Aspergillus oryzae spore carbon / nickel-cobalt electrolytic water hydrogen evolution electrocatalyst and preparation method and application thereof
By using Aspergillus oryzae spore carbon/nickel cobalt electrocatalyst in electrolytic water hydrogen production technology, using carbon/nickel cobalt composites doped with N, P, and S elements, the high price of precious metal platinum and poor packaging effect of artificial carbon materials is solved. The problem is that efficient and low-cost electrocatalytic performance and environmentally friendly hydrogen energy production have been achieved.
Patent Information
- Application Number
- CN202411357417.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-27
- Publication Date
- 2024-12-31
AI Technical Summary
In the existing electrolytic hydrogen production technology, although precious metal platinum (Pt) and its alloys have excellent performance, they have high prices and low natural abundance, which hinder the commercialization process of electrolytic hydrogen production. In addition, artificial carbon materials have a negative impact on metal nickel particles. The packaging effect is poor, resulting in poor hydrogen evolution performance.
Using Aspergillus oryzae spore carbon/nickel cobalt electrocatalyst, the reaction between nickel acetate and cobalt acetate and Aspergillus oryzae spores at high temperatures to form nickel cobalt nanoclusters and dopant N, P, and S elements on the conductive carbon substrate to enhance the catalyst Activity and stability to prevent nickel particles from falling off.
It achieves efficient and low-cost electrocatalytic performance, and the preparation method is simple and easy to scale. Aspergillus oryzae comes from moldy rice, which realizes turning waste into treasure, saving energy and reducing emissions.
Smart Images
Figure CN119215954A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of water electrolysis for hydrogen evolution, and in particular to an Aspergillus oryzae spore carbon / nickel-cobalt water electrolysis for hydrogen evolution electrocatalyst, and a preparation method and application thereof. Background Art
[0002] At present, the energy crisis is becoming increasingly serious and environmental pollution is becoming increasingly severe. Hydrogen energy is safe, non-toxic and has a high density, which is superior to other new energy sources. It is currently widely regarded as the best new energy carrier in the future. There are many ways to produce hydrogen. Among them, water electrolysis is one of the current mainstream hydrogen production methods because of its simple production technology, safety, reliability, low cost and low pollution. Water electrolysis requires a certain amount of electricity to decompose water to produce hydrogen energy. In order to reduce the consumption of electricity, the development of high-performance electrocatalysts is imminent. At present, the electrocatalysts with the best performance are precious metal platinum (Pt) and its alloys. However, the high price and low natural abundance hinder its commercialization process of water electrolysis. Therefore, the design and construction of efficient and low-cost non-precious metal electrocatalysts are of great research significance to promote the commercial development of water electrolysis hydrogen production. Summary of the invention
[0003] The purpose of the present invention is to overcome the defects of the prior art, and to provide an Aspergillus oryzae spore carbon / nickel-cobalt water electrolysis hydrogen evolution electrocatalyst and its preparation method and application. The Aspergillus oryzae spore carbon / nickel-cobalt water electrolysis hydrogen evolution electrocatalyst has excellent electrocatalytic performance and lower price, and the preparation method is simple and convenient, and easy to prepare on a large scale. In addition, Aspergillus oryzae is derived from moldy rice, which turns waste into treasure and saves energy and reduces emissions.
[0004] The purpose of the present invention can be achieved through the following technical solutions:
[0005] A method for preparing an Aspergillus oryzae spore carbon / nickel-cobalt water electrolysis hydrogen evolution electrocatalyst comprises the following steps:
[0006] S1. Weigh nickel acetate and cobalt acetate and dissolve them in deionized water to prepare a mixed solution;
[0007] S2, placing the Aspergillus oryzae spores and the mixed solution in an oven for heating reaction;
[0008] S3, centrifuging the mixed solution after the heating reaction to obtain Aspergillus oryzae spores / nickel-cobalt precursor;
[0009] S4. Place the Aspergillus oryzae spore / nickel-cobalt precursor in a tubular furnace and introduce inert gas for high-temperature sintering to obtain the Aspergillus oryzae spore carbon / nickel-cobalt electrocatalyst.
[0010] Furthermore, in step S2, the mixed solution container is a blue-capped bottle, the heating temperature is 50-90° C., and the reaction time is 1-10 h.
[0011] Furthermore, in step S4, the high temperature sintering temperature is 600-850° C., and the sintering time is 1-3 hours.
[0012] The present invention also provides an Aspergillus oryzae spore carbon / nickel-cobalt water electrolysis hydrogen evolution electrocatalyst, which is prepared by the above preparation method.
[0013] The present invention also provides application of the Aspergillus oryzae spore carbon / nickel-cobalt catalyst in hydrogen evolution by water electrolysis.
[0014] It should be further explained that the activity and stability of nickel-based catalysts can be improved by constructing metal nickel-cobalt nanoclusters and confining them in a conductive carbon substrate. However, the artificial carbon materials used in most reports do not have a good effect on the encapsulation or attachment of metal nickel particles. Under high current density, nickel particles are easily agglomerated or fall off the carbon substrate, thus showing poor hydrogen evolution performance. In addition, artificial carbon materials lack the doping of non-metallic atoms, making it difficult to enhance the hydrogen proton evolution of the catalyst.
[0015] In this regard, the present invention proposes to use Aspergillus oryzae derived carbon in situ doped with N, P and S elements as a carrier to prepare a new carbon / nickel-cobalt-based composite electrocatalyst. On the one hand, the catalyst uses moldy rice as a carbon source, turning waste into treasure. On the other hand, the miscellaneous elements such as N, P, and S in Aspergillus oryzae can better grasp the metal particles and prevent them from falling off during hydrogen evolution under high current. In addition, the miscellaneous elements N, P and S can further enhance the activity of the nickel-cobalt catalyst. In summary, the present invention has taken a unique approach and proposed a method for constructing a new carbon / nickel-cobalt-based composite, which is expected to achieve pioneering results in enhancing the performance of non-precious metal electrocatalysts and expand the scientific frontier.
[0016] Beneficial effects of the present invention:
[0017] The Aspergillus oryzae spore carbon / nickel-cobalt electrocatalyst prepared by the invention has excellent electrocatalytic performance and lower price; meanwhile, the preparation method is simple and convenient, and easy to prepare on a large scale. In addition, Aspergillus oryzae is derived from moldy rice, which turns waste into treasure and saves energy and reduces emissions. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] The present invention will be further described below in conjunction with the accompanying drawings.
[0019] Figure 1 The figure is a schematic flow chart of a method for preparing an Aspergillus oryzae spore carbon / nickel-cobalt catalyst according to an embodiment of the present invention.
[0020] Figure 2 1 is a schematic diagram of the structure of the Aspergillus oryzae spore carbon / nickel-cobalt catalyst prepared according to Example 1 of the present invention.
[0021] Figure 3 This is a high-resolution transmission electron micrograph of the Aspergillus oryzae spore carbon / nickel-cobalt catalyst prepared according to Example 2 of the present invention.
[0022] Figure 4 It is a linear sweep voltammetric curve of the hydrogen production performance of the Aspergillus oryzae spore carbon / nickel-cobalt catalyst prepared according to Example 3 of the present invention. DETAILED DESCRIPTION
[0023] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0024] The embodiment of the present invention provides a method for preparing an Aspergillus oryzae spore carbon / nickel-cobalt hydrogen evolution electrocatalyst. Figure 1 The process of the preparation method is shown, as Figure 1 As shown, the preparation method comprises the following steps:
[0025] S1. Weigh nickel acetate and cobalt acetate and dissolve them in deionized water to prepare a mixed solution.
[0026] S2, placing the Aspergillus oryzae spores and the mixed solution in an oven for heating reaction. The mixed solution container is a blue-capped bottle, the heating temperature is 50-90° C., and the reaction time is 1-10 hours.
[0027] S3. Centrifuge the mixed solution after the heating reaction to obtain Aspergillus oryzae spores / nickel-cobalt precursor.
[0028] S4. Place the Aspergillus oryzae spore / nickel-cobalt precursor in a tubular furnace and introduce argon gas for high-temperature sintering to obtain an Aspergillus oryzae spore carbon / nickel-cobalt electrocatalyst. The high-temperature sintering temperature is 600-1050° C. and the sintering time is 1-3 hours.
[0029] The preparation method is described below in conjunction with specific examples.
[0030] Example 1
[0031] Weigh 0.1g nickel acetate and 0.1g cobalt acetate and dissolve them in 60mL deionized water, stirring for 20 minutes until completely dissolved. Transfer the Aspergillus oryzae spores and the above mixed solution to a blue-capped bottle and hydrothermally react at 90°C for 5 hours. After the reaction, cool to room temperature and centrifuge the solution after the heating reaction to obtain an Aspergillus oryzae spore / nickel-cobalt precursor. Finally, place the Aspergillus oryzae spore / nickel-cobalt precursor in a tubular furnace, introduce argon gas and sinter at 950°C for 1 hour and 30 minutes to obtain the Aspergillus oryzae spore carbon / nickel-cobalt electrocatalyst target product. Figure 2 This is a scanning electron microscope image of the Aspergillus oryzae spore carbon / nickel-cobalt electrocatalyst prepared in Example 1.
[0032] Example 2
[0033] Weigh 0.2g of nickel acetate and 0.2g of cobalt acetate and dissolve them in 120mL of deionized water, and stir for 10 minutes until completely dissolved. Transfer the Aspergillus oryzae spores and the above mixed solution to a blue-capped bottle and heat the reaction at 80°C for 8 hours. After the heating reaction, cool to room temperature and centrifuge the solution after the heating reaction to obtain an Aspergillus oryzae spore / nickel-cobalt precursor. Finally, place the Aspergillus oryzae spore / nickel-cobalt precursor in a tubular furnace, introduce argon gas and sinter at 1050°C for 2 hours to obtain the Aspergillus oryzae spore carbon / nickel-cobalt electrocatalyst target product. Figure 3 This is a high-resolution transmission electron microscope image of the Aspergillus oryzae spore carbon / nickel-cobalt electrocatalyst prepared in Example 2.
[0034] Example 3
[0035] Weigh 0.25g of nickel acetate and 0.25g of cobalt acetate and dissolve them in 125mL of deionized water, and stir for 20 minutes until completely dissolved. Transfer the Aspergillus oryzae spores and the above mixed solution to a blue-capped bottle and heat the reaction at 75°C for 10 hours. After the heating reaction, cool to room temperature and centrifuge the solution after the heating reaction to obtain the Aspergillus oryzae spore / nickel-cobalt precursor. Finally, place the Aspergillus oryzae spore / nickel-cobalt precursor in a tubular furnace, introduce argon gas and sinter at 950°C for 2 hours to obtain the Aspergillus oryzae spore carbon / nickel-cobalt electrocatalyst target product. Figure 4 This is a linear sweep voltammogram of the hydrogen production performance of the Aspergillus oryzae spore carbon / nickel-cobalt electrocatalyst prepared in Example 3.
[0036] The performance of the Aspergillus oryzae spore carbon / nickel-cobalt electrocatalysts prepared in Examples 1 to 3 was tested below.
[0037] 10 mg of Aspergillus oryzae spore carbon / nickel-cobalt electrocatalyst prepared in Examples 1 to 3 was mixed with 2 mL of water and 20 μL of Nafion (5 wt% ethanol) and ultrasonicated for 15 minutes to obtain a uniform slurry. Then, the slurry was drop-coated on a 1×1 cm 2 Aspergillus oryzae spore carbon / nickel-cobalt electrodes were formed on carbon paper, and the above electrodes were directly used as test electrodes for electrochemical tests in a three-electrode battery system, with saturated calomel electrode (SCE), carbon rod and 1 M KOH solution as reference electrode, comparison electrode and electrolyte, respectively.
[0038] The results of the performance test are as follows:
[0039] The Aspergillus oryzae spore carbon / nickel-cobalt electrocatalysts prepared in Examples 1 to 3 were subjected to an electrochemical reaction at 10 mA·cm -2The overpotentials under current density are 98mV, 101mV and 94mV respectively. After 2000 CV cycles, the overpotential retention rate of the Aspergillus oryzae spore carbon / nickel cobalt electrocatalyst is more than 99%. It can be seen that the Aspergillus oryzae spore carbon / nickel cobalt electrocatalyst obtained in the above embodiment has low overpotential and good cycle stability. Therefore, the designed Aspergillus oryzae spore carbon / nickel cobalt has the characteristics of high cycle life and low overpotential, and Aspergillus oryzae spores are derived from moldy rice, turning waste into treasure, low price, and can be applied to fields such as electrolysis of water to produce hydrogen.
[0040] The above specific implementation method part specifically introduces the analytical method involved in the present invention. It should be noted that the above introduction is only to help those skilled in the art better understand the method and ideas of the present invention, rather than limiting the relevant content. Without departing from the principle of the present invention, those skilled in the art may also make appropriate adjustments or modifications to the present invention, and the above adjustments and modifications shall also fall within the scope of protection of the present invention.
Claims
1. A method for preparing an Aspergillus oryzae spore carbon / nickel-cobalt water electrolysis hydrogen evolution electrocatalyst, characterized in that: The following steps are involved: S1. Weigh nickel acetate and cobalt acetate and dissolve them in deionized water to prepare a mixed solution; S2, placing the Aspergillus oryzae spores and the mixed solution in an oven for heating reaction; S3, centrifuging the mixed solution after the heating reaction to obtain Aspergillus oryzae spores / nickel-cobalt precursor; S4. Place the Aspergillus oryzae spore / nickel-cobalt precursor in a tubular furnace and introduce inert gas for high-temperature sintering to obtain the Aspergillus oryzae spore carbon / nickel-cobalt electrocatalyst.
2. The method for preparing an Aspergillus oryzae spore carbon / nickel-cobalt water electrolysis hydrogen evolution electrocatalyst according to claim 1, characterized in that: In step S2, a blue-capped bottle is used as the mixed solution container.
3. The method for preparing an Aspergillus oryzae spore carbon / nickel-cobalt water electrolysis hydrogen evolution electrocatalyst according to claim 1, characterized in that: In step S2, the heating temperature is 50-90°C and the reaction time is 1-10 hours.
4. The method for preparing an Aspergillus oryzae spore carbon / nickel-cobalt water electrolysis hydrogen evolution electrocatalyst according to claim 1, characterized in that: In step S4, the high temperature sintering temperature is 600-850° C., and the sintering time is 1-3 hours.
5. An Aspergillus oryzae spore carbon / nickel-cobalt water electrolysis hydrogen evolution electrocatalyst, characterized in that: Prepared according to the preparation method described in any one of claims 1 to 4.
6. Use of the Aspergillus oryzae spore carbon / nickel-cobalt water electrolysis hydrogen evolution electrocatalyst according to claim 5 in water electrolysis hydrogen evolution.