Nickel ion-doped carbonate green rust material as well as preparation method and application thereof
By doping nickel ions into carbonate green rust materials, forming a layered bimetallic structure, using the redox capacity of the divalent iron site to generate hydrogen in an anaerobic alkaline environment, the problems of high carbon emissions and cost in existing hydrogen energy production are solved, and efficient hydrogen production is achieved.
Patent Information
- Application Number
- CN202510833644.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-20
- Publication Date
- 2025-09-02
AI Technical Summary
The existing hydrogen energy production process has problems of high carbon emissions and production costs, and it is necessary to develop a low-cost and efficient hydrogen production method.
By doping nickel ions into the carbonate green rust material, a layered bimetallic structure is formed, and hydrogen is generated in an anaerobic alkaline environment using the redox capacity of the divalent iron site.
It achieves rapid hydrogen production during the redox process, and the hydrogen production capacity reaches a theoretical value of 83%, reducing production costs and improving the stability of the material.
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Figure CN120573757A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of clean energy manufacturing, and in particular to a carbonate green rust material doped with nickel ions, and a preparation method and application thereof. Background Art
[0002] The use of fossil energy has led to large-scale emissions of greenhouse gases such as carbon dioxide, which has had a serious impact on the global ecosystem and climate, and in turn caused hazards such as loss of biodiversity, global warming, increased average temperature, rising sea levels, ocean acidification, and reduced agricultural production.
[0003] In this context, focusing on the development of clean, sustainable non-fossil energy has become the core point and key path to resolving the above-mentioned series of problems. Among the many clean energy sources, hydrogen energy has attracted much attention due to its high calorific value, wide application, and pollution-free characteristics. At present, the main way to obtain hydrogen energy is industrial hydrogen production, including hydrogen production from fossil energy reforming, hydrogen production from industrial by-products, and hydrogen production from water electrolysis. However, the above-mentioned process still has problems such as carbon emissions during the production process and high production costs. Therefore, the formation of natural hydrogen energy with low development cost and huge reserves through water-rock reaction is highly anticipated. The core of the water-rock reaction is the oxidation and reduction of water by divalent iron to produce hydrogen. The present invention enhances the redox hydrogen production capacity of divalent iron ions in carbonate green rust by doping nickel ions into the carbonate green rust containing divalent iron. Summary of the Invention
[0004] In view of the shortcomings of the existing technology, the present invention provides a carbonate green rust material doped with nickel ions. The carbonate green rust material doped with nickel ions provided by the present invention has excellent redox performance, and the material can quickly reduce water to produce hydrogen during the oxidation process.
[0005] To achieve the above objectives, the present invention is implemented through the following technical solutions: A method for preparing a carbonate green rust material doped with nickel ions comprises the following steps: S1: mixing a divalent iron source, a trivalent iron source and a divalent nickel source under anaerobic conditions to obtain a mixed solution; S2: adding alkali solution to the mixed solution obtained in S1, and obtaining a suspension of carbonate green rust material doped with nickel ions after stirring and aging reaction; S3: Centrifugal separation of the suspension of the nickel ion-doped carbonate green rust material obtained in S2; S4: The solid carbonate green rust material doped with nickel ions obtained in S3 is washed twice with oxygen-free water and centrifuged to obtain a solid carbonate green rust material doped with nickel ions.
[0006] Preferably, the specific steps of adding alkali solution to the mixed solution obtained in S1 and obtaining a suspension of carbonate green rust material doped with nickel ions after stirring and aging reaction are as follows: S101: The source of ferrous iron in S1 includes FeSO4·7H2O and / or anhydrous FeCl2; S102: The ferric iron source in S1 includes Fe2(SO4)3· X H2O and / or FeCl3·6H2O; S103: The divalent nickel source in S1 is NiSO4·6H2O and / or NiCl2; The ratio of the sum of divalent iron and divalent nickel to the amount of trivalent iron in S104:S1 is 2.5:1; The molar ratio of divalent nickel to the sum of divalent nickel and divalent iron in S105:S1 is 5:100.
[0007] Preferably, S2: adding alkali solution to the mixed solution obtained in S1, and obtaining a suspension of carbonate green rust material doped with nickel ions after stirring and aging reaction, specifically the steps of: S201: The alkali solution in S2 is composed of a mixed solution of 0.466 mol / L anhydrous Na2CO3 and 0.8 mol / L NaOH; S202: The stirring rate in S2 is based on the uniform stirring of the solution, with a speed range of 400-450 r / min; S203: The aging time in S2 is 2 hours; S204: The temperature in S2 is 25 degrees Celsius.
[0008] Preferably, S3: the specific steps of centrifuging the suspension of the nickel ion-doped carbonate green rust material obtained in S2 are: S301: The centrifugal separation speed in S3 is 3000 r / min.
[0009] Preferably, the nickel ion-doped carbonate green rust material solid obtained in S3 is washed twice with oxygen-free water and centrifuged to obtain the nickel ion-doped carbonate green rust material solid by the following specific steps: S401: The amount of oxygen-free water used for washing in S4 is 50 mL each time.
[0010] A carbonate green rust material doped with nickel ions comprises a carbonate green rust body and nickel ions doped in the crystal structure of the carbonate green rust material. The structure of the carbonate green rust material doped with nickel ions is a layered bimetallic structure with carbonate ions interlayered between the layers. The molar ratio of divalent iron to trivalent iron in the carbonate green rust material doped with nickel ions is (2-3):1, and the molar ratio of divalent nickel to the sum of divalent nickel and divalent iron is 5:100. Synthesis of the carbonate green rust material doped with nickel ions needs to be carried out under anaerobic conditions.
[0011] The invention discloses an application of a carbonate green rust material doped with nickel ions. The carbonate green rust material doped with nickel ions is used in generating hydrogen.
[0012] The present invention provides a nickel ion-doped carbonate green rust material and its preparation method and application. It has the following beneficial effects: 1. The present invention forms a nickel-doped carbonate green rust material by coprecipitating ferrous and ferric ions with a certain amount of nickel ions in an anaerobic alkaline environment. This material possesses strong redox activity, capable of binding water molecules in solution to the ferrous sites on the nickel-doped carbonate green rust material. Through the redox activity of the ferrous sites, water molecules are adsorbed and cleaved on the surface of the nickel-doped carbonate green rust material, generating hydrogen and transforming into a solid Fe₃O₄ (magnetite). Results from the examples show that the nickel-doped carbonate green rust material provided by the present invention can produce hydrogen through the oxidation and reduction of water, reaching 83% of its theoretical output value. 2. The present invention uses a divalent iron source, a trivalent iron source and a divalent nickel source as raw materials, and adopts a co-precipitation method to make Ni 2+ By doping into the interior of the carbonate green rust material crystals and improving the surface of the carbonate green rust material, a material with a strong ability to produce hydrogen by oxidizing and reducing water is obtained. BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Figure 1 This is the SEM image of pure carbonate green rust; Figure 2 This is the SEM image of carbonate green rust doped with nickel ions; Figure 3 This is the SEM image of the solid product after pure carbonate green rust material oxidizes and reduces water to produce hydrogen; Figure 4 This is the SEM image of the solid product after the nickel ion-doped carbonate green rust oxidizes and reduces water to produce hydrogen; Figure 5 This is a graph showing the change in the amount of hydrogen produced by the oxidation-reduction water of the pure carbonate green rust and the carbonate green rust doped with nickel ions prepared in performance test 1 over time under the same conditions; Figure 6 This is a graph showing the change in the amount of hydrogen produced by the pure carbonate green rust and the carbonate green rust containing different proportions of nickel ions under the same conditions of oxidation and reduction of water as prepared in performance test 1; Figure 7 This is a graph showing the change in the amount of hydrogen produced over time by the redox water of carbonate green rust containing 5% nickel ions prepared in performance test 2 under different pH conditions; Figure 8 This is a graph showing the change in the amount of hydrogen produced by the oxidized-reduced water of the carbonate green rust containing 5% nickel ions prepared in performance test 3 over time under different temperature conditions; Figure 9 It is a schematic diagram of the main steps of the present invention; Figure 10 This is a detailed schematic diagram of step S1 of the present invention; Figure 11 This is a detailed schematic diagram of step S2 of the present invention; Figure 12 This is a detailed schematic diagram of step S3 of the present invention; Figure 13 This is a detailed schematic diagram of step S4 of the present invention. DETAILED DESCRIPTION
[0014] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.
[0015] Example 1: like Figure 1-13 As shown, an embodiment of the present invention provides a method for preparing a carbonate green rust material doped with nickel ions, comprising the following steps: S1: mixing a divalent iron source, a trivalent iron source and a divalent nickel source under anaerobic conditions to obtain a mixed solution; S2: adding alkali solution to the mixed solution obtained in S1, and obtaining a suspension of carbonate green rust material doped with nickel ions after stirring and aging reaction; S3: Centrifugal separation of the suspension of the nickel ion-doped carbonate green rust material obtained in S2; S4: The solid carbonate green rust material doped with nickel ions obtained in S3 is washed twice with oxygen-free water and centrifuged to obtain a solid carbonate green rust material doped with nickel ions.
[0016] The specific steps of adding alkali solution to the mixed solution obtained in S1 and stirring and aging to obtain a suspension of carbonate green rust material doped with nickel ions are as follows: S101: The source of ferrous iron in S1 includes FeSO4·7H2O and / or anhydrous FeCl2; S102: The ferric iron source in S1 includes Fe2(SO4)3· X H2O and / or FeCl3·6H2O; S103: The divalent nickel source in S1 is NiSO4·6H2O and / or NiCl2; The ratio of the sum of divalent iron and divalent nickel to the amount of trivalent iron in S104:S1 is 2.5:1; The molar ratio of divalent nickel to the sum of divalent nickel and divalent iron in S105:S1 is 5:100.
[0017] S2: adding alkali solution to the mixed solution obtained in S1, and obtaining a suspension of carbonate green rust material doped with nickel ions after stirring and aging reaction. The specific steps are: S201: The alkali solution in S2 is composed of a mixed solution of 0.466 mol / L anhydrous Na2CO3 and 0.8 mol / L NaOH; S202: The stirring rate in S2 is based on the uniform stirring of the solution, with a speed range of 400-450 r / min; S203: The aging time in S2 is 2 hours; S204: The temperature in S2 is 25 degrees Celsius.
[0018] The specific steps of centrifugal separation of the suspension of the nickel ion-doped carbonate green rust material obtained based on S2 are: S301: The centrifugal separation speed in S3 is 3000 r / min.
[0019] The nickel ion-doped carbonate green rust material solid obtained in S3 is washed twice with oxygen-free water and centrifuged to obtain the nickel ion-doped carbonate green rust material solid. The specific steps are: S401: The amount of oxygen-free water used for washing in S4 is 50 mL each time.
[0020] S1 mixes a divalent iron source, a ferric iron source and a divalent nickel source to obtain a mixed solution. S2 adds alkali solution to the mixed solution obtained in step S1, and after stirring and aging reaction, obtains a carbonate green rust material slurry doped with nickel ions, and mixes the divalent iron source, the ferric iron source and the divalent nickel source to obtain a mixed solution. The mixing operation of the divalent iron source, the ferric iron source and the divalent nickel source is required to be carried out in an anaerobic glove box. The mixing of the divalent iron source, the ferric iron source and the divalent nickel source is preferably carried out under stirring, and the stirring rate is preferably 400 r / min-500 r / min, more preferably 450 r / min-500 r / min. The stirring time is preferably 2 hours. The stirring device is preferably a magnetic stirrer. The ratio of the amount of divalent iron to the amount of ferrous iron of the pure carbonate green rust material is preferably 2-3:1, more preferably 2.5:1. The molar ratio of divalent nickel to the sum of divalent nickel and divalent iron in the nickel-doped carbonate green rust material is preferably 5:100. After obtaining a mixed solution, an alkali solution is added to the mixed solution to obtain the nickel-doped carbonate green rust material through a coprecipitation reaction. The alkali solution is preferably a mixture of 0.8 mol / L NaOH and 0.466 mol / L anhydrous Na2CO3. The mixed alkali solution of NaOH and anhydrous Na2CO3 is used to replace sulfate ions between crystal layers in the nickel-doped carbonate green rust material during the precipitation process. The alkali solution is injected into the mixture of the divalent iron source, the ferric iron source, and the divalent nickel source in the sealed reaction flask via a syringe. The amount of alkali solution used is preferably such that the molar ratio of carbonate ions to sulfate ions is 6:5. The precipitation reaction is preferably carried out under stirring. In the present invention, the stirring time is preferably 2 hours. After the precipitation reaction is completed, the slurry generated by the precipitation reaction is preferably centrifuged and then washed twice with oxygen-free water. The washed precipitated solid is shaken with 50 mL of oxygen-free water for later use.
[0021] A carbonate green rust material doped with nickel ions comprises a carbonate green rust body and nickel ions doped in the crystal structure of the carbonate green rust material. The structure of the carbonate green rust material doped with nickel ions is a layered bimetallic structure with carbonate ions interlayered between the layers. The molar ratio of divalent iron to trivalent iron in the carbonate green rust material doped with nickel ions is (2-3):1, and the molar ratio of divalent nickel to the sum of divalent nickel and divalent iron is 5:100. Synthesis of the carbonate green rust material doped with nickel ions needs to be carried out under anaerobic conditions.
[0022] The nickel-ion-doped carbonate green rust material provided by the present invention comprises a pure carbonate green rust material as a main body. In the present invention, the pure carbonate green rust material is preferably a pure carbonate green rust material having a molar ratio of divalent iron to trivalent iron of 2.5:1. The present invention uses the pure carbonate green rust material as a main body to prepare a carbonate green rust material containing 5% nickel ions. The carbonate green rust material containing 5% nickel ions exposes a large number of divalent iron sites on the surface, which can serve as sites for the nickel-ion-doped carbonate green rust material to oxidize and reduce water to produce hydrogen. In addition, carbonate green rust once existed in large quantities in nature and was environmentally friendly during the production process. At the same time, its own redox reaction promotes the material cycle of iron elements in nature. The experimental drugs used in the present invention were purchased from Shanghai Aladdin Chemical Reagent Co., Ltd. The molar ratio of divalent nickel to the sum of divalent nickel and divalent iron in the nickel-ion-doped carbonate green rust material is preferably 5:100. The stability of the pure carbonate green rust material is further improved, and divalent iron sites with redox ability are provided. The carbonate green rust material doped with nickel ions provided by the present invention is mainly based on a pure carbonate green rust material with a certain redox ability. By doping a certain amount of nickel ions during the precipitation formation process, the stability of the pure carbonate green rust material is further improved, and the ability of the material to produce hydrogen by oxidizing and reducing water is further improved.
[0023] Carbonate green rust materials doped with nickel ions are used in generating hydrogen.
[0024] A carbonate green rust material doped with nickel ions is preferably used as an oxidant for reducing water to produce hydrogen. The process of using a carbonate green rust material doped with nickel ions to produce hydrogen from water includes the following steps: 1.9 mL of a slurry of the carbonate green rust material doped with nickel ions is placed in a reaction flask, followed by the addition of 8.1 mL of oxygen-free water. The reaction is heated in a water bath at 90 degrees Celsius. The amount of hydrogen produced is measured at 0, 0.5, 1, 1.5, 2, 2.5, 3, 4, and 5 hours. Carbonate green rust materials containing different proportions of nickel ions are synthesized to determine the effect of adding different proportions of nickel ions on the production of hydrogen from the oxidation and reduction of water by the carbonate green rust material. The pH of the reaction solution of the experimental group of carbonate green rust materials doped with nickel ions at the optimal ratio is adjusted to 7, 8.5, 10, and 11.5 to determine the effect of different pH values on the production of hydrogen from the oxidation and reduction of water by the carbonate green rust material doped with nickel ions. Take the optimal ratio of nickel ion-doped carbonate green rust material and the optimal reaction pH, change the temperature of the experimental group reaction solution to 25, 50, 70, and 90 degrees Celsius, and determine the effect of different temperatures on the production of hydrogen by the redox water of the nickel ion-doped carbonate green rust material. Under the optimal reaction conditions in the above process, the experimental group after the redox hydrogen production of the nickel ion-doped carbonate green rust material is filtered and solid-liquid separation is performed. In the present invention, the divalent iron concentration of the nickel ion-doped carbonate green rust material is 0.04 mol / L, and the reaction volume is 10 mL. The reaction time is 5 hours, and the reaction temperature is 90 The steps of the present invention need to be carried out in an oxygen-free environment.
[0025] Example 2: (1) Aerate ultrapure water with high-purity argon for 20 minutes, then evacuate for 5 minutes, and aerate for another 5 minutes, repeating this cycle twice to obtain oxygen-free water. (2) Weigh 1.0924g Fe2(SO4)3· X H2O, 2.8207g FeSO4·7H2O, and 0.2807g NiSO4·6H2O (the molar ratio of divalent nickel to the sum of divalent nickel and divalent iron is 5:100, and the molar ratio of the sum of divalent iron and divalent nickel to ferric iron is 2.5:1). Dissolve the ferric iron source in 20 mL of oxygen-free water in an anaerobic glove box. Dissolve the ferrous iron source and the divalent nickel source together in 20 mL of oxygen-free water. (3) In an anaerobic glove box, the solutions of the ferrous iron source, the ferric nickel source, and the iron source were mixed in a 200 mL reaction bottle and stirred continuously with a magnetic stirrer at a speed of 500 r / min. (4) In an anaerobic glove box, inject 35 mL of a mixed alkali solution of 0.8 mol / L NaOH and 0.466 mol / L anhydrous Na2CO3 into the continuously stirred mixed solution through a syringe and age the solution for 2 hours; (5) The resulting suspension was centrifuged at 3000 r / min for 5 minutes. After discarding the supernatant in an anaerobic glove box, 50 mL of oxygen-free water was added, shaken and washed, and then centrifuged again. Repeat this process twice to remove sodium and sulfate ions. (6) Finally, add 50 mL of oxygen-free water to the solid after centrifugation and shake well to obtain a carbonate green rust material slurry containing 5% nickel ions.
[0026] Application examples: The effect of varying nickel ion ratios on hydrogen production by carbonate green rust redox water was determined. In an anaerobic glove box, 1.9 mL of carbonate green rust slurry doped with varying nickel ion concentrations was placed in a reaction flask. 8.1 mL of oxygen-free water was added to a 10 mL reaction volume. After the reaction flask was sealed, it was removed and evacuated using a vacuum pump for 2 minutes. High-purity argon was then filled into the flask for 2 minutes, and this process was repeated twice. The reaction was then heated in a 90°C oil bath. 1 mL of headspace gas was sampled using a gas microsampler at 0, 0.5, 1, 1.5, 2, 2.5, 3, 4, and 5 hours. 0.5 mL of the sample was then analyzed for hydrogen content by gas chromatography (GC). This study determined the effect of varying nickel ion concentrations on hydrogen production by carbonate green rust redox water.
[0027] The experimental group with the greatest influence of nickel ion concentration on the production of hydrogen by carbonate green rust redox water was selected. The external environmental factors of the experimental group (temperature: room temperature (25) 50, 70, 90 degrees Celsius) and the initial pH of the reaction solution were adjusted (7, 8.5, 10, 11.5) to determine the changing pattern of the external environmental factors on the production of hydrogen by carbonate green rust redox water over time.
[0028] In an anaerobic glove box, 1.9 mL of the 5% nickel-containing hydroxycarbonate green rust slurry prepared in Example was placed in a 65 mL reaction flask. 8.1 mL of oxygen-free water was then added to adjust the solution's pH to 11.5. After removal from the glove box, the flask was vacuumed for 2 minutes and aerated with high-purity argon for 2 minutes, repeated twice. The reaction was heated at 90°C. The amount of hydrogen produced by the 5% nickel-containing carbonate green rust material was measured by gas chromatography at 0, 0.5, 1, 1.5, 2, 2.5, 3, 4, and 5 hours. After the reaction reached equilibrium, the yield was determined to be 83%.
[0029] Performance testing: (1) Hydrogen production experiment of carbonate green rust materials containing different proportions of nickel ions: The ability of pure carbonate green rust materials, carbonate green rust materials containing 2.5% nickel ions, carbonate green rust materials containing 5% nickel ions and carbonate green rust materials containing 10% nickel ions to produce hydrogen by oxidizing and reducing water was tested. Specifically, 1.9 mL of carbonate green rust material slurry containing different proportions of nickel ions was extracted, and then 8.1 mL of oxygen-free water was added to a 65 mL reaction bottle, the pH was adjusted to 11.5, and the reaction was heated in a water bath at 90 degrees Celsius. The amount of hydrogen produced was measured by gas chromatography at 0, 0.5, 1, 1.5, 2, 2.5, 3, 4, and 5 hours and recorded. The experimental results are shown in Figure 5 As can be seen from the figure, under the same conditions, the nickel ion-doped carbonate green rust material prepared by the present invention has the best hydrogen production effect when the nickel ion content is 5%; (2) Experiment on the effect of pH on hydrogen production: The experimental group of carbonate green rust material containing 5% nickel ions was adjusted with 0.1 mol / L HCl and 0.1 mol / L NaOH solution to test the effect of hydrogen production at pH 7, 8.5, 10, and 11.5. The experimental results are shown in Figure 6 As can be seen from the figure, as the pH increases, the hydrogen production effect becomes better and better; (3) Experiment on the effect of temperature on hydrogen production: In the experimental group of carbonate green rust material with pH of 11.5 and containing 5% nickel ions, the effect of temperature on hydrogen production was tested at 25, 50, 70 and 90 degrees Celsius. The experimental results are shown in Figure 7 As can be seen from the figure, the hydrogen production effect is positively correlated with the increase in temperature, and can reach up to 83% of the theoretical hydrogen production.
[0030] It can be seen from the above examples that the carbonate green rust material containing 5% nickel ions provided by the present invention has a strong ability to oxidize and reduce water to produce hydrogen.
[0031] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.
Claims
1. A method for preparing a carbonate green rust material doped with nickel ions, characterized in that: The following steps are involved: S1: mixing a divalent iron source, a trivalent iron source and a divalent nickel source under anaerobic conditions to obtain a mixed solution; S2: adding alkali solution to the mixed solution obtained in S1, and obtaining a suspension of carbonate green rust material doped with nickel ions after stirring and aging reaction; S3: Centrifugal separation of the suspension of the nickel ion-doped carbonate green rust material obtained in S2; S4: The solid carbonate green rust material doped with nickel ions obtained in S3 is washed twice with oxygen-free water and centrifuged to obtain a solid carbonate green rust material doped with nickel ions.
2. The method for preparing a nickel ion-doped carbonate green rust material according to claim 1, wherein: The specific steps of adding alkali solution to the mixed solution obtained in S1 and stirring and aging to obtain a suspension of carbonate green rust material doped with nickel ions are as follows: S101: The source of ferrous iron in S1 includes FeSO4·7H2O and / or anhydrous FeCl2; S102: The ferric iron source in S1 includes Fe2(SO4)3· X H2O and / or FeCl3·6H2O; S103: The divalent nickel source in S1 is NiSO4·6H2O and / or NiCl2; The ratio of the sum of divalent iron and divalent nickel to the amount of trivalent iron in S104:S1 is 2.5:1; The molar ratio of divalent nickel to the sum of divalent nickel and divalent iron in S105:S1 is 5:
100.
3. The method for preparing a nickel ion-doped carbonate green rust material according to claim 1, characterized in that: S2: adding alkali solution to the mixed solution obtained in S1, and obtaining a suspension of carbonate green rust material doped with nickel ions after stirring and aging reaction. The specific steps are: S201: The alkali solution in S2 is composed of a mixed solution of 0.466 mol / L anhydrous Na2CO3 and 0.8 mol / L NaOH; S202: The stirring rate in S2 is based on the uniform stirring of the solution, with a speed range of 400-450 r / min; S203: The aging time in S2 is 2 hours; S204: The temperature in S2 is 25 degrees Celsius.
4. The method for preparing a nickel ion-doped carbonate green rust material according to claim 1, wherein: S3: The specific steps of centrifuging the suspension of the nickel ion-doped carbonate green rust material obtained in S2 are as follows: S301: The centrifugal separation speed in S3 is 3000 r / min.
5. The method for preparing a nickel ion-doped carbonate green rust material according to claim 1, characterized in that: The nickel ion-doped carbonate green rust material solid obtained in S3 is washed twice with oxygen-free water and centrifuged to obtain the nickel ion-doped carbonate green rust material solid. The specific steps are as follows: S401: The amount of oxygen-free water used for washing in S4 is 50 mL each time.
6. A carbonate green rust material doped with nickel ions, characterized in that: The carbonate green rust main body and the nickel ions doped in the crystal structure of the carbonate green rust material; the structure of the carbonate green rust material doped with nickel ions is a layered bimetallic structure with carbonate ions interlayered; the molar ratio of divalent iron to trivalent iron in the carbonate green rust material doped with nickel ions is (2-3):1; the molar ratio of divalent nickel to the sum of divalent nickel and divalent iron is 5:100; and the synthesis of the carbonate green rust material doped with nickel ions needs to be carried out under anaerobic conditions.
7. An application of a carbonate green rust material doped with nickel ions, characterized by: Carbonate green rust materials doped with nickel ions are used in generating hydrogen.