Copper-indium diatom modified boron nitride catalyst material as well as preparation method and application thereof

Abstract

The invention provides a copper-indium diatom modified boron nitride catalyst material as well as a preparation method and application thereof. The catalyst is obtained by loading copper nitrate salt and indium nitrate salt on a boron nitride material and then carrying out calcination treatment. Cu and In are reaction active sites and coordinate to regulate and control formation and desorption of an intermediate (* OOH), and electro-catalytic hydrogen peroxide production is promoted. The prepared catalyst is loaded on a glassy carbon electrode on the disc surface of a rotating ring disc electrode (RRDE) as a working electrode, a platinum ring electrode is a ring electrode, and saturated mercury / mercuric oxide and a graphite electrode are respectively a reference electrode and a counter electrode to jointly form a four-electrode testing system. The electrocatalytic hydrogen peroxide production performance is tested through a rotating ring disk electrode (RRDE), considerable selectivity is obtained, and further decentralized electrocatalytic hydrogen peroxide production is facilitated.

Description

Technical Field

[0001] The present invention relates to the technical field of material preparation and application, and particularly to a copper indium dual-atom modified boron nitride catalyst material, a preparation method thereof, and an application thereof. Background Art

[0002] Hydrogen peroxide (H2O2) is one of the 100 important chemicals in the world. It has a wide range of applications and is a green and pollution-free inorganic compound. It is most widely used in fields such as fiber and paper production, water treatment, and environmental remediation in acidic and neutral media, playing an important role. Pure hydrogen peroxide is also called hydrogen peroxide and is a light blue viscous liquid. A hydrogen peroxide solution can be obtained by mixing it with water in any ratio. Moreover, since the oxidation products of hydrogen peroxide are water and oxygen, it is called the most environmentally friendly oxidant.

[0003] The main production method for preparing hydrogen peroxide still relies on the expensive and energy-intensive anthraquinone method. The anthraquinone method means that 2-ethylanthraquinone (EAQ) is catalytically hydrogenated, oxidized, extracted, and diluted to the required product concentration. However, this technology requires a huge infrastructure capital investment and is an energy-intensive technology. A large amount of hazardous waste will also be emitted during the operation process. To minimize the transportation cost from the manufacturing point to the end user, H2O2 is concentrated to 70 wt%, but the potential explosion risk brings safety problems. In addition, adding stabilizers to prevent the degradation of H2O2 usually has a negative impact on the chemical activity of H2O2, and chemical residues will also raise concerns in water treatment applications. Therefore, there is an urgent hope to use electric energy to achieve the sustainable production of H2O2, so as to provide a portable and safe H2O2 supply for dispersed or remote areas.

[0004] Electrocatalytic two-electron oxygen reduction (2e ORR) is a synthetic strategy with great application prospects for preparing H2O2 under mild conditions. However, the slow kinetics and high overpotential of the reaction result in low activity and selectivity of the catalyst. Therefore, this method is still challenging. An efficient electrocatalyst for H2O2 synthesis must exhibit high activity and selectivity. However, this prerequisite is mainly met by noble metal catalysts, including Ag, Pt, Au, etc. Economical counterparts composed of non-noble metals with similar selectivity are still scarce, which has led to great interest in the development of non-noble analogs with similar performance. Therefore, how to select a catalyst with both high selectivity and activity has become the key to promoting the production of hydrogen peroxide by 2e ORR. Utilizing the advantages of In metal catalysts and obtaining composite catalyst materials by modifying with other non-noble metals provides potential research value for the decentralized production of hydrogen peroxide by 2e ORR. Summary of the Invention

[0005] The present invention aims to provide a copper-indium diatomic modified boron nitride catalyst material and a preparation method and application thereof, so as to solve the technical problems existing in the hydrogen peroxide synthesis process, such as high raw material and catalyst costs, simple production process, and low reaction selectivity.

[0006] To achieve the above object, the present invention provides a method for preparing a copper-indium diatomic modified boron nitride catalyst material, the specific steps of which are as follows:

[0007] (1) firstly, mixing and grinding boron nitride nanosheets (BNNS) with potassium hydroxide (KOH) and sodium hydroxide (NaOH) to obtain a uniformly mixed powder;

[0008] (2) the mixed powder is sealed, heated and reacted, and post-treated to obtain BN-OH;

[0009] (3) then adding BN-OH, indium nitrate hydrate (In(NO3)3), and copper nitrate hexahydrate (Cu(NO3)2·6H2O) into deionized water, stirring and dispersing, and drying by stirring in a water bath to obtain a solid powder;

[0010] (4) Finally, the solid powder is transferred to a mortar, moved to a tube furnace, calcined in a nitrogen atmosphere, and naturally cooled to room temperature to obtain the copper indium diatomic modified boron nitride catalyst material (BN-CuIn).

[0011] Preferably, in step (1), the mass ratio of boron nitride nanosheets, potassium hydroxide and sodium hydroxide is 2:4.1:5.4, and the particle size of the boron nitride nanosheets is 100 nm.

[0012] Preferably, in step (2), the process conditions for the sealed heating reaction are: sealed heating reaction at 180° C. for 2 hours.

[0013] Preferably, in step (2), the post-treatment comprises: naturally cooling to room temperature, filtering out the filter residue, washing with distilled water, and vacuum drying.

[0014] Preferably, in step (3), the usage ratio of BN-OH, indium nitrate hydrate, copper nitrate hexahydrate and deionized water is 0.25 g: 0.0602 g: 0.0296 g: 50 mL.

[0015] Preferably, in step (3), the stirring and dispersing time is 30 minutes; and the process conditions for water bath stirring and drying are: stirring in a water bath at 60° C. for 8 to 9 hours.

[0016] Preferably, in step (4), the calcination process conditions are: calcination at 900° C. for 4 hours.

[0017] The present invention also provides a copper-indium diatomic modified boron nitride catalyst material, which is obtained by the above-mentioned preparation method.

[0018] The present invention also provides the application of the foregoing copper-indium dual-atom modified boron nitride catalyst material in the preparation of hydrogen peroxide by electrocatalytic oxygen reduction reaction.

[0019] Preferably, a four-electrode measurement system is adopted. The electrode coated with the foregoing catalyst material is used as the working electrode, the glassy carbon electrode ring area on the electrode is used as the ring electrode, a platinum wire is used as the counter electrode, and a saturated calomel electrode is used as the reference electrode. The four electrodes are used to perform the electrochemically oxygen reduction test for producing hydrogen peroxide in an oxygen-saturated KOH aqueous solution.

[0020] More preferably, the working electrode is prepared by the following method: First, the foregoing catalyst material is added to a mixed solution of isopropanol and Nafion solution, and ultrasonic dispersion is performed to obtain a catalyst slurry, and then the catalyst slurry is coated on the electrode surface; wherein, the dosage ratio of the catalyst material to the mixed solution is 5 mg: 1 mL, the volume ratio of isopropanol to Nafion solution is 9:1, and the mass concentration of the Nafion solution is 5%.

[0021] Even more preferably, the process conditions for ultrasonic dispersion are: ultrasonic dispersion at 200 kHz for 30 minutes.

[0022] Further preferably, the concentration of the KOH aqueous solution is 0.01 - 1 mo1 / L, and even more preferably 0.1 mol / L.

[0023] The present invention also provides a method for synthesizing hydrogen peroxide, which uses the foregoing catalyst material as a catalyst to prepare hydrogen peroxide by electrocatalytic oxygen reduction reaction.

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

[0025] The present invention discloses a copper-indium dual-atom modified boron nitride catalyst material, its preparation method and application. The catalyst is obtained by loading copper nitrate salt and indium nitrate salt onto a boron nitride material and then performing a calcination treatment. Both Cu and In are reactive sites, and they coordinately regulate the formation and desorption of the intermediate (*OOH), promoting the electrocatalytic production of hydrogen peroxide. The prepared catalyst is loaded on the glassy carbon electrode on the disk surface of a rotating ring-disk electrode (RRDE) as the working electrode, a platinum ring electrode is used as the ring electrode, and a saturated mercury / mercuric oxide and a graphite electrode are used as the reference electrode and the counter electrode respectively, jointly constituting a four-electrode test system. The electrocatalytic hydrogen peroxide production performance is tested by a rotating ring-disk electrode (RRDE), and a relatively remarkable selectivity is obtained, which is beneficial for further decentralized electrocatalytic hydrogen peroxide production. Specifically as follows:

[0026] 1. A CuIn dual-atom modified boron nitride catalyst material prepared by the present invention has a preparation method that is divided into preparing a boron nitride support, formulating In precursor and Cu precursor solutions, modifying the dual atoms, and then performing post-calcination treatment. In and Cu are uniformly distributed on the surface of the support in the form of dual atoms, and the particles are relatively small, with the dual atoms tightly bonded to the support. This catalyst has good performance, and the synthesis method has the advantages of environmental protection, simplicity, mild conditions, low cost, high conversion rate, and good selectivity.

[0027] 2. The CuIn dual-atom modified boron nitride catalyst material of the present invention is used for the electrocatalytic production of hydrogen peroxide reaction. Through RRDE testing, the selectivity of hydrogen peroxide is as high as 91.9%, and the number of transferred electrons is 2.16, which is very close to the theoretical value of 2.0. This indicates that the CuIn dual-atom modified boron nitride catalyst material prepared by the present invention has good selectivity activity in the production of hydrogen peroxide through electrochemical oxygen reduction reaction; at the same time, it exhibits good stability, meets the requirements for decentralized production of hydrogen peroxide, and has development potential. Among them, Cu and In each perform their own functions and jointly coordinate and regulate the adsorption and desorption of reaction intermediates, promoting efficient electrocatalytic production of hydrogen peroxide.

[0028] In addition to the purposes, features, and advantages described above, the present invention has other purposes, features, and advantages. The following will refer to the drawings to further elaborate on the present invention in detail. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The drawings constituting a part of this application are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0030] Figure 1 For the four-electrode in the RRDE testing process and the reaction equation of the present invention;

[0031] Figure 2 For the scanning electron microscope image of Example 1;

[0032] Figure 3 For the CV activation diagram of Example 1;

[0033] Figure 4 For the LSV curve diagram of Example 1;

[0034] Figure 5 For the hydrogen peroxide selectivity and current density diagram of Example 1;

[0035] Figure 6 For the hydrogen peroxide selectivity and current density diagram of Example 2;

[0036] Figure 7 For the hydrogen peroxide selectivity and current density diagram of Example 3;

[0037] Figure 8 Selectivity of hydrogen peroxide and current density diagram for Example 4;

[0038] Figure 9 Selectivity of hydrogen peroxide and current density diagram for Example 5;

[0039] Figure 10 Selectivity of hydrogen peroxide and current density diagram for Comparative Example 1;

[0040] Figure 11 Selectivity of hydrogen peroxide and current density diagram for Comparative Example 2;

[0041] Figure 12 Selectivity diagram of hydrogen peroxide for Examples 1-5 and Comparative Examples 1 and 2 of the present invention;

[0042] Figure 13 Number of transferred electrons diagram of hydrogen peroxide for Examples 1-5 and Comparative Examples 1 and 2 of the present invention. Detailed implementation mode

[0043] The following will describe in detail the embodiments of the present invention with reference to the accompanying drawings. However, the present invention can be implemented in many different ways defined and covered by the claims.

[0044] Example 1: Preparation method and application of a dual-atom modified BN-CuIn1-3 catalyst material

[0045] (1) Take 2 g of commercial BN (100 nm, flaky) and mix it with 4.1 g of KOH and 5.4 g of NaOH, and grind them into a powder;

[0046] (2) Transfer the powder in step (1) to a hydrothermal reactor, seal and heat it at 180 °C for 2 hours, cool it to room temperature, perform suction filtration, wash the filter residue with distilled water, and then freeze-dry it at -54 °C. The obtained substance is denoted as BN-OH.

[0047] (3) Weigh 0.25 g of BN-OH, 0.0296 g of Cu(NO3) 2· 6H2O and 0.0903 g of In(NO3)3, add them to 50 mL of deionized water, and stir at room temperature for 30 min. Stir and dry under a water bath to obtain a solid powder.

[0048] (4) Then transfer the solid powder obtained in step (3) to a mortar, grind it into a powder, put it into a porcelain boat, wrap it with tin foil, and place it in a tube furnace. Calcinate it in an inert gas atmosphere, calcinate it at 900 °C for 4 hours, and after cooling to room temperature, finally obtain the copper-indium catalyst supported on boron nitride, denoted as BN-CuIn1-3. The TEM of the catalyst material is as Figure 2 shown.

[0049] The catalytic performance of the BN-CuIn1-3 catalyst prepared in Example 1 was tested. The specific method is as follows:

[0050] S1 Weigh 5 mg of the prepared BN-CuIn1-3 catalyst powder, add 900 μL of isopropanol and 100 μL of Nafion solution (the mass fraction of the Nafion solution is 5%), and ultrasonicate for 30 min at a vibration frequency of 200 kHz to completely disperse the catalyst in the mixed solution, obtaining a uniform catalyst slurry.

[0051] S2 Using a four-electrode measurement system, the electrode coated with the BN-CuIn1-3 catalyst material is used as the working electrode, the platinum electrode ring area on the electrode is used as the ring electrode, the graphite electrode is used as the counter electrode, and the mercury / mercuric oxide electrode is used as the reference electrode. The four electrodes are used for electrochemical oxygen reduction to produce hydrogen peroxide testing in an oxygen-saturated KOH aqueous solution.

[0052] Furthermore, for describing the test steps, based on different electrochemical workstations and different parameters, all the potentials involved in the present invention are converted after the reversible hydrogen electrode (RHE), and the calibrated hydrogen peroxide collection rate N of the electrochemical device is 0.383. The specific test steps are as follows:

[0053] (A) Cyclic voltammetry (CV) activation: In a 0.1 M KOH electrolyte solution, continuously introduce N2 for 20 min for degassing, scan negatively from 1.2 V to 0 V at a rate of 50 mV / s, and then a cycle from 0 V to 1.2 V (cycle) with a scanning time of 48 seconds, for a total of 15 cycles (cycle), that is, the total activation time is 12 min. The obtained CV diagram is as Figure 3 shown.

[0054] (B) RRDE test under O2 atmosphere saturation ( Figure 1 ) Experimental data:

[0055] Introduce O2 into the 0.1 M KOH electrolyte solution for 30 min to ensure that O2 in the solution reaches saturation. Turn on the RRDE working electrode rotation switch, adjust the button to make the rotation speed stable at 1600 rpm, and then perform linear sweep voltammetry testing. Obtain the LSV curve of the material at this rotation speed, as Figure 4 shown.

[0056] (C) Data processing: Denote the black line ring current in the LSV curve obtained in step (B) as I r , and the disk current of the red curve as I d According to the following formula,

[0057] Hydrogen peroxide selectivity (%) = 200 (I r / N) × (I r / N + |I d|)(1)

[0058] Faraday efficiency (%) = I r / (|I d |×N)(2)

[0059] Number of electrons transferred n = 4I d ×(I r / N + |I d |)(3)

[0060] In the above formula, I d and I r represent the disk current and the ring current respectively, and N is the ring-disk collection rate, taking 0.383.

[0061] Data post-processing is performed according to formulas (1) and (2). As Figure 5 shown, when the reversible hydrogen electrode is 0.4 V, the hydrogen peroxide selectivity of BN-CuIn1-3 is measured to be 87.3%, and the Faraday efficiency is 77.5%.

[0062] Example 2: Preparation method and application of a dual-atom modified BN-CuIn1-2 catalyst material

[0063] (1) Take 2 g of commercial BN (100 nm, flaky), mix it with 4.1 g of KOH and 5.4 g of NaOH, and grind it into a powder;

[0064] (2) Heat and react it hermetically at 180 °C for 2 hours, cool it to room temperature, perform suction filtration, wash the filter residue with distilled water, and then freeze-dry it at -54 °C. The obtained substance is denoted as BN-OH.

[0065] (3) Weigh 0.25 g of BN-OH, 0.0296 g of Cu(NO3) 2· 6H2O and 0.0602 g of In(NO3)3, add them to 50 mL of deionized water, and stir at room temperature for 30 min. Stir and dry it under water bath to obtain a solid powder.

[0066] (4) Then transfer the solid powder obtained in step 3 to a mortar, grind it into a powder, put it into a porcelain boat, wrap it with tin foil, and place it in a tubular furnace. Calcinate it in an inert gas atmosphere at 900 °C for 4 hours. After cooling to room temperature, finally obtain the copper-indium catalyst supported on boron nitride, denoted as BN-CuIn1-2.

[0067] Repeat the RRDE test steps in Example 1. The test results of BN-CuIn1-2 obtained after treatment are as Figure 6 shown. The hydrogen peroxide selectivity of BN-CuIn1-2 is measured to be 87.1%, and the Faraday efficiency is 77.1%.

[0068] Example 3: Preparation Method and Application of a Dual-Atom Modified BN-CuIn1-1 Catalyst Material

[0069] (1) Take 2 g of commercial BN (100 nm, flaky), mix it with 4.1 g of KOH and 5.4 g of NaOH, and grind them into a powder.

[0070] (2) Heat and react hermetically at 180 °C for 2 hours, cool to room temperature, perform suction filtration, wash the filter residue with distilled water, and then freeze-dry it at -54 °C. The obtained substance is denoted as BN-OH.

[0071] (3) Weigh 0.25 g of BN-OH, 0.0296 g of Cu(NO3) 2· 6H2O and 0.0301 g of In(NO3)3, add them to 50 mL of deionized water, stir at room temperature for 30 min, and stir and dry under water bath to obtain a solid powder.

[0072] (4) Then transfer the solid powder obtained in step (3) to a mortar, grind it into a powder, put it into a porcelain boat, wrap it with tin foil, and place it in a tube furnace. Calcinate it in an inert gas atmosphere at 900 °C for 4 hours. After cooling to room temperature, the obtained copper-indium catalyst supported on boron nitride is denoted as BN-CuIn1-1.

[0073] Repeat the RRDE test procedure in Example 1. The test results of BN-CuIn1-1 obtained after treatment are as Figure 7 shown.

[0074] Example 4: Preparation Method and Application of a Dual-Atom Modified BN-CuIn2-1 Catalyst Material

[0075] (1) Take 2 g of commercial BN (100 nm, flaky), mix it with 4.1 g of KOH and 5.4 g of NaOH, and grind them into a powder.

[0076] (2) Heat and react hermetically at 180 °C for 2 hours, cool to room temperature, perform suction filtration, wash the filter residue with distilled water, and then freeze-dry it at -54 °C. The obtained substance is denoted as BN-OH.

[0077] (3) Weigh 0.25 g of BN-OH, 0.0592 g of Cu(NO3) 2· 6H2O and 0.0301 g of In(NO3)3, add them to 50 mL of deionized water, stir at room temperature for 30 min, and stir and dry under water bath to obtain a solid powder.

[0078] (4) Then transfer the solid powder obtained in 3 to a mortar and grind it into powder. Load it into a porcelain boat, wrap it with tin foil, and place it in a tube furnace. Calcinate it in an inert gas atmosphere at 900 °C for 4 hours. After cooling to room temperature, finally obtain the copper-indium catalyst supported on boron nitride, denoted as BN-CuIn2-1.

[0079] Repeat the RRDE test procedure in Example 1. The test results of BN-CuIn2-1 obtained after treatment are as Figure 8 shown.

[0080] Example 5: Preparation method and application of a dual-atom modified BN-CuIn3-1 catalyst material:

[0081] (1) Take 2 g of commercial BN (100 nm, flaky), mix it with 4.1 g of KOH and 5.4 g of NaOH, and grind them into a powder.

[0082] (2) Heat and react hermetically at 180 °C for 2 hours, cool to room temperature, perform suction filtration. After washing the filter residue with distilled water, then freeze-dry it at -54 °C. The obtained substance is denoted as BN-OH.

[0083] (3) Weigh 0.25 g of BN-OH, 0.0888 g of Cu(NO3) 2· 6H2O and 0.0301 g of In(NO3)3, add them to 50 mL of deionized water, and stir at room temperature for 30 min. Stir and dry under a water bath to obtain a solid powder.

[0084] (4) Then transfer the solid powder obtained in 3 to a mortar and grind it into powder. Load it into a porcelain boat, wrap it with tin foil, and place it in a tube furnace. Calcinate it in an inert gas atmosphere at 900 °C for 4 hours. After cooling to room temperature, finally obtain the copper-indium catalyst supported on boron nitride, denoted as BN-CuIn3-1.

[0085] Repeat the RRDE test procedure in Example 1. The test results of BN-CuIn3-1 obtained after treatment are as Figure 9 shown.

[0086] Comparative Example 1: Preparation method and application of a Cu atom modified BN-Cu catalyst material:

[0087] (1) Take 2 g of commercial BN (100 nm, flaky), mix it with 4.1 g of KOH and 5.4 g of NaOH, and grind them into a powder.

[0088] (2) Heat and react hermetically at 180 °C for 2 hours, cool to room temperature, perform suction filtration. After washing the filter residue with distilled water, then freeze-dry it at -54 °C. The obtained substance is denoted as BN-OH.

[0089] (3) Weigh 0.25 g of BN-OH and 0.0296 g of Cu(NO3) 2· 6H2O, add them to 50 mL of deionized water, and stir at room temperature for 30 min. Stir and dry under a water bath to obtain a solid powder.

[0090] (4) Then transfer the solid powder obtained in (3) to a mortar and grind it into a powder. Load it into a porcelain boat, wrap it with tin foil, and place it in a tubular furnace. Calcinate it in an inert gas atmosphere at 900 °C for 4 hours. After cooling to room temperature, finally obtain the copper-indium catalyst supported on boron nitride, denoted as BN-Cu.

[0091] Repeat the RRDE test procedure in Example 1, and after treatment, obtain the test results of BN-Cu, as Figure 10 shown.

[0092] Comparative Example 2: Preparation method and application of an In atom-modified BN-Cu catalyst material:

[0093] (1) Take 2 g of commercial BN (100 nm, flaky), mix it with 4.1 g of KOH and 5.4 g of NaOH, and grind them into a powder;

[0094] (2) Heat and react hermetically at 180 °C for 2 hours, cool to room temperature, perform suction filtration. After washing the filter residue with distilled water, then freeze-dry it at -54 °C. The obtained substance is denoted as BN-OH.

[0095] (3) Weigh 0.25 g of BN-OH and 0.0301 g of In(NO3)3, add them to 50 mL of deionized water, and stir at room temperature for 30 min. Stir and dry under a water bath to obtain a solid powder.

[0096] (4) Then transfer the solid powder obtained in (3) to a mortar and grind it into a powder. Load it into a porcelain boat, wrap it with tin foil, and place it in a tubular furnace. Calcinate it in an inert gas atmosphere at 900 °C for 4 hours. After cooling to room temperature, finally obtain the copper-indium catalyst supported on boron nitride, denoted as BN-In.

[0097] Repeat the RRDE test procedure in Example 1, and after treatment, obtain the test results of BN-In, as Figure 11 shown.

[0098] Table 1 summarizes the results of hydrogen peroxide production by the catalyst materials in Examples 1-5 and Comparative Examples 1-2.

[0099] Table 1. Selectivity of hydrogen peroxide production by different catalyst materials

[0100] Example Selectivity of hydrogen peroxide % Number of transferred electrons Example 1 BN-CuIn1-3 87.3 2.25 Example 2 BN-CuIn1-2 87.1 2.26 Example 3 BN-CuIn1-1 75.3 2.50 Example 4 BN-CuIn2-1 91.9 2.16 Example 5 BN-CuIn3-1 87.8 2.24 Comparative Example 1 BN-Cu 52.8 2.94 Comparative Example 2 BN-In 71.3 2.57

[0101] According to Figure 12 、 Figure 13As can be seen from Table 1, the CuIn dual-atom modified boron nitride catalyst materials prepared in Examples 1-5 of the present invention have good performance in electrocatalytic hydrogen peroxide production.

[0102] From Figure 12 , Figure 13 the results of H2O2 selectivity, it can be seen that the selectivity of Example 4 is the highest, and its selectivity value can reach 91.9% at a voltage of 0.4 V RHE, and the corresponding number of transferred electrons is 2.16, which is very close to the theoretical value of 2.0. This shows that it has high hydrogen peroxide selectivity.

[0103] By analyzing the results of Examples 1-5, it can be proved that the CuIn dual-atom modified boron nitride catalyst prepared by the present invention can only play the role of electrocatalytic hydrogen peroxide production when both Cu and In are present. It is speculated that In regulates the process of water dissociation to form *H, and the process of Cu adsorbing *H to form *OOH adsorbs *H again to form the product hydrogen peroxide. In summary, it can be seen that changing the InCu ratio and carrier preparation conditions has a great impact on the final electrocatalytic hydrogen peroxide production. An optimal experimental condition can be obtained through regulation, which is beneficial to cost saving and improving hydrogen peroxide selectivity. At the same time, the overall mechanical properties of the catalyst are good, pollution-free, and ultimately can promote the decentralized application of electrocatalytic hydrogen peroxide production.

[0104] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method of a copper-indium dual-atom modified boron nitride catalyst material, characterized in that, The specific steps are as follows: (1) First, mix and grind boron nitride nanosheets, potassium hydroxide, and sodium hydroxide evenly to obtain a mixed powder; (2) Heat the mixed powder in a sealed manner for reaction, and then conduct post-treatment to obtain BN-OH; (3) Then add BN-OH, indium nitrate hydrate, and copper nitrate hexahydrate to deionized water, stir and disperse, and conduct water bath stirring and drying to obtain a solid powder; (4) Finally, transfer the solid powder to a mortar, grind it, transfer it to a tube furnace, calcine it under a nitrogen atmosphere, and naturally cool it to room temperature to obtain the copper-indium dual-atom modified boron nitride catalyst material.

2. The preparation method according to claim 1, characterized in that, In step (1), the mass ratio of boron nitride nanosheets, potassium hydroxide, and sodium hydroxide is 2:4.1:5.4, and the particle size of the boron nitride nanosheets is 100 nm.

3. The preparation method according to claim 1, wherein In step (2), the process conditions for the sealed high-temperature and high-pressure reaction are: sealed high-temperature and high-pressure reaction at 180 °C for 2 hours.

4. The preparation method according to claim 1, wherein, In step (2), the post-treatment includes: naturally cooling to room temperature, filtering by suction to obtain the filter residue, washing with distilled water, and vacuum drying.

5. The preparation method according to claim 1, wherein, In step (3), the dosage ratio of BN-OH, indium nitrate hydrate, copper nitrate hexahydrate, and deionized water is 0.25 g:0.0602 g:0.0296 g:50 mL.

6. The preparation method according to claim 1, characterized in that, In step (3), the stirring and dispersion time is 30 minutes; the process conditions for water bath stirring and drying are: water bath stirring at 60 °C for 8 - 9 hours.

7. The preparation method according to claim 1, wherein In step (4), the process conditions for calcination are: calcination at 900 °C for 4 hours.

8. A copper-indium dual-atom modified boron nitride catalyst material, characterized in that, It is obtained by the preparation method described in any one of claims 1 to 7.

9. Use of the copper-indium dual-atom modified boron nitride catalyst material described in claim 8 in the preparation of hydrogen peroxide by electrocatalytic oxygen reduction reaction.

10. A method for synthesizing hydrogen peroxide, characterized in that, It uses the catalyst material described in claim 8 as a catalyst to prepare hydrogen peroxide by electrocatalytic oxygen reduction reaction.

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