-11-22 | 2019-11-22 | CuO nanosheet and top-down preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110970630A true CN110970630A (en) | 2020-04-07 |
| CN110970630B CN110970630B (en) | 2022-10-04 |
Family
ID=70031355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911155860.1A Active CN110970630B (en) | 2019-11-22 | 2019-11-22 | CuO nanosheet and top-down preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110970630B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112897567A (en) * | 2021-03-31 | 2021-06-04 | 江南大学 | Preparation method of copper oxide with nanometer flower-like structure |
| CN113735157A (en) * | 2021-09-18 | 2021-12-03 | 武汉大学 | Preparation method of petal-shaped copper oxide nanosheet and application of petal-shaped copper oxide nanosheet |
| CN114438519A (en) * | 2022-01-28 | 2022-05-06 | 西安理工大学 | Construction of polycrystalline interface CuO for electrocatalysis of CO2Reduction preparation method |
| CN114672847A (en) * | 2022-05-09 | 2022-06-28 | 中国科学技术大学 | Controllable preparation of high-performance electrocatalyst and application of high-performance electrocatalyst in preparation of urea by electrocatalysis coupling of carbon dioxide and nitrate radical |
| CN114763268A (en) * | 2021-01-13 | 2022-07-19 | 中国科学院上海高等研究院 | Flaky nano copper oxide and preparation method and application thereof |
| CN115490258A (en) * | 2021-06-18 | 2022-12-20 | 中国科学院大连化学物理研究所 | Copper oxide nanosheet catalyst, preparation method and application in electrocatalytic reduction of carbon dioxide and carbon monoxide |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792172A (en) * | 2010-03-03 | 2010-08-04 | 天津理工大学 | Method for preparing copper hydroxide and copper oxide nano material and application |
| US20150068917A1 (en) * | 2012-02-28 | 2015-03-12 | Fritz Haber Institut Der Max Planck Gesellschaft | Electrolytic water splitting using a carbon-supported mnox-composite |
| CN105819488A (en) * | 2016-03-28 | 2016-08-03 | 安阳师范学院 | Method for preparing nitrogen-doped graphene loaded Cu2O-CuO nanoneedle composite material |
| US20160236939A1 (en) * | 2013-09-24 | 2016-08-18 | Irene DE MIGUEL TURULLOIS | Exfoliation of graphite with deep eutectic solvents |
| US20160348256A1 (en) * | 2014-01-17 | 2016-12-01 | The Board Of Regents Of The University Of Texas System | Photoelectrochemical devices, methods, and systems with a cupric oxide/cuprous oxide coated electrode |
| US20170320039A1 (en) * | 2016-05-03 | 2017-11-09 | Massachusetts Institute Of Technology | Synthesis of Nanoparticles by Sonofragmentation of Ultra-Thin Substrates |
| CN108560018A (en) * | 2018-05-07 | 2018-09-21 | 北京化工大学 | A kind of Nanometer Copper electrode material, preparation method and the usage |
| CN109516507A (en) * | 2017-09-18 | 2019-03-26 | 浙江工业大学 | A kind of preparation method of porous cobaltosic oxide nano piece |
-
2019
- 2019-11-22 CN CN201911155860.1A patent/CN110970630B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792172A (en) * | 2010-03-03 | 2010-08-04 | 天津理工大学 | Method for preparing copper hydroxide and copper oxide nano material and application |
| US20150068917A1 (en) * | 2012-02-28 | 2015-03-12 | Fritz Haber Institut Der Max Planck Gesellschaft | Electrolytic water splitting using a carbon-supported mnox-composite |
| US20160236939A1 (en) * | 2013-09-24 | 2016-08-18 | Irene DE MIGUEL TURULLOIS | Exfoliation of graphite with deep eutectic solvents |
| US20160348256A1 (en) * | 2014-01-17 | 2016-12-01 | The Board Of Regents Of The University Of Texas System | Photoelectrochemical devices, methods, and systems with a cupric oxide/cuprous oxide coated electrode |
| CN105819488A (en) * | 2016-03-28 | 2016-08-03 | 安阳师范学院 | Method for preparing nitrogen-doped graphene loaded Cu2O-CuO nanoneedle composite material |
| US20170320039A1 (en) * | 2016-05-03 | 2017-11-09 | Massachusetts Institute Of Technology | Synthesis of Nanoparticles by Sonofragmentation of Ultra-Thin Substrates |
| CN109516507A (en) * | 2017-09-18 | 2019-03-26 | 浙江工业大学 | A kind of preparation method of porous cobaltosic oxide nano piece |
| CN108560018A (en) * | 2018-05-07 | 2018-09-21 | 北京化工大学 | A kind of Nanometer Copper electrode material, preparation method and the usage |
Non-Patent Citations (1)
| Title |
|---|
| MING MA 等: "Selective electrochemical reduction of CO2 to CO on CuO-derived Cu nanowires", 《PHYS.CHEM.CHEM.PHYS.》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114763268A (en) * | 2021-01-13 | 2022-07-19 | 中国科学院上海高等研究院 | Flaky nano copper oxide and preparation method and application thereof |
| CN114763268B (en) * | 2021-01-13 | 2023-11-17 | 中国科学院上海高等研究院 | Flake nano copper oxide and preparation method and application thereof |
| CN112897567A (en) * | 2021-03-31 | 2021-06-04 | 江南大学 | Preparation method of copper oxide with nanometer flower-like structure |
| CN115490258A (en) * | 2021-06-18 | 2022-12-20 | 中国科学院大连化学物理研究所 | Copper oxide nanosheet catalyst, preparation method and application in electrocatalytic reduction of carbon dioxide and carbon monoxide |
| CN115490258B (en) * | 2021-06-18 | 2024-02-23 | 中国科学院大连化学物理研究所 | Copper oxide nano-sheet catalyst, preparation method and application thereof in electrocatalytic reduction of carbon dioxide and carbon monoxide |
| CN113735157A (en) * | 2021-09-18 | 2021-12-03 | 武汉大学 | Preparation method of petal-shaped copper oxide nanosheet and application of petal-shaped copper oxide nanosheet |
| CN113735157B (en) * | 2021-09-18 | 2022-06-03 | 武汉大学 | Preparation method of petal-shaped copper oxide nanosheet and application of petal-shaped copper oxide nanosheet |
| CN114438519A (en) * | 2022-01-28 | 2022-05-06 | 西安理工大学 | Construction of polycrystalline interface CuO for electrocatalysis of CO2Reduction preparation method |
| CN114672847A (en) * | 2022-05-09 | 2022-06-28 | 中国科学技术大学 | Controllable preparation of high-performance electrocatalyst and application of high-performance electrocatalyst in preparation of urea by electrocatalysis coupling of carbon dioxide and nitrate radical |
| CN114672847B (en) * | 2022-05-09 | 2024-03-29 | 中国科学技术大学 | Controllable preparation of high-performance electrocatalyst and application of controllable preparation in preparation of urea by electrocatalytic coupling of carbon dioxide and nitrate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110970630B (en) | 2022-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110970630B (en) | CuO nanosheet and top-down preparation method and application thereof | |
| CN106784865B (en) | A kind of nitrogen co-doped carbosphere of iron and preparation method, purposes and oxygen reduction electrode | |
| CN109989070B (en) | Three-dimensional grading FeP nanosheet hydrogen evolution electro-catalytic material and preparation method and application thereof | |
| CN107299362B (en) | A kind of preparation method and its electrochemical applications of activated carbon supported cobalt-nickel alloy material | |
| CN110745784B (en) | Metal oxide nano-particles and preparation method and application thereof | |
| CN108097269B (en) | A kind of ultra-thin porous Ce-Ni-O-S nanometer sheets and its preparation method and application | |
| CN112853396A (en) | Two-dimensional ultrathin metal organic framework nanosheet electrocatalyst, and preparation method and application thereof | |
| CN102873337A (en) | Poly-allylamine oriented platinum nano cube preparation method | |
| CN111250076A (en) | Nano bismuth catalyst and preparation method and application thereof | |
| CN110965076A (en) | Preparation method of electrolytic water electrode with double-function three-dimensional layered core-shell structure | |
| CN111841598B (en) | S-doped Co @ NC composite material with high oxygen evolution catalytic activity and preparation method thereof | |
| CN111048324A (en) | Manganese dioxide-porous carbon composite material and preparation method and application thereof | |
| CN112376077A (en) | Ternary metal catalyst, preparation method thereof and application of ternary metal catalyst in preparation of deuterium gas by electrolyzing heavy water | |
| CN109621989B (en) | Fluorine-doped catalyst for electrochemically synthesizing ammonia, preparation method and cathode material | |
| CN108043437A (en) | A kind of preparation method of hollow SiC carrier models Ir-Ru catalyst | |
| CN103464211B (en) | A kind of MnOxthe preparation method of/C-PTFE catalyst mastic | |
| CN112670526B (en) | Preparation method and application of amorphous manganese dioxide modified shrimp shell carbon base frame | |
| CN113699549A (en) | Ruthenium and tin bimetallic oxide electrocatalytic material and preparation method and application thereof | |
| CN108823602A (en) | A kind of vulcanization ruthenium particulate composite, preparation method and the usage | |
| CN114614027B (en) | Preparation method of CoFe-S@3D-S-NCNT electrode and quasi-solid zinc-air battery | |
| CN110120527B (en) | Controllable synthesized lanthanum-doped cobalt oxide nanosheet and preparation method and application thereof | |
| CN105854864B (en) | Electrochemically reducing carbon dioxide is formic acid or the catalyst and preparation method thereof of its salt | |
| CN110272115B (en) | Cu-Ce-Y spherical cavity composite material and preparation method and application thereof | |
| CN110668406B (en) | Preparation method and application of nickel selenide nanosheet | |
| CN114635153B (en) | Defect-rich copper-based nano catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230801 Address after: Room 2204, 22nd Floor, Building 1, Meixi Commercial Plaza, No. 168 Youyou Road, Xiangzhou District, Zhuhai City, Guangdong Province, 519075 Patentee after: Guangdong Zhida yinowei Technology Co.,Ltd. Address before: 510640 No. five, 381 mountain road, Guangzhou, Guangdong, Tianhe District Patentee before: SOUTH CHINA University OF TECHNOLOGY |
|
| TR01 | Transfer of patent right |