A bi-ni nano-alloy particle loaded carbon material, a preparation method and use thereof

Abstract

The application discloses BiNi nano-alloy particle loaded carbon material, which is BiNi nano-alloy particle uniformly loaded on sheet graphite carbon, the intensity ratio of D band and G band of the sheet graphite carbon is about 0.94, and the particle size of the BiNi nano-alloy particle is 2.0-20.0 nm. The application further discloses a preparation method and application of the BiNi nano-alloy particle loaded carbon material.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of materials, and particularly relates to a BiNi nano-alloy particle loaded carbon material, a preparation method and application thereof. BACKGROUND

[0002] Hydrogen peroxide, as a green oxidant, has a very wide application in the fields of chemical synthesis, disinfection, wastewater treatment, etc. Compared with the traditional anthraquinone method for preparing hydrogen peroxide, the two-electron oxygen reduction reaction method is concerned due to its environmental protection and energy saving advantages. However, there is competition between the two-electron oxygen reduction reaction and the four-electron oxygen reduction reaction, resulting in low selectivity and yield of hydrogen peroxide. In theory, the selectivity of the oxygen reduction reaction is highly dependent on the adsorption energy and adsorption mode of the *OOH intermediate on the active site. When the *OOH intermediate is adsorbed on the surface of the material in the “side-on configuration”, the adsorption energy of *OOH is too strong, which leads to the rupture of the O-O bond and induces the four-electron oxygen reduction reaction path; if the adsorption mode of *OOH is “end-on adsorption”, the adsorption energy is moderate, which is conducive to the occurrence of the two-electron oxygen reduction reaction. Therefore, it is of great significance to develop electrode materials with adjustable electronic structure to adjust the adsorption performance of *OOH and the oxygen reduction reaction path.

[0003] In recent years, nickel-based electrode materials have been widely used in the field of two-electron oxygen reduction reaction; however, the nickel-based materials without modification or improper modification have poor two-electron oxygen reduction reaction activity and selectivity. Most nickel-based materials have the problem of too strong adsorption energy of *OOH intermediate, which is easy to occur four-electron oxygen reduction reaction. In order to improve the selectivity of two-electron oxygen reduction reaction, various strategies such as crystal type regulation, vacancy engineering, single atom engineering, etc. are used to regulate the electronic structure of nickel-based materials. ACSCatalysis 2022, 12, 5911-5920 reports that *OOH intermediate is more inclined to be adsorbed on the amorphous NiO x surface in “end-on mode”, thereby effectively promoting the two-electron oxygen reduction reaction process; Advanced Materials 2022, 34, e2106541 reports that by cation engineering strategy, Ni cation vacancies (V Ni ) are successfully introduced into nickel phosphide (Ni 2-x P-V Ni ) material, V NiThe induced geometry and electronic structure optimization makes the OOH adsorption model to be in an "end-to-end configuration". Although substantial progress has been made by the above methods, the electronic structure of Ni is still difficult to accurately control, and the activity and stability of the obtained Ni-based electrochemical materials are still limited; in addition, the synthesis route of these nickel-based electrochemical materials is complicated, which hinders their practical application. Alloying is an effective strategy for synthesizing high-performance two-electron oxygen reduction reaction electrode materials. For alloy electrode materials, active metal sites can be separated by another metal, thereby extending the distance or spacing of the active metal sites, thereby promoting the occurrence of the "end-to-end adsorption" configuration of OOH. So far, palladium-mercury, silver-mercury and platinum-mercury and other noble metal alloys are efficient electrode materials for preparing hydrogen peroxide (see Advanced Science 2021, 8, 2100076), these noble metal alloy materials have the advantages of small overpotential and high hydrogen peroxide selectivity, and the inherent inertness of the noble metal alloy can ensure the durability of the material in practical application. However, these noble metal alloy materials have the disadvantages of high cost, scarcity and toxicity, which seriously hinder their practical application; in addition, some metals in the noble metal alloy material, such as mercury, can only act as non-active sites to isolate active metal sites (palladium, platinum, silver), resulting in low atomic utilization of the noble metal alloy material. Alloying the highly active Ni metal with other non-noble metals for electrode materials is likely to be an ideal strategy to improve the two-electron oxygen reduction reaction for preparing hydrogen peroxide. Therefore, the present application is proposed. SUMMARY

[0004] In view of the problems in the prior art, the present application provides a BiNi nano-alloy particle loaded carbon material and a preparation method thereof. The present application first adopts a method combining hydrothermal method and high-temperature calcination method, realizes the size control of BiNi alloy particles by adjusting the proportion of metal sources in the hydrothermal reaction process; realizes the growth of alloy particles and the formation of carbon skeleton through high-temperature calcination, and finally obtains BiNi alloy nano-particles uniformly loaded on the surface of sheet graphite carbon. The material of the present application has excellent two-electron oxygen reduction performance for preparing hydrogen peroxide electrode material.

[0005] The technical scheme of the present application is as follows:

[0006] The first aspect of the present application discloses a BiNi nano-alloy particle loaded carbon material, which is BiNi nano-alloy particles uniformly loaded on sheet graphite carbon, the intensity ratio of D band to G band of the sheet graphite carbon is about 0.94; the particle size of the BiNi nano-alloy particles is 2.0-20.0 nm.

[0007] Preferably, the molar ratio of Bi to Ni in the BiNi alloy is 0.125.

[0008] The second aspect of the present application discloses a preparation method of the BiNi nano-alloy particle loaded carbon material, comprising the following steps:

[0009] (1) Preparation of Bi / Ni-MOF: terephthalic acid is dissolved in a mixed solution of N,N-dimethylformamide, anhydrous ethanol and deionized water, and ultrasonic treatment is performed for a period of time; then, bismuth salt and nickel salt with a certain molar ratio are added, and ultrasonic treatment is performed for a period of time to obtain a mixed solution; the above mixed solution is subjected to hydrothermal reaction at a certain temperature for a period of time, and then separated, washed and dried to obtain Bi / Ni-MOF;

[0010] (2) BiNi nano-alloy particle loaded carbon material: the Bi / Ni-MOF prepared in step (1) is placed in a nitrogen atmosphere and calcined at high temperature for a period of time, and then cooled to room temperature to obtain the BiNi nano-alloy particle loaded carbon material.

[0011] Preferably, in step (1), the bismuth salt is bismuth nitrate pentahydrate, and the nickel salt is nickel chloride hexahydrate; the molar ratio of bismuth nitrate pentahydrate to nickel chloride hexahydrate is 0.100-2.000.

[0012] Preferably, in step (1), the ultrasonic treatment time is 5-30 minutes; the hydrothermal reaction temperature is 160-200℃, and the hydrothermal reaction time is 12-20 hours; the washing is performed by deionized water and anhydrous ethanol for no less than three times.

[0013] Preferably, in step (2), the high-temperature calcination has a heating rate of 5℃ / min, the calcination temperature is 600-800℃, and the calcination time is 2-6 hours.

[0014] The third aspect of the present application discloses the use of the BiNi nano-alloy particle loaded carbon material as an electrode material.

[0015] Preferably, the BiNi nano-alloy particle loaded carbon material is used for preparing a hydrogen peroxide electrode material.

[0016] The present application has the following beneficial effects:

[0017] 1. The BiNi nano-alloy particle-supported carbon material of the present invention consists of BiNi nano-alloy particles uniformly loaded on sheet graphite carbon, wherein the intensity ratio of the D-band to the G-band of the sheet graphite carbon is approximately 0.94; the particle size of the BiNi nano-alloy particles is 2.0-20.0 nm. The BiNi nano-alloy particle-supported carbon material of the present invention is used as an electrode material for preparing hydrogen peroxide. When the molar ratio of Bi to Ni is 0.125, the resulting BiNi nano-alloy particles exhibit the best performance in the two-electron oxygen reduction reaction for preparing hydrogen peroxide. When the molar ratio of Bi to Ni is 0.125, in addition to forming BiNi nano-alloy particles with a Bi to Ni atom ratio of 1:1, elemental Ni is also present. At this time, Bi in the BiNi nano-alloy particles acts as an isolating site, achieving physical and electronic isolation of Ni sites, greatly reducing the electron cloud density of Ni sites, thereby facilitating the occurrence of the "end-to-end adsorption" mode of the *OOH intermediate, and thus improving the selectivity and activity of the two-electron oxygen reduction reaction for preparing hydrogen peroxide. Furthermore, noble metal alloys often have only one metal as an active site, resulting in low atomic utilization. However, the material of this invention, due to the unique electronic structure of the BiNi alloy, achieves maximum atomic utilization. Compared to highly active nickel-based electrical materials reported in the prior art, the material of this invention exhibits superior performance.

[0018] 2. The preparation method of this invention first obtains Bi / Ni-MOF (Metal Organic Framework), and then achieves the growth of alloy nanoparticles and the formation of a graphitic carbon framework through high-temperature calcination, ultimately resulting in BiNi alloy nanoparticles uniformly loaded on the surface of sheet-like graphitic carbon material. This preparation method has advantages such as a simple synthesis route, controllable BiNi alloy nanoparticle size, and reasonable optimization of the Ni electronic structure, which is beneficial to enhancing the industrial application value and potential of this method. This preparation method also addresses, to some extent, the problems of high cost, scarcity, and high toxicity of noble metal alloy electrode materials.

[0019] 3. The BiNi nano-alloy particles of the present invention are supported on carbon materials. The microstructure diagram of the BiNi alloy when the molar ratio of Bi to Ni is 0.125 is shown in the figure. Figure 8 As shown, in Figure 8In the present application, BiNi nano-alloy particles and part of metal Ni particles are uniformly dispersed and supported on the surface of carbon material or in the pore of carbon material. The single metal-based material often has the problem of poor stability, which is caused by serious leaching of metal ions in the electrocatalytic process. In the present application, BiNi nano-alloy particles are supported on the sheet graphite carbon skeleton, and the protection of carbon material improves the stability of BiNi nano-alloy particles to a certain extent. In addition, the sheet graphite carbon material as a carrier has abundant pore structure, which is conducive to the exposure of active sites and accelerates the mass transfer process. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 is a preparation method flow chart of BiNi nano-alloy particle loaded carbon material of the present application.

[0021] Figure 2 is the SEM image of BiNi nano-alloy particle loaded carbon material prepared in Example 1-6, which is the SEM image of BiNi / C-2 (a), BiNi / C-1 (b), BiNi / C-0.5 (c), BiNi / C-0.375 (d), BiNi / C-0.25 (e), BiNi / C-0.125 (f), respectively.

[0022] Figure 3 is the XRD image of BiNi / C-2, BiNi / C-1, BiNi / C-0.5, BiNi / C-0.375, BiNi / C-0.25, BiNi / C-0.125 obtained in Example 1-6.

[0023] Figure 4 is the SEM image of Bi / Ni-MOF-0.125 prepared in step one of Example 6.

[0024] Figure 5 is the TEM image (a), high-magnification TEM image (b), element distribution map (c), particle size statistical distribution map (d), linear scanning spectrum (e) and (f) of BiNi / C-0.125 prepared in Example 6.

[0025] Figure 6 is the Raman image of BiNi / C-0.125 prepared in Example 6.

[0026] Figure 7 is the XRD image of the material obtained in Example 7.

[0027] Figure 8 is a schematic diagram of the microstructure of BiNi nano-alloy particle loaded carbon material (BiNi / C-0.125) of Example 6.

[0028] Figure 9are the performance plots of two-electron oxygen reduction reaction of the BiNi nanoscale alloy particle supported carbon material of Examples 1-6 for the production of hydrogen peroxide; (a) linear sweep voltammograms, (b) selectivity of hydrogen peroxide (H2O2%), and (c) number of electrons transferred (n) of the reaction. DETAILED DESCRIPTION

[0029] The technical solutions of the present application will be further described in combination with the specific embodiments. It should be noted that the following examples are only used to specifically describe and explain the present application, and the application range of the present application is not limited by the conditions in the examples.

[0030] Example 1: BiNi nanoscale alloy particle supported carbon material (BiNi / C-2) was prepared according to the procedure described in Example 1. Figure 1 The preparation steps are as follows,

[0031] Step one, preparation of Bi / Ni-MOF-2: 0.25 g of terephthalic acid was dissolved in a mixed solution of 64 mL of N,N-dimethylformamide, 4 mL of anhydrous ethanol and 4 mL of deionized water, and ultrasonic was performed for 15 min; then, bismuth nitrate pentahydrate and nickel chloride hexahydrate with a molar ratio of 2 (1 mmol of bismuth nitrate pentahydrate and 0.5 mmol of nickel chloride hexahydrate) were added, and ultrasonic was performed for 15 min; the above mixed solution was transferred into a 100 mL stainless steel reaction kettle with a polytetrafluoroethylene liner, and hydrothermal reaction was performed at 160℃ for 12 h; after the reaction was completed, filtration was performed, and the solid was washed with deionized water and anhydrous ethanol three times, respectively, and dried at 60℃ to obtain Bi / Ni-MOF-2.

[0032] Step two, preparation of BiNi alloy supported carbon material (BiNi / C-2): the Bi / Ni-MOF prepared in step one was placed in a tube furnace in a nitrogen atmosphere for high-temperature calcination, the calcination temperature was 675℃, the calcination time was 2 h, and the heating rate was 5℃ / min; after cooling to room temperature, the obtained BiNi nanoscale alloy particle supported carbon material (BiNi / C-2) had a morphology structure as shown in Figure 2 a.

[0033] Example 2: BiNi nanoscale alloy particle supported carbon material (BiNi / C-1) was prepared.

[0034] Step one, preparation of Bi / Ni-MOF-1: 0.25 g of terephthalic acid was dissolved in a mixed solution of 64 mL of N,N-dimethylformamide, 4 mL of anhydrous ethanol and 4 mL of deionized water, and ultrasonic was applied for 15 min. Then, 1 molar ratio of bismuth nitrate pentahydrate and nickel chloride hexahydrate (0.75 mmol of bismuth nitrate pentahydrate and 0.75 mmol of nickel chloride hexahydrate) was added, and ultrasonic was applied for 15 min; the above mixed solution was transferred into a 100 mL stainless steel reactor with a polytetrafluoroethylene liner, and hydrothermal reaction was carried out at 160 °C for 12 h; after the reaction was completed, suction filtration was performed, the solid was washed with deionized water and anhydrous ethanol for three times respectively, and drying was carried out at 60 °C to obtain Bi / Ni-MOF-1;

[0035] Step two, same as example 1: BiNi nano-alloy particle loaded carbon material (BiNi / C-1) was obtained, and the morphology structure thereof is shown in Figure 2 b;

[0036] Example 3: BiNi nano-alloy particle loaded carbon material (BiNi / C-0.5) was prepared.

[0037] Step one, preparation of Bi / Ni-MOF-0.5: 0.25 g of terephthalic acid was dissolved in a mixed solution of 64 mL of N,N-dimethylformamide, 4 mL of anhydrous ethanol and 4 mL of deionized water, and ultrasonic was applied for 15 min. Then, 0.5 molar ratio of bismuth nitrate pentahydrate and nickel chloride hexahydrate (0.5 mmol of bismuth nitrate pentahydrate and 1 mmol of nickel chloride hexahydrate) was added, and ultrasonic was applied for 15 min; the above mixed solution was transferred into a 100 mL stainless steel reactor with a polytetrafluoroethylene liner, and hydrothermal reaction was carried out at 160 °C for 12 h; after the reaction was completed, suction filtration was performed, the solid was washed with deionized water and anhydrous ethanol for three times respectively, and drying was carried out at 60 °C to obtain Bi / Ni-MOF-0.5;

[0038] Step two, same as example 1: BiNi nano-alloy particle loaded carbon material (BiNi / C-0.5) was obtained, and the morphology structure thereof is shown in Figure 2 c.

[0039] Example 4: BiNi nano-alloy particle loaded carbon material (BiNi / C-0.375) was prepared.

[0040] Step one, preparation of Bi / Ni-MOF-0.375. 0.25 g of terephthalic acid was dissolved in a mixed solution of 64 mL of N,N-dimethylformamide, 4 mL of anhydrous ethanol and 4 mL of deionized water, and ultrasonic treatment was performed for 15 min. Then, bismuth nitrate pentahydrate and nickel chloride hexahydrate with a molar ratio of 0.375 (0.409 mmol of bismuth nitrate pentahydrate and 1.091 mmol of nickel chloride hexahydrate) were added, and ultrasonic treatment was performed for 15 min. The above mixed solution was transferred into a 100 mL stainless steel reaction kettle with a polytetrafluoroethylene liner, and hydrothermal reaction was performed at 160 °C for 12 h. After the reaction was completed, suction filtration was performed, and the solid was washed with deionized water and anhydrous ethanol three times, respectively, and dried at 60 °C to obtain Bi / Ni-MOF-0.375.

[0041] Step two, same as Example 1: BiNi nano-alloy particle loaded carbon material (BiNi / C-0.375) was obtained, and the morphology structure thereof is shown in Figure 2 d.

[0042] Example 5: BiNi nano-alloy particle loaded carbon material (BiNi / C-0.25) was prepared

[0043] Step one, preparation of Bi / Ni-MOF-0.25: 0.25 g of terephthalic acid was dissolved in a mixed solution of 64 mL of N,N-dimethylformamide, 4 mL of anhydrous ethanol and 4 mL of deionized water, and ultrasonic treatment was performed for 15 min. Then, bismuth nitrate pentahydrate and nickel chloride hexahydrate with a molar ratio of 0.25 (0.3 mmol of bismuth nitrate pentahydrate and 1.2 mmol of nickel chloride hexahydrate) were added, and ultrasonic treatment was performed for 15 min. The above mixed solution was transferred into a 100 mL stainless steel reaction kettle with a polytetrafluoroethylene liner, and hydrothermal reaction was performed at 160 °C for 12 h. After the reaction was completed, suction filtration was performed, and the solid was washed with deionized water and anhydrous ethanol three times, respectively, and dried at 60 °C to obtain Bi / Ni-MOF-0.25.

[0044] Step two, same as Example 1: BiNi nano-alloy particle loaded carbon material (BiNi / C-0.25) was obtained, and the morphology structure thereof is shown in Figure 2 e.

[0045] Example 6: BiNi nano-alloy particle loaded carbon material (BiNi / C-0.125) was prepared

[0046] Step one: Preparation of Bi / Ni-MOF-0.125: 0.25 g of terephthalic acid was dissolved in a mixed solution of 64 mL of N,N-dimethylformamide, 4 mL of anhydrous ethanol and 4 mL of deionized water, and ultrasonic treatment was performed for 15 min. Then, bismuth nitrate pentahydrate and nickel chloride hexahydrate with a molar ratio of 0.125 (0.167 mmol of bismuth nitrate pentahydrate and 1.333 mmol of nickel chloride hexahydrate) were added, and ultrasonic treatment was performed for 15 min. The above mixed solution was transferred into a 100 mL stainless steel reactor with a polytetrafluoroethylene liner, and hydrothermal reaction was performed at 160°C for 12 h. After the reaction was completed, suction filtration was performed, and the solid was washed with deionized water and anhydrous ethanol three times, respectively. Bi / Ni-MOF-0.125 was obtained by drying at 60°C, and the morphology and structure thereof are shown in FIG. 1. Figure 4

[0047] Step two: The same as Example 1: BiNi nanometer alloy particle loaded carbon material (BiNi / C-0.125) was obtained, and the morphology and structure thereof are shown in FIG. 2f. Figure 2

[0048] Example 7: Preparation of BiNi nanometer alloy particle loaded carbon material (BiNi / C-0.1)

[0049] Step one: Preparation of Bi / Ni-MOF-0.1: 0.25 g of terephthalic acid was dissolved in a mixed solution of 64 mL of N,N-dimethylformamide, 4 mL of anhydrous ethanol and 4 mL of deionized water, and ultrasonic treatment was performed for 15 min. Then, bismuth nitrate pentahydrate and nickel chloride hexahydrate with a molar ratio of 0.1 (0.136 mmol of bismuth nitrate pentahydrate and 1.364 mmol of nickel chloride hexahydrate) were added, and ultrasonic treatment was performed for 15 min. The above mixed solution was transferred into a 100 mL stainless steel reactor with a polytetrafluoroethylene liner, and hydrothermal reaction was performed at 160°C for 12 h. After the reaction was completed, suction filtration was performed, and the solid was washed with deionized water and anhydrous ethanol three times, respectively. Bi / Ni-MOF-0.1 was obtained by drying at 60°C.

[0050] Step two: The same as Example 1: The XRD pattern of the obtained material is shown in FIG. 3, and it can be known from the figure that the obtained material is Ni / NiO / C material, rather than BiNi nanometer alloy particle loaded carbon material. Therefore, BiNi nanometer alloy particle loaded carbon material cannot be obtained when the BiNi molar ratio is less than 0.1. Figure 7 Figure 7

[0051] Figure 2 are SEM images of the BiNi nanometer alloy particle loaded carbon material obtained in Examples 1-6. As can be seen from the figures, with the decrease of the molar ratio of bismuth nitrate pentahydrate and nickel chloride hexahydrate, the size of the obtained alloy particles gradually decreases; and when the molar ratio is 0.125, the BiNi alloy particles obtained are the smallest and most uniform.​​​​Figure 2 f). Therefore, the alloy particle size can be controlled by adjusting the molar ratio of the metal source in step one. However, BiNi alloy nanoparticles cannot be obtained when the molar ratio of Bi to Ni is less than 0.1.

[0052] Figure 3 The left graph is the XRD pattern of the BiNi alloy nanoparticle loaded carbon material obtained in Example 1-5, Figure 3 The right graph is the XRD pattern of the BiNi alloy loaded carbon material obtained in Example 6. As can be seen from the graph, all the materials have obvious characteristic peaks observed at 25.2° (400), 30.3° (224), 33.4° (008), 42.3° (-228), 44.4° (040), 54.7° (444), 56.6° (048), 57.8° (116), 63.0° (448), 73.0° (-264), 75.8° (-4412), 76.4° (1008), which are attributed to BiNi alloy, indicating the successful synthesis of BiNi alloy. In addition, as the molar ratio of bismuth nitrate pentahydrate to nickel chloride hexahydrate decreases, the prepared material also gradually appears characteristic peaks attributed to metallic nickel at 44.5° (111) and 51.8° (200).

[0053] Figure 4 is the SEM image of Bi / Ni-MOF-0.125 prepared in step one of Example 6. It can be seen that Bi / Ni-MOF-0.125 is a micron-sized flower-like structure assembled by sheets. In combination with Figure 2 f, it can be seen that BiNi / C-0.125 obtained after high-temperature calcination still maintains the morphology of Bi / Ni-MOF-0.125. This indicates that the structure of the material has strong stability.

[0054] Figure 5 is the TEM image (a), high-magnification TEM image (b), element distribution map (c), particle size statistical distribution map (d), linear scanning spectrum (e) and (f) of BiNi / C-0.125 prepared in Example 6. As can be seen from Figure 5 a, the metal nanoparticles are uniformly loaded on the carbon skeleton. As can be seen from the particle size statistical distribution map Figure 5 d, the average size of the metal particles in the statistical range of 8-14 nanometers is 10.8 nanometers; some metal particles with sizes less than or greater than this range are not in the statistical graph. As can be seen from Figure 5 b, it can be seen that the spacing of the lattice fringes is about 0.267 nanometers, which is attributed to the (002) crystal plane of BiNi, which further indicates the successful preparation of BiNi alloy. Figure 5 c is the element distribution map of BiNi alloy. As can be seen from Figure 5It can be seen that Bi, Ni and O elements are uniformly distributed on the metal particles, and C element is uniformly distributed around the metal particles; this indicates that the BiNi alloy is successfully immobilized on the surface of the carbon material, and the BiNi alloy is slightly oxidized. From the EDS mapping of the metal particles in Fig. 6, it can be seen that the signal intensities of Bi and Ni are comparable, which further verifies the successful synthesis of the BiNi alloy. Figure 5 f is Figure 5 e The line scanning spectrum of the metal particles can be seen that the signal intensities of Bi and Ni are comparable, which further verifies the successful synthesis of the BiNi alloy.

[0055] Figure 6 is the Raman spectrum of the BiNi / C-0.125 prepared in Example 6; it can be seen from the figure that the characteristic peak at 94 cm −1 belongs to Bi-Ni; the properties of the graphite carbon can be reflected by the intensity ratio of the D band and the G band, and the ratio of the intensity ratio of the D band and the G band is about 0.94; this indicates that the carbon material of the BiNi / C-0.125 has a rich defect structure; the analysis results of the Raman test further confirm the microstructure of the BiNi / C-0.125, i.e. the BiNi nano-alloy particles are loaded on the surface of the carbon material.

[0056] Figure 7 is the XRD pattern of the material prepared in Example 7; wherein the peaks at 37.2° (111), 43.3° (200), 62.9° (220), and 75.4° (311) belong to the characteristic peaks of NiO; the peaks at 44.5° (111) and 51.9° (200) belong to the characteristic peaks of Ni; indicating that the main components of the obtained material are Ni and NiO. It can be known that as the molar ratio of bismuth nitrate pentahydrate and nickel chloride hexahydrate is further reduced, when the molar ratio of Bi to Ni is less than 0.1, no BiNi alloy is generated in the obtained material; this may be due to the too small amount of the added metal bismuth source.

[0057] Figure 8 is the microstructure schematic diagram of the BiNi nano-alloy particle loaded carbon electric material (BiNi / C-0.125) of the application; Figure 8 is the microstructure schematic diagram drawn according to the analysis results of Figure 3 and Figure 5 . At this time, the BiNi nano-alloy particles and part of the metal nickel particles are uniformly dispersed and immobilized on the surface of the carbon material or in the pores of the carbon material.

[0058] Example 8: Performance evaluation of the BiNi nano-alloy particle loaded carbon material of Examples 1-6 for preparing hydrogen peroxide electrode material.

[0059] The performance of the BiNi nano-alloy particles loaded with carbon prepared in Examples 1-6 in preparing hydrogen peroxide via a two-electrode oxygen reduction reaction was evaluated using a rotating ring-disk electrode in a standard three-electrode system. In the three-electrode system, the counter electrode was a platinum mesh, the reference electrode was an Ag / AgCl electrode, and the rotating ring-disk electrode containing the BiNi nano-alloy particles loaded with carbon prepared in Examples 1-6 was used as the working electrode. 5.0 mg of the BiNi nano-alloy particles loaded with carbon prepared in Examples 1-6 were dispersed in 1.0 mL of a mixed solution containing 800 μL isopropanol, 170 μL deionized water, and 30 μL of Nafion solution (5 wt%), and sonicated for at least 1 hour to form a homogeneous suspension. 5 μL of the suspension was then dropped onto the disk surface of the rotating ring-disk electrode. Before electrochemical testing, the sample was reacted in a 0.1 MkOH electrolyte saturated with N2 at 100 mV·s⁻¹. -1 Cyclic voltammetry was performed at a scan rate of 40 cycles to activate the electrode surface; all potentials were relative to the standard hydrogen electrode (RHE):E RHE = E Ag / AgCl + 0.197 + 0.059 × pH; Rotating ring-disc electrode tests were performed at 1600 rpm in O2-saturated 0.1 MkOH electrolyte with a scan rate of 5 mV·s. -1 The ring potential was set to 1.4 V vs. RHE. The selectivity of hydrogen peroxide (H₂O₂%) and the number of electrons transferred (n) were calculated using the following formulas:

[0060]

[0061] The performance of the two-electron oxygen reduction reaction for preparing hydrogen peroxide using BiNi nano-alloy particles loaded with carbon materials in Examples 1-6 is as follows: Figure 9 As shown; Figure 9 a is a linear sweep voltammogram, from which... Figure 9 As can be seen from a, as the molar ratio of bismuth nitrate pentahydrate to nickel chloride hexahydrate decreases, the onset potential of the obtained material gradually increases, and the disk current and ring current also gradually increase; among them, BiNi / C-0.125 has an onset potential of 0.76 V vs. RHE, and has a large disk current and ring current, indicating its excellent two-electron oxygen reduction reaction performance. Figure 9 b and 9c represent the selectivity of hydrogen peroxide (H2O2%) and the number of electrons transferred in the reaction (n), respectively. Figure 9 As shown in b, within a wide potential window of 0.2-0.6V, BiNi / C-0.125 exhibits the highest hydrogen peroxide selectivity, reaching up to 98%; Figure 9It can be known that the electron transfer number of BiNi / C-0.125 is closest to 2, which indicates that BiNi / C-0.125 has the best two-electron oxygen reduction performance for preparing hydrogen peroxide; BiNi / C-2, BiNi / C-1, BiNi / C-0.5, BiNi / C-0.375 and BiNi / C-0.25 have poor two-electron oxygen reduction performance for preparing hydrogen peroxide, which may be caused by the following reasons: first, the size of the BiNi alloy particles is large (100nm-20um) and uneven, which leads to low exposure of metal active sites; second, the large size of the BiNi alloy particles cannot be stably supported on the surface of the carbon material, which leads to reduced stability; third, the accumulation of a large amount of BiNi alloy particles with large size leads to low specific surface area of the material, and the reactants are difficult to reach the active sites; fourth, as the molar ratio of bismuth nitrate pentahydrate to nickel chloride hexahydrate increases, the conductivity of the obtained material gradually decreases, which hinders the electron transfer process.

[0062] As can be seen from the above examples, the preparation method proposed in the present application can well realize the preparation of BiNi nano-alloy particle loaded carbon material, and by changing the proportion of metal sources, nano non-noble metal alloy particles can be prepared and loaded on the sheet graphite carbon material; among them, the electron transfer number of BiNi / C-0.125 nano-alloy particle loaded carbon material in the two-electron oxygen reduction reaction for preparing hydrogen peroxide is closest to 2, and the selectivity of hydrogen peroxide is the highest, which can reach 98%.

[0063] The above is only used to introduce the specific embodiments of the present application, but the technical solutions proposed in the present application are not limited to the above methods. Without departing from the basic principles of the present technology, equivalent modifications and changes made by those skilled in the art to the technical solutions proposed in the present application should be covered in the scope of the claims of the present application.

Claims

1. A BiNi nanoalloy particle supported carbon material, characterized in that, It is BiNi nano-alloy particles uniformly loaded on sheet graphite carbon, the intensity ratio of D band and G band of the sheet graphite carbon is 0.94; the particle size of the BiNi nano-alloy particles is 2.0-20.0 nm; the preparation method of the BiNi nano-alloy particle loaded carbon material comprises the following steps: (1) preparing Bi / Ni-MOF: dissolving terephthalic acid in a mixed solution of N,N-dimethylformamide, anhydrous ethanol and deionized water, and ultrasonic for a period of time; then, adding bismuth salt and nickel salt with a certain molar ratio, and ultrasonic for a period of time to obtain a mixed solution; hydrothermal reaction of the above mixed solution at a certain temperature for a period of time, separation, washing and drying to obtain Bi / Ni-MOF; (2) BiNi nano-alloy particle loaded carbon material: placing the Bi / Ni-MOF prepared in step (1) in a nitrogen atmosphere and calcining at high temperature for a period of time, and cooling to room temperature to obtain the BiNi nano-alloy particle loaded carbon material; the bismuth salt in step (1) is bismuth nitrate pentahydrate, and the nickel salt is nickel chloride hexahydrate; the molar ratio of bismuth nitrate pentahydrate and nickel chloride hexahydrate is 0.

125.

2. The method for preparing BiNi nano-alloy particles-supported carbon materials according to claim 1, characterized in that, It comprises the following steps: (1) preparing Bi / Ni-MOF: dissolving terephthalic acid in a mixed solution of N,N-dimethylformamide, anhydrous ethanol and deionized water, and ultrasonic for a period of time; then, adding bismuth salt and nickel salt with a certain molar ratio, and ultrasonic for a period of time to obtain a mixed solution; hydrothermal reaction of the above mixed solution at a certain temperature for a period of time, separation, washing and drying to obtain Bi / Ni-MOF; (2) BiNi nano-alloy particle loaded carbon material: placing the Bi / Ni-MOF prepared in step (1) in a nitrogen atmosphere and calcining at high temperature for a period of time, and cooling to room temperature to obtain the BiNi nano-alloy particle loaded carbon material; The bismuth salt in step (1) is bismuth nitrate pentahydrate, and the nickel salt is nickel chloride hexahydrate; the molar ratio of bismuth nitrate pentahydrate and nickel chloride hexahydrate is 0.

125.

3. The production method according to claim 2, characterized by, The ultrasonic time in step (1) is 5-30 minutes; the hydrothermal reaction temperature is 160-200℃, and the hydrothermal reaction time is 12-20 hours; the washing is deionized water and anhydrous ethanol, and the washing is not less than three times.

4. The production method according to claim 2, characterized by, The high-temperature calcination heating rate in step (2) is 5℃ / min, the calcination temperature is 600-800℃, and the calcination time is 2-6 hours.

5. The use of the BiNi nano-alloy particle loaded carbon material according to claim 1 for electrode material.

6. Use according to claim 5, characterized in that, The use of the BiNi nano-alloy particle loaded carbon material for preparing hydrogen peroxide electrode material.

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