La-doped cuprous oxide electrocatalyst loaded on graphene oxide and preparation method thereof

Abstract

The invention discloses a La-doped cuprous oxide electrocatalyst loaded on graphene oxide and a preparation method of the La-doped cuprous oxide electrocatalyst. The preparation method comprises the following steps: 1) preparing a single-layer graphene oxide dispersion liquid; and 2) the La-doped cuprous oxide electrocatalyst loaded on graphene oxide is prepared by using the single-layer graphene oxide dispersion liquid, and the stability of the catalyst prepared by the method is relatively high.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrocatalytic CO2 reduction and relates to a La-doped cuprous oxide electrocatalyst supported on graphene oxide and a preparation method thereof. Background Art

[0002] As global climate change intensifies, electrocatalytic CO2 reduction technology has attracted significant attention due to its ability to utilize renewable energy to convert CO2 into high-value-added chemicals and fuels. This technology not only helps reduce greenhouse gas emissions but also enables the recycling of carbon resources. However, challenges such as the high chemical inertness of CO2 molecules, complex reaction pathways, and insufficient catalyst performance continue to hinder its development. Current research focuses on developing efficient catalysts, revealing reaction mechanisms, optimizing electrolytic cell design, and promoting integration with renewable energy to advance the practical application of this technology and provide solutions to alleviate the energy crisis and achieve sustainable development.

[0003] Currently, Cu-based catalysts have been found to be the most effective catalysts for the generation of C 2+ The most effective catalyst for the product is attributed to the weak adsorption of Cu on *H and the favorable adsorption on *CO. The weak adsorption of Cu on *H indicates that Cu can inhibit the hydrogen evolution reaction (HER) in the electrochemical reaction and improve the FE of carbon-containing products. The excellent *CO adsorption can improve the stability and reactivity of *CO on the electrocatalyst surface, promote the CC coupling reaction, and thus improve the C 2+ However, copper-based electrocatalysts still have certain limitations, such as poor stability and insufficient selectivity for target products. Summary of the Invention

[0004] The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide a La-doped cuprous oxide electrocatalyst supported on graphene oxide and a preparation method thereof. The catalyst prepared by this method has high stability.

[0005] To achieve the above object, the present invention discloses a method for preparing a La-doped cuprous oxide electrocatalyst supported on graphene oxide, comprising the following steps:

[0006] 1) preparing a monolayer graphene oxide dispersion;

[0007] 2) Using the single-layer graphene oxide dispersion, preparing a La-doped cuprous oxide electrocatalyst supported on graphene oxide.

[0008] The further improvement of the preparation method of the La-doped cuprous oxide electrocatalyst supported on graphene oxide of the present invention is:

[0009] Furthermore, the specific operations of step 1) are:

[0010] 11) Immersing the graphite oxide in concentrated sulfuric acid, centrifugally washing, and then washing with ultrapure water until neutral to obtain a washed product;

[0011] 12) The washed product is treated with an ultrasonic cell disruptor, and the upper dispersion is taken to obtain a single-layer graphene oxide dispersion.

[0012] Furthermore, the process of step 12) is as follows:

[0013] The washed product was treated continuously for 6 hours using an ultrasonic cell disruptor in an ice bath at a power of 520 W, and the upper dispersion was taken to obtain a single-layer graphene oxide dispersion.

[0014] Furthermore, the specific operations of step 2) are:

[0015] 21) Ultrasonic dissolution of Cu(NO3)2 and La(NO3)3 in ultrapure water, then dropwise add the graphene oxide dispersion obtained in step 1), and then magnetically stir in an ice bath to obtain a mixture.

[0016] 22) NaOH aqueous solution was added dropwise to the mixture obtained in step 21), and then NaBH4 aqueous solution was added dropwise, and the mixture was stirred with magnetic stirring in an ice bath, and then washed and freeze-dried to obtain a La-doped cuprous oxide electrocatalyst supported on graphene oxide.

[0017] Furthermore, the ratio of Cu(NO3)2, La(NO3)3, graphene oxide dispersion, NaOH aqueous solution and NaBH4 aqueous solution is 0.05-0.2g:0.05-0.2g:1-2mL:0.5-3mL:1-10mL.

[0018] Furthermore, the specific operations of step 22) are:

[0019] To the mixture obtained in step 21), a NaOH aqueous solution was added dropwise, and then a NaBH4 aqueous solution was added dropwise, and the mixture was stirred with magnetic stirring for 4 hours in an ice bath, and then washed with ultrapure water and ethanol, and freeze-dried for 12 hours to obtain a La-doped cuprous oxide electrocatalyst supported on graphene oxide.

[0020] Furthermore, the concentration of the NaOH aqueous solution is 0.9 wt.%.

[0021] Furthermore, the concentration of the NaBH4 aqueous solution is 0.9 wt.%.

[0022] Furthermore, the immersion time in step 11) is 24 hours.

[0023] The invention discloses a La-doped cuprous oxide electrocatalyst supported on graphene oxide, which is prepared based on a preparation method of the La-doped cuprous oxide electrocatalyst supported on graphene oxide.

[0024] The present invention has the following beneficial effects:

[0025] The La-doped cuprous oxide electrocatalyst supported on graphene oxide and its preparation method of the present invention, in specific operation, is obtained by loading La-Cu2O on the surface of graphene oxide to obtain an electrocatalyst with high stability and high specific surface area. Doping with La can effectively modify the electronic structure of Cu2O, thereby accelerating the adsorption of CC coupling intermediates, thereby improving C 2+ The La-Cu2O / GO electrocatalyst synthesized by sodium borohydride reduction has a higher specific surface area and higher C 2+ The selectivity of the product and the electrocatalytic CO2 reduction ability have been greatly improved. The operation is simple and the cost is low. The obtained La-Cu2O / GO electrocatalyst has high stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The accompanying drawings, which constitute part of the present invention, are intended to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are intended to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0027] Figure 1a TEM image of the catalyst obtained in Example 3;

[0028] Figure 1b HRTEM image of the catalyst obtained in Example 3;

[0029] Figure 2 X-ray diffraction patterns of La-Cu2O / GO and Cu2O / GO samples in Example 3;

[0030] Figure 3a This is the La-Cu2O / GO electrocatalytic CO2 reduction activity diagram in Example 3;

[0031] Figure 3b This is the electrocatalytic CO2 reduction activity diagram of the Cu2O / GO sample in Example 3;

[0032] Figure 4a The LSV spectra and Tafel plots of La-Cu2O / GO and Cu2O / GO samples in Example 3 are shown;

[0033] Figure 4b The Tafel curves of La-Cu2O / GO and Cu2O / GO samples in Example 3 are shown;

[0034] Figure 5a In-situ ATR-FTIR analysis of the La-Cu2O / GO sample in Example 3

[0035] Figure 5b This is the in-situ ATR-FTIR analysis diagram of the Cu2O / GO sample in Example 3. DETAILED DESCRIPTION

[0036] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0037] In the description of the present invention, it is to be understood that the terms “include” and “comprise” indicate the presence of the described features, wholes, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, wholes, steps, operations, elements, components and / or collections thereof.

[0038] It should also be understood that the terms used in the present specification are only for the purpose of describing particular embodiments and are not intended to limit the present invention. As used in the present specification and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms unless the context clearly indicates otherwise.

[0039] It should be further understood that the term "and / or" as used in the present specification and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items. For example, A and / or B may represent: A exists alone, A and B exist simultaneously, and B exists alone. In addition, the character " / " in the present invention generally indicates that the associated objects are in an "or" relationship.

[0040] It should be understood that although the terms "first," "second," and "third" may be used to describe preset ranges in embodiments of the present invention, these preset ranges should not be limited to these terms. These terms are merely used to distinguish one preset range from another. For example, without departing from the scope of embodiments of the present invention, the first preset range may also be referred to as the second preset range, and similarly, the second preset range may also be referred to as the first preset range.

[0041] The word "if," as used herein, may be interpreted as "at the time of" or "when" or "in response to determining" or "in response to detecting," depending on the context. Similarly, the phrases "if it is determined" or "if (stated condition or event) is detected" may be interpreted as "when it is determined" or "in response to the determination" or "when detecting (stated condition or event)" or "in response to detecting (stated condition or event)," depending on the context.

[0042] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Generally, the components of the embodiments of the present invention described and shown in the drawings herein can be arranged and designed in various different configurations. Therefore, the following detailed description of the embodiments of the present invention provided in the drawings is not intended to limit the scope of the claimed invention, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0043] The accompanying drawings illustrate various schematic diagrams of structures according to embodiments disclosed herein. These figures are not drawn to scale; for clarity, some details are exaggerated and some details may be omitted. The shapes of the various regions and layers shown in the figures, as well as their relative sizes and positional relationships, are merely exemplary and may deviate in practice due to manufacturing tolerances or technical limitations. Those skilled in the art may design regions / layers with different shapes, sizes, and relative positions as needed.

[0044] The preparation method of the La-doped cuprous oxide electrocatalyst supported on graphene oxide of the present invention comprises the following steps:

[0045] 1) preparing a monolayer graphene oxide dispersion;

[0046] The specific operations of step 1) are:

[0047] 11) Immerse 5-10 g of graphite oxide in concentrated sulfuric acid for 24 hours, centrifuge and wash with ultrapure water until neutral to obtain a washed product;

[0048] 12) The washed product was treated with an ultrasonic cell disruptor in an ice bath at 520 W for 6 hours, and the upper dispersion was collected to obtain a single-layer graphene oxide dispersion.

[0049] 2) Preparation of La-doped cuprous oxide electrocatalyst supported on graphene oxide (La-Cu2O / GO catalyst);

[0050] The specific operations of step 2) are:

[0051] 21) Ultrasonic dissolution of 0.05-0.2 g of Cu(NO3)2 and 0.05-0.2 g of La(NO3)3 in ultrapure water was performed, and then 1-2 mL of the graphene oxide dispersion obtained in step 1) was added dropwise, followed by magnetic stirring in an ice bath for 1 h to obtain a mixture.

[0052] 22) To the mixture obtained in step 21), 0.5-3 mL of a 0.9 wt.% aqueous NaOH solution was added dropwise, followed by the dropwise addition of 1-10 mL of a 0.9 wt.% aqueous NaBH4 solution. The mixture was stirred under magnetic stirring for 4 h in an ice bath, then washed with ultrapure water and ethanol, and freeze-dried for 12 h to obtain a La-doped cuprous oxide electrocatalyst supported on graphene oxide (La-Cu2O / GO catalyst).

[0053] Example 1

[0054] The preparation method of the La-doped cuprous oxide electrocatalyst supported on graphene oxide of the present invention comprises the following steps:

[0055] 1) preparing a monolayer graphene oxide dispersion;

[0056] The specific process of step 1) is:

[0057] 11) 8 g of graphite oxide was immersed in concentrated sulfuric acid for 24 h, centrifuged and washed with ultrapure water until neutral.

[0058] 12) Using an ultrasonic cell disruptor in an ice bath at 520 W power for 7 hours, the upper dispersion was collected to obtain a single-layer graphene oxide dispersion.

[0059] 2) Prepared La-Cu2O / GO catalyst;

[0060] 21) Ultrasonic dissolution of 0.15 g of Cu(NO3)2 and 0.15 g of La(NO3)3 in ultrapure water was performed, and 1 mL of graphene oxide dispersion was added dropwise to the resulting aqueous solution, and magnetic stirring was performed under ice bath for 1 h to obtain a mixture;

[0061] 22) To the mixture was added dropwise 1.5 mL of a 0.9 wt.% aqueous NaOH solution, followed by dropwise addition of 4 mL of a 0.9 wt.% NaBH4 solution. The mixture was stirred under magnetic stirring in an ice bath for 4 h, washed multiple times with ultrapure water and ethanol, and freeze-dried for 12 h to obtain a La-Cu2O / GO catalyst.

[0062] Example 2

[0063] The preparation method of the La-doped cuprous oxide electrocatalyst supported on graphene oxide of the present invention comprises the following steps:

[0064] 1) preparing a monolayer graphene oxide dispersion;

[0065] 11) Immerse 7 g of graphite oxide in concentrated sulfuric acid for 24 h, centrifuge and wash with ultrapure water until neutral.

[0066] 12) Using an ultrasonic cell disruptor in an ice bath at 520 W for 6 hours, the upper dispersion was collected to obtain a single-layer graphene oxide dispersion.

[0067] 2) Preparation of La-Cu2O / GO catalyst;

[0068] 21) 0.1 g of Cu(NO3)2 and 0.5 g of La(NO3)3 were ultrasonically dissolved in ultrapure water, and 1.5 mL of graphene oxide dispersion was dropped into the resulting aqueous solution and magnetically stirred in an ice bath for 1 h.

[0069] 22) To the mixture was added dropwise 1 mL of a 0.9 wt.% aqueous NaOH solution, followed by dropwise addition of 3 mL of a 0.9 wt.% aqueous NaBH4 solution. The mixture was stirred under magnetic stirring in an ice bath for 4 h, washed multiple times with ultrapure water and ethanol, and freeze-dried for 12 h to obtain a La-Cu2O / GO catalyst.

[0070] Example 3

[0071] The preparation method of the La-doped cuprous oxide electrocatalyst supported on graphene oxide of the present invention comprises the following steps:

[0072] 1) preparing a monolayer graphene oxide dispersion;

[0073] 11) Immerse 10 g of graphite oxide in concentrated sulfuric acid for 24 h, centrifuge and wash with ultrapure water until neutral.

[0074] 12) Using an ultrasonic cell disruptor in an ice bath at 520 W power for more than 10 hours, taking the upper dispersion to obtain a single-layer graphene oxide dispersion.

[0075] 2) Preparation of La-Cu2O / GO catalyst;

[0076] 21) 0.1 g Cu(NO3)2 and 0.17 g La(NO3)3 were ultrasonically dissolved in ultrapure water, and 2 mL of graphene oxide dispersion was dropped into the resulting aqueous solution and magnetically stirred in an ice bath for 1 h.

[0077] 22) To the mixture was added dropwise 1 mL of a 0.9 wt.% aqueous NaOH solution, followed by dropwise addition of 4 mL of a 0.9 wt.% aqueous NaBH4 solution. The mixture was stirred under magnetic stirring in an ice bath for 4 h, washed multiple times with ultrapure water and ethanol, and freeze-dried for 12 h to obtain a La-Cu2O / GO catalyst.

[0078] Example 4

[0079] The preparation method of the La-doped cuprous oxide electrocatalyst supported on graphene oxide of the present invention comprises the following steps:

[0080] 1) preparing a monolayer graphene oxide dispersion;

[0081] 11) 8 g of graphite oxide was immersed in concentrated sulfuric acid for 24 h, centrifuged and washed with ultrapure water until neutral.

[0082] 12) Using an ultrasonic cell disruptor in an ice bath at 520 W power for more than 7 hours, the upper dispersion was collected to obtain a single-layer graphene oxide dispersion.

[0083] 2) Preparation of La-Cu2O / GO catalyst;

[0084] 21) 0.2 g of Cu(NO3)2 and 0.25 g of La(NO3)3 were ultrasonically dissolved in ultrapure water, and 3 mL of graphene oxide dispersion was dropped into the resulting aqueous solution and magnetically stirred in an ice bath for 1 h.

[0085] 22) To the mixture was added dropwise 2 mL of a 0.9 wt.% aqueous NaOH solution, followed by dropwise addition of 6 mL of a 0.9 wt.% aqueous NaBH4 solution. The mixture was stirred under magnetic stirring in an ice bath for 4 h, washed multiple times with ultrapure water and ethanol, and freeze-dried for 12 h to obtain a La-Cu2O / GO catalyst.

[0086] Example 5

[0087] The preparation method of the La-doped cuprous oxide electrocatalyst supported on graphene oxide of the present invention comprises the following steps:

[0088] 1) preparing a monolayer graphene oxide dispersion;

[0089] 11) Immerse 5 g of graphite oxide in concentrated sulfuric acid for 24 h, centrifuge and wash with ultrapure water until neutral.

[0090] 12) Using an ultrasonic cell disruptor in an ice bath at 520 W power for more than 5 hours, taking the upper dispersion to obtain a single-layer graphene oxide dispersion.

[0091] 2) The specific steps of the La-Cu2O / GO catalyst preparation method are as follows:

[0092] 21) 0.05 g of Cu(NO3)2 and 0.05 g of La(NO3)3 were ultrasonically dissolved in ultrapure water, and 1 mL of graphene oxide dispersion was dropped into the resulting aqueous solution and magnetically stirred in an ice bath for 1 h.

[0093] 22) To the mixture was added dropwise 0.5 mL of a 0.9 wt.% aqueous NaOH solution, followed by dropwise addition of 2 mL of a 0.9 wt.% aqueous NaBH4 solution. The mixture was stirred under magnetic stirring in an ice bath for 4 h, washed multiple times with ultrapure water and ethanol, and freeze-dried for 12 h to obtain a La-Cu2O / GO catalyst.

[0094] Example 6

[0095] The preparation method of the La-doped cuprous oxide electrocatalyst supported on graphene oxide of the present invention comprises the following steps:

[0096] 1) preparing a monolayer graphene oxide dispersion;

[0097] 11) Immerse 10 g of graphite oxide in concentrated sulfuric acid for 24 h, centrifuge and wash with ultrapure water until neutral.

[0098] 21) Use an ultrasonic cell disruptor in an ice bath at 520W for more than 10 hours. Take the upper portion of the dispersion and protect it from light and refrigerate it for later use.

[0099] 2) Preparation of La-Cu2O / GO catalyst;

[0100] 21) 0.3 g Cu(NO3)2 and 0.3 g La(NO3)3 were ultrasonically dissolved in ultrapure water, and 4 mL of graphene oxide dispersion was dropped into the obtained aqueous solution and magnetically stirred in an ice bath for 2 h.

[0101] 22) Then, 3 mL of 0.9 wt.% NaOH aqueous solution was added dropwise to the mixture, followed by the dropwise addition of 8 mL of 0.9 wt.% NaBH4 aqueous solution. The mixture was stirred under magnetic stirring in an ice bath for 4 h, washed multiple times with ultrapure water and ethanol, and freeze-dried for 12 h to obtain a La-Cu2O / GO catalyst.

[0102] Example 7

[0103] The preparation method of the La-doped cuprous oxide electrocatalyst supported on graphene oxide of the present invention comprises the following steps:

[0104] 1) preparing a monolayer graphene oxide dispersion;

[0105] The specific operations of step 1) are:

[0106] 11) Immerse 10 g of graphite oxide in concentrated sulfuric acid for 24 h, centrifuge and wash with ultrapure water until neutral to obtain the washed product;

[0107] 12) The washed product was treated with an ultrasonic cell disruptor in an ice bath at 520 W for 6 hours, and the upper dispersion was collected to obtain a single-layer graphene oxide dispersion.

[0108] 2) Preparation of La-doped cuprous oxide electrocatalyst supported on graphene oxide (La-Cu2O / GO catalyst);

[0109] The specific operations of step 2) are:

[0110] 21) Ultrasonic dissolution of 0.2 g of Cu(NO3)2 and 0.2 g of La(NO3)3 in ultrapure water was performed, and then 2 mL of the graphene oxide dispersion obtained in step 1) was added dropwise, followed by magnetic stirring in an ice bath for 1 h to obtain a mixture.

[0111] 22) To the mixture obtained in step 21), 3 mL of a 0.9 wt.% aqueous NaOH solution was added dropwise, followed by the dropwise addition of 10 mL of a 0.9 wt.% aqueous NaBH4 solution. The mixture was stirred under magnetic stirring for 4 h in an ice bath, then washed with ultrapure water and ethanol, and freeze-dried for 12 h to obtain a La-doped cuprous oxide electrocatalyst supported on graphene oxide (La-Cu2O / GO catalyst).

[0112] Example 8

[0113] The preparation method of the La-doped cuprous oxide electrocatalyst supported on graphene oxide of the present invention comprises the following steps:

[0114] 1) preparing a monolayer graphene oxide dispersion;

[0115] The specific operations of step 1) are:

[0116] 11) Immerse 5 g of graphite oxide in concentrated sulfuric acid for 24 h, then centrifuge and wash with ultrapure water until neutral to obtain the washed product;

[0117] 12) The washed product was treated with an ultrasonic cell disruptor in an ice bath at 520 W for 6 hours, and the upper dispersion was collected to obtain a single-layer graphene oxide dispersion.

[0118] 2) Preparation of La-doped cuprous oxide electrocatalyst supported on graphene oxide (La-Cu2O / GO catalyst);

[0119] The specific operations of step 2) are:

[0120] 21) Ultrasonic dissolution of 0.05 g of Cu(NO3)2 and 0.05 g of La(NO3)3 in ultrapure water was performed, and 1 mL of the graphene oxide dispersion obtained in step 1) was added dropwise, followed by magnetic stirring in an ice bath for 1 h to obtain a mixture.

[0121] 22) To the mixture obtained in step 21), 0.5 mL of a 0.9 wt.% aqueous NaOH solution was added dropwise, followed by the dropwise addition of 1 mL of a 0.9 wt.% aqueous NaBH4 solution. The mixture was stirred under magnetic stirring for 4 h in an ice bath, then washed with ultrapure water and ethanol, and freeze-dried for 12 h to obtain a La-doped cuprous oxide electrocatalyst supported on graphene oxide (La-Cu2O / GO catalyst).

[0122] Figure 1a This is the transmission electron microscopy (TEM) characterization result of the La-Cu2O / GO sample in Example 3. La-Cu2O is in cubic form with a size range of 20-100 nm and is uniformly dispersed on graphene oxide. Figure 1b This is a high-resolution transmission electron microscopy (HRTEM) image of the sample in Example 3, which proves the successful construction of the La-Cu2O / GO heterostructure.

[0123] Figure 2 The X-ray diffraction (XRD) patterns of the La-Cu2O / GO and Cu2O / GO samples in Example 3 were analyzed using XRD. The La-Cu2O / GO and Cu2O / GO nanomaterials exhibit the same peaks, which is due to the lower La doping level.

[0124] Figure 3a and Figure 3b The results of the electrocatalytic CO2 reduction activity comparison between La-Cu2O / GO and Cu2O / GO samples in Example 3 are as follows: La-Cu2O / GO has a significant effect on the conversion of CO2 to C 2+ It exhibits excellent performance, with a Faradaic efficiency (FE) of 45.4%, which is 3.68 times that of Cu2O / GO.

[0125] Figure 4a and Figure 4b The LSV spectra and Tafel curves of La-Cu2O / GO and Cu2O / GO samples in Example 3 show that at the same potential, La-Cu2O / GO exhibits a higher current density than the original Cu2O / GO, confirming that the incorporation of La can significantly improve the electrocatalytic activity and increase the number of electrons involved in the reaction. The Tafel slope spectrum shows that the addition of La has a significant effect on the electrocatalytic activity of C 2+ The reaction kinetics of the product were improved.

[0126] Figure 5a and Figure 5b In situ ATR-FTIR analysis of La-Cu2O / GO and Cu2O / GO samples in Example 3 confirmed that La incorporation into Cu2O / GO significantly promoted the dimerization of *CO, thereby further increasing the C 2+ selectivity.

[0127] Those skilled in the art will readily identify other embodiments of the present invention after considering the specification and disclosure of the invention. This application is intended to cover any variations, uses, or adaptations of the present invention that follow the general principles of the invention and include common knowledge or customary techniques in the art not disclosed herein. The description and examples are to be considered as exemplary only, with the true scope and spirit of the invention being indicated by the following claims.

[0128] It should be understood that the present invention is not limited to the exact construction described above and shown in the drawings, and that various modifications and changes may be made without departing from the scope thereof. The scope of the present invention is limited only by the appended claims.

[0129] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent structural change made to the above embodiment based on the technical essence of the present invention shall still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A method for preparing a La-doped cuprous oxide electrocatalyst supported on graphene oxide, characterized in that: The following steps are involved: 1) preparing a monolayer graphene oxide dispersion; 2) Using the single-layer graphene oxide dispersion, preparing a La-doped cuprous oxide electrocatalyst supported on graphene oxide.

2. The method for preparing the La-doped cuprous oxide electrocatalyst supported on graphene oxide according to claim 1, wherein: The specific operations of step 1) are: 11) Immersing the graphite oxide in concentrated sulfuric acid, centrifugally washing, and then washing with ultrapure water until neutral to obtain a washed product; 12) The washed product is treated with an ultrasonic cell disruptor, and the upper dispersion is taken to obtain a single-layer graphene oxide dispersion.

3. The method for preparing the La-doped cuprous oxide electrocatalyst supported on graphene oxide according to claim 1, wherein: The process of step 12) is: The washed product was treated continuously for 6 hours using an ultrasonic cell disruptor in an ice bath at a power of 520 W, and the upper dispersion was taken to obtain a single-layer graphene oxide dispersion.

4. The method for preparing the La-doped cuprous oxide electrocatalyst supported on graphene oxide according to claim 1, wherein: The specific operations of step 2) are: 21) Ultrasonic dissolution of Cu(NO3)2 and La(NO3)3 in ultrapure water, then dropwise adding the graphene oxide dispersion obtained in step 1), and then magnetically stirring in an ice bath to obtain a mixture; 22) NaOH aqueous solution was added dropwise to the mixture obtained in step 21), and then NaBH4 aqueous solution was added dropwise, and the mixture was stirred with magnetic stirring in an ice bath, and then washed and freeze-dried to obtain a La-doped cuprous oxide electrocatalyst supported on graphene oxide.

5. The method for preparing the La-doped cuprous oxide electrocatalyst supported on graphene oxide according to claim 4, wherein: The ratio of Cu(NO3)2, La(NO3)3, graphene oxide dispersion, NaOH aqueous solution and NaBH4 aqueous solution is 0.05-0.2g:0.05-0.2g:1-2mL:0.5-3mL:1-10mL.

6. The method for preparing the La-doped cuprous oxide electrocatalyst supported on graphene oxide according to claim 4, wherein: The specific operations of step 22) are: To the mixture obtained in step 21), a NaOH aqueous solution was added dropwise, and then a NaBH4 aqueous solution was added dropwise, and the mixture was stirred with magnetic stirring for 4 hours in an ice bath, and then washed with ultrapure water and ethanol, and freeze-dried for 12 hours to obtain a La-doped cuprous oxide electrocatalyst supported on graphene oxide.

7. The method for preparing the La-doped cuprous oxide electrocatalyst supported on graphene oxide according to claim 4, wherein: The concentration of the NaOH aqueous solution was 0.9 wt.%.

8. The method for preparing the La-doped cuprous oxide electrocatalyst supported on graphene oxide according to claim 4, wherein: The concentration of the NaBH4 aqueous solution was 0.9 wt.%.

9. The method for preparing the La-doped cuprous oxide electrocatalyst supported on graphene oxide according to claim 2, wherein: The immersion time in step 11) is 24 hours.

10. A La-doped cuprous oxide electrocatalyst supported on graphene oxide, characterized in that: It is prepared based on the preparation method of the La-doped cuprous oxide electrocatalyst supported on graphene oxide according to any one of claims 1 to 9.

Images