A nickel-based catalytic material, a preparation method thereof and application thereof in synthesis of hydrogen peroxide
By preparing nickel-based catalytic materials, the problems of poor regulation of active sites and insufficient structural stability in existing catalytic materials were solved, achieving efficient synthesis of hydrogen peroxide with a yield of over 85%.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- BEIJING NORMAL UNIV AT ZHUHAI
- Filing Date
- 2026-02-12
- Publication Date
- 2026-06-05
AI Technical Summary
Existing catalytic materials suffer from problems such as poor active site regulation, slow reaction kinetics, low selectivity, and insufficient structural stability in the synthesis of hydrogen peroxide, resulting in low hydrogen peroxide yield and low Faraday efficiency.
A method for preparing nickel-based catalytic materials was developed, which synthesized nickel-based catalytic materials under an oxygen-free environment through specific raw materials and reaction processes. The method involved mixing 2,5-diaminobenzene-1,4-diphenol or its hydrochloride with nickel salt, adding an alkaline solvent and heating the reaction, separating and drying the mixture to prepare nickel-based catalytic materials with high catalytic activity.
It achieved a significant increase in hydrogen peroxide yield, exceeding 50% in existing technologies, reaching over 85%, while maintaining good catalytic stability.
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Figure CN122145326A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of catalyst technology, and specifically relates to a nickel-based catalytic material, its preparation method, and its application in the synthesis of hydrogen peroxide. Background Technology
[0002] In existing technologies for synthesizing hydrogen peroxide using the electrochemical two-electron oxygen reduction reaction, the insufficient performance of catalytic materials is the core bottleneck limiting its yield and industrial application prospects.
[0003] Currently, widely studied transition metal-based catalysts, especially non-noble metal materials, generally suffer from the critical problem of balancing intrinsic activity and selectivity. On the one hand, the active sites of most catalytic materials exhibit poor energy barrier regulation for the oxygen reduction reaction, leading to sluggish reaction kinetics and low current density, directly limiting the hydrogen peroxide formation rate. More significantly, their electronic structures often fail to precisely match the two-electron reaction pathway, resulting in either excessively strong or weak adsorption energies for the key intermediate *OOH, causing a significant decrease in selectivity and triggering severe side reactions. A large amount of reactant oxygen is directly reduced to water, resulting in a double loss of target product yield and Faraday efficiency. On the other hand, existing catalysts are prone to dissolution, aggregation, or surface oxidation of active components during long-term operation, exhibiting insufficient structural stability and leading to rapid degradation of catalytic performance, failing to meet the requirements of continuous and efficient production.
[0004] Therefore, developing a new type of high-efficiency electrocatalyst is of great significance for solving the problem of low hydrogen peroxide yield in existing technologies. Summary of the Invention
[0005] This invention aims to at least solve one of the technical problems existing in the prior art. To this end, this invention proposes a nickel-based catalytic material, its preparation method, and its application in the synthesis of hydrogen peroxide. The nickel-based catalytic material of this invention can efficiently catalyze the synthesis of hydrogen peroxide without using precious metals, resulting in a significantly higher yield than existing technologies (the yield of hydrogen peroxide synthesized by non-precious metal catalysts in existing technologies is generally around 50%), for example, a yield exceeding 85%.
[0006] The first aspect of the present invention provides a method for preparing a nickel-based catalytic material.
[0007] A method for preparing a nickel-based catalytic material includes the following steps:
[0008] Under a protective gas atmosphere, 2,5-diaminobenzene-1,4-diphenol (DABDH) or 2,5-diaminobenzene-1,4-diphenol dihydrochloride (DABDH･2HCl), nickel salt, and solvent are mixed, then an alkali is added, and the mixture is heated to carry out the reaction, and the nickel-based catalyst material is obtained by separation.
[0009] Preferably, the protective gas includes a rare gas. The rare gas can be argon, helium, or krypton. The purpose of the protective gas atmosphere is to provide an oxygen-free environment.
[0010] Preferably, the molar ratio of the 2,5-diaminobenzene-1,4-diphenol or 2,5-diaminobenzene-1,4-diphenol dihydrochloride to the nickel salt is 0.4:(0.8-1.5). For example, it is 0.4:1.2.
[0011] Preferably, the nickel salt comprises nickel nitrate or nickel nitrate hexahydrate.
[0012] Preferably, the solvent includes deionized water.
[0013] Preferably, the ratio of nickel salt to solvent is 1.2 mmol: (20-50) mL. For example, 1.2 mmol: 30 mL.
[0014] Preferably, the base comprises ethylenediamine.
[0015] Preferably, the volume of the solvent to ethylenediamine is 30 mL: (50-100) μL. For example, 30 mL: 75 μL.
[0016] Preferably, the reaction is carried out by heating to 75-85°C and reacting for 10-12 hours. For example, heating to 80°C and reacting for 12 hours.
[0017] Preferably, the separation process includes centrifugation, washing, and drying.
[0018] Preferably, the washing is performed using deionized water and ethanol.
[0019] Preferably, the drying is performed at 90-110°C for 10-12 hours.
[0020] A second aspect of the present invention provides a method for preparing a nickel-based catalytic material.
[0021] A nickel-based catalytic material is prepared by the above-described preparation method.
[0022] A third aspect of the present invention provides an application of a nickel-based catalytic material.
[0023] The application of the nickel-based catalyst material prepared by the above method in the synthesis of hydrogen peroxide.
[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0025] The preparation method described in this invention, through specific raw materials and reaction processes, enables the prepared nickel-based catalytic material to have good ORR (oxygen reduction reaction) catalytic activity, and can efficiently catalyze the synthesis of hydrogen peroxide, resulting in a hydrogen peroxide yield that is significantly higher than that of existing technologies (the yield of hydrogen peroxide synthesized by non-precious metal catalysts in existing technologies is generally around 50%), for example, the yield of hydrogen peroxide is higher than 85%. Attached Figure Description
[0026] Figure 1 The XRD patterns of the catalysts prepared in Example 1 and Comparative Examples 1-3 are shown below.
[0027] Figure 2 XPS spectra of the catalytic materials prepared in Example 1 and Comparative Examples 2-3;
[0028] Figure 3 Cyclic voltammetry curves of the catalysts prepared in Example 1 and Comparative Examples 2-3 in oxygen-saturated 0.1 M KOH solution;
[0029] Figure 4 The hydrogen peroxide yield during the electrocatalytic synthesis of hydrogen peroxide using the catalytic materials prepared in Examples 1 and 2-3 is shown.
[0030] Figure 5 The hydrogen peroxide yield was measured during the cyclic electrocatalytic synthesis of hydrogen peroxide using the catalytic material prepared in Example 1 at a constant potential of 0.4V. Detailed Implementation
[0031] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.
[0032] Unless otherwise specified, the raw materials, reagents or devices used in the following examples are available from conventional commercial sources or can be obtained by existing known methods.
[0033] Example 1
[0034] A method for preparing a nickel-based catalytic material includes the following steps:
[0035] In an oxygen-free glove box (with argon as the protective gas), 0.4 mmol of 2,5-diaminobenzene-1,4-diphenol dihydrochloride (DABDH·2HCl) and 1.2 mmol of nickel nitrate hexahydrate were dissolved in 15 mL of deionized water with stirring. 75 μL of ethylenediamine was added and stirred until homogeneous. 15 mL of oxygen-free deionized water was then added and stirred until homogeneous. The mixture was then transferred to a reaction vessel, which was removed from the glove box and placed in a forced-air drying oven at 80 °C for 12 hours. After the reaction was completed, the product was obtained by centrifugation. The product was washed twice with deionized water and once with ethanol. The washed product was then placed in a vacuum oven and vacuum dried for 12 hours to obtain the nickel-based catalyst (denoted as Ni-DABDH).
[0036] Example 2
[0037] A method for preparing a nickel-based catalytic material includes the following steps:
[0038] In an oxygen-free glove box (with argon as the protective gas), 0.4 mmol of 2,5-diaminobenzene-1,4-diphenol dihydrochloride (DABDH·2HCl) and 1.4 mmol of nickel nitrate hexahydrate were dissolved in 15 mL of deionized water with stirring. 85 μL of ethylenediamine was added and stirred until homogeneous. 15 mL of deionized water was added and stirred until homogeneous. The mixture was then transferred to a reaction vessel, which was removed from the glove box and placed in a forced-air drying oven at 85°C for 10 hours. After the reaction was completed, the product was obtained by centrifugation. The product was washed twice with deionized water and once with ethanol. The washed product was then placed in a vacuum oven and vacuum dried for 12 hours to obtain the nickel-based catalyst (denoted as Ni-DABDH-2).
[0039] Comparative Example 1
[0040] A method for preparing a cobalt-based catalytic material includes the following steps:
[0041] In an oxygen-free glove box (with argon as the protective gas), 0.5 mmol of 2,5-diaminobenzene-1,4-diphenol dihydrochloride was dissolved in 15 mL of deionized water with stirring, and 0.5 mmol of anhydrous cobalt chloride was dissolved in 15 mL of deionized water with stirring. After the two solutions were mixed evenly, 200 μL of ammonia water was added and the mixture was stirred for 5 minutes. Then, the mixture was transferred to a reaction vessel, which was then removed from the glove box and placed in a forced-air drying oven at 120°C for 12 hours. After the reaction was completed, the product was obtained by centrifugation. The product was washed repeatedly with deionized water and acetone until the pH of the supernatant was neutral. The washed product was then placed in a vacuum oven and dried under vacuum at 80°C for 12 hours to obtain the cobalt-based catalyst (denoted as Co-DABDH).
[0042] Comparative Example 2
[0043] A method for preparing a nickel-based catalytic material includes the following steps:
[0044] In an oxygen-free glove box (with argon as the protective gas), 0.2 mmol of 2,5-diamino-1,4-benzenedithiol dihydrochloride was dissolved in 20 mL of DMF (N,N-dimethylformamide) with stirring, and 0.2 mmol of nickel chloride hexahydrate was dissolved in 20 mL of deionized water with stirring. After the two solutions were mixed evenly, 400 μL of 0.6 mol / L ammonia water was added and the mixture was stirred for 5 minutes. The mixture was then transferred to a reaction vessel, which was removed from the glove box and placed in a forced-air drying oven at 100 °C for 12 hours. After the reaction was completed, the product was obtained by centrifugation. The product was washed repeatedly with deionized water and acetone until the pH of the supernatant was neutral. The washed product was then placed in a vacuum oven and dried under vacuum at 100 °C for 12 hours to obtain the nickel-based catalyst (denoted as Ni-DABDT).
[0045] Comparative Example 3
[0046] A method for preparing a nickel-based catalytic material includes the following steps:
[0047] 1 mmol of 2,3,5,6−tetra(amino)-p-benzoquinone (TABQ) was placed in a 100 mL beaker and dissolved in 50 mL of DMF. 2 mmol of nickel chloride hexahydrate was dissolved in 25 mL of deionized water and 8.35 mL of concentrated ammonia (26.5% by mass) was added. The two solutions were mixed and stirred at room temperature for 12 hours. After the reaction was completed, a black product was obtained by centrifugation. The product was washed repeatedly with deionized water and acetone until the pH of the supernatant was neutral. The washed product was then placed in a vacuum oven and dried under vacuum at 80 °C for 12 hours to obtain the nickel-based catalyst (denoted as Ni-TABQ).
[0048] Product effectiveness test
[0049] 1. Structural characterization
[0050] Figure 1 The XRD patterns of the catalytic materials prepared in Example 1 and Comparative Examples 1-3 are shown; where “Intensity” represents intensity and “2θ (degree)” represents diffraction angle (degrees).
[0051] The crystal structures of the catalytic materials prepared in Example 1 and Comparative Examples 1-3 were analyzed by powder XRD. The results are as follows: Figure 1 As shown, Ni-DABDH exhibits distinct XRD peaks at 11.74°, 17.74°, and 20.22°, and the sharp peak shapes indicate that it has high crystallinity.
[0052] Since Ni-DABDH has not been reported before, this invention fits its structure. It can be seen that the characteristic peaks of the experimental XRD spectrum of Ni-DABDH and the theoretical simulated XRD spectrum correspond completely, further verifying that the present invention has successfully synthesized Ni-DABDH crystal.
[0053] The characteristic peaks of the XRD pattern of Co-DABDH are consistent with those of Ni-DABDH. Ni-DABDT and Ni-TABQ, as controls, also show a certain degree of crystallinity.
[0054] Figure 2 XPS spectra of the catalytic materials prepared in Example 1 and Comparative Examples 2-3; where "Intensity" represents intensity and "Binding energy" represents binding energy.
[0055] The valence states of the catalytic materials prepared in Example 1 and Comparative Examples 2-3 were characterized by XPS spectra. Figure 2 This is also a fine spectrum of Ni2p, with the peak at 854.1 corresponding to Ni. 2+ 2p 3 / 2 This indicates that nickel ions in Ni-DABDH, Ni-DABDT, and Ni-TABQ exist in a +2 valence state.
[0056] 2. Performance testing of hydrogen peroxide synthesis
[0057] Figure 3 Cyclic voltammetry curves of the catalysts prepared in Example 1 and Comparative Examples 2-3 in oxygen-saturated 0.1 M KOH solution; Figure 4 ("Potential (V vs. RHE)" represents the potential relative to the reversible hydrogen electrode, and "Currentdensity" represents the current density.) The test was conducted at a rotation speed of 1600 rpm and a scan rate of 5 mV / s. −1 .
[0058] Figure 4 The hydrogen peroxide yield is the result of electrocatalytic synthesis of hydrogen peroxide using the catalytic materials prepared in Examples 1 and Comparative Examples 2-3. Here, "Peroxide yield" represents the hydrogen peroxide yield, and "Potential (V vs. RHE)" represents the potential relative to the reversible hydrogen electrode.
[0059] First, the 2e-ORR performance of Ni-DABDH prepared in Example 1 and Ni-DABDT, Ni-TABQ, and Co-DABDH prepared in Comparative Examples 1-3 were evaluated. For example, the ORR polarization curves are shown below. Figure 3As shown, the peak potential of Ni-DABDH is approximately 0.71 V, that of Ni-DABDT and Ni-TABQ is approximately 0.80 V, and that of Co-DABDH is approximately 0.66 V, indicating that all four catalytic materials have good ORR performance.
[0060] like Figure 4 As shown, Ni-DABDH exhibits a hydrogen peroxide yield of nearly 90% in the voltage range of 0.3-0.65V, which is much higher than that of Ni-DABDT (55%), Ni-TABQ (35%) and Co-DABDH (45%), indicating that Ni-DABDH has excellent 2e-ORR performance.
[0061] The formula for calculating the hydrogen peroxide yield is as follows:
[0062] ;
[0063] It is the current in the disk. It is the ring disk current, and the N collection rate is 0.37. This indicates the yield of hydrogen peroxide.
[0064] Figure 5 The hydrogen peroxide yield is calculated using the catalytic material prepared in Example 1 during cyclic electrocatalytic synthesis of hydrogen peroxide at a constant potential of 0.4V. Here, "Peroxide yield" represents the hydrogen peroxide yield, and "Time (h)" represents the time (hours).
[0065] from Figure 5 As can be seen, after 10 hours of constant potential testing, the hydrogen peroxide yield of the catalyst material (Ni-DABDH) prepared in Example 1 can still be maintained at close to 90%, indicating that the catalyst material has good catalytic stability.
Claims
1. A method for preparing a nickel-based catalytic material, characterized in that, Includes the following steps: Under a protective gas atmosphere, 2,5-diaminobenzene-1,4-diphenol or 2,5-diaminobenzene-1,4-diphenol dihydrochloride is mixed with nickel salt and solvent, then alkali is added, and the mixture is heated to carry out the reaction, and the nickel-based catalyst material is obtained by separation.
2. The preparation method according to claim 1, characterized in that, The molar ratio of the 2,5-diaminobenzene-1,4-diphenol or 2,5-diaminobenzene-1,4-diphenol dihydrochloride to the nickel salt is 0.4:(0.8-1.5).
3. The preparation method according to claim 1, characterized in that, The nickel salt includes nickel nitrate or nickel nitrate hexahydrate.
4. The preparation method according to claim 1, characterized in that, The solvent includes deionized water.
5. The preparation method according to claim 1, characterized in that, The ratio of nickel salt to solvent is 1.2 mmol: (20-50) mL.
6. The preparation method according to claim 1, characterized in that, The base includes ethylenediamine.
7. The preparation method according to claim 6, characterized in that, The volume of the solvent and ethylenediamine is 30 mL: (50-100) μL.
8. The preparation method according to claim 1, characterized in that, The reaction is carried out by heating to 75-85℃ and reacting for 10-12 hours.
9. A nickel-based catalytic material, characterized in that, It is prepared by the preparation method according to any one of claims 1-8.
10. The application of the nickel-based catalyst material prepared by the preparation method according to any one of claims 1-8 in the synthesis of hydrogen peroxide.