CN112808274A - High-performance iron-doped nickel or cobalt-based amorphous oxyhydroxide catalyst prepared by room temperature method and research on efficient water electrolysis hydrogen production thereof - Google Patents
High-performance iron-doped nickel or cobalt-based amorphous oxyhydroxide catalyst prepared by room temperature method and research on efficient water electrolysis hydrogen production thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a high-performance iron-doped nickel or cobalt-based amorphous oxyhydroxide catalyst prepared by a room temperature method and a research on efficient water electrolysis hydrogen production, belonging to the technical field of electrocatalytic material hydrogen production. The technical scheme of the invention is as follows: using FeCl3·6H2O and ethanol are mixed to form a precursor solution to slowly corrode the surface of the conductive substrate such as foam nickel, cobalt and the like produced in a macroscopic quantity mode, and a ferronickel or cobalt-iron oxide catalyst grows on the surface in situ. We creatively introduce a chemical reduction reaction to obtain an excellent oxygen evolution catalyst on a commercial metal conductive substrate by utilizing chemical corrosion at room temperature. The unique material synthesis wayThe non-noble metal cobalt or nickel-based oxygen evolution catalyst shows excellent oxygen evolution activity in an alkaline environment after being subjected to in-situ iron doping, and the oxygen evolution activity is 500 mA/cm at high current2The over-potential of the electrode is reduced to about 280 millivolts and is 1.5A/cm2Or the operation in a large-current environment is stable, the method is suitable for industrial large-scale application, and the hydrogen fuel automobile and the hydrogen energy industry in China are assisted.
Description
Technical Field
The invention relates to the field of research of hydrogen production by electrolyzing water by using an electro-catalytic material, in particular to a preparation method of an FeOOH/M-OOH nanosheet array oxygen evolution catalyst based on in-situ growth on the surface of metal foam or a porous conductive material such as foamed nickel, cobalt, copper or iron and the like and application of the catalyst to an electrolyzed water oxygen evolution reaction in an alkaline solution, wherein M refers to a low-price single metal or double transition metal such as iron, cobalt, nickel, copper and the like.
Background
The continuing concern over energy shortages and environmental pollution has driven attention to clean energy sources that can replace fossil fuels. New energy sources in various forms such as wind energy, hydropower, solar energy, geothermal energy and the like are rapidly applied and developed, have the advantages of large storage capacity, cleanness, no harm to the environment, inexhaustibility and the like, and are expected to become mainstream energy sources required by human beings in the future. However, the wind power or solar power generation has large fluctuation due to climate influence and has uncontrollable property, and the problems of seasonality of hydraulic resources, excessive power at night and the like still exist. The new energy layout in China is relatively centralized, the renewable energy power and the local absorption capacity are insufficient, the delivery capacity is limited and is not coordinated, the three abandon problems of wind abandonment, light abandonment and water abandonment in China cannot be avoided, and the cost of new energy power generation is increased. One potential approach to solving these problems is to utilize hydrogen energy storage technology. Intermittent wind power, solar energy or redundant water power at night can be converted into electric energy for driving the electrolyzed water to produce hydrogen, so that the electric energy is stored in a hydrogen fuel cell on a large scale for reuse when needed. The hydrogen energy is a secondary clean energy which has development potential, is clean and environment-friendly at present, and is expected to play an important role in the future electric power energy industry.
The vast ocean on earth provides abundant water resources for human beings, and the total energy of the hydrogen fuel obtained by water decomposition is about 9000 times of that of the fossil fuel on earth. Various daily life water, river water, industrial wastewater and seawater can be used as natural hydrogen production raw materials. Therefore, the water electrolysis hydrogen production technology is an ideal hydrogen production scheme, can convert surplus electric power of renewable energy sources such as solar energy, wind energy and the like into clean hydrogen fuel, is expected to occupy a very important position in the future hydrogen production technology, and has extremely high social and economic benefits for the rapid development of hydrogen energy industry in China. Under the current technical conditions, although the alkaline water electrolyzer is widely used industrially because of its cheap catalyst and mature technology, its water decomposition voltage is high and the electric energy consumption is so large that the industrial application is not paid sufficient attention. In order to reduce the cost of hydrogen production in practical applications, innovation of inexpensive catalyst materials and improvement of technology remain important. One of the half reaction-anodic oxygen evolution reaction has low catalytic efficiency, and the oxygen evolution overpotential is high, which results in high energy consumption, and is a major bottleneck that causes low energy conversion efficiency of hydrogen production by decomposing alkaline water and restricts the large-scale development of the technology. Under the condition that the equipment is basically not changed, an effective way for improving the water electrolysis efficiency is to find and prepare a high-performance non-noble metal catalyst material, so that the overpotential of catalytic hydrogen evolution and oxygen evolution reactions is remarkably reduced, and particularly the design and synthesis of an anode oxygen evolution catalyst are realized. However, at present, most of the synthesis of oxygen evolution catalysts is based on a complex material preparation process, or requires harsh growth conditions, such as high temperature, toxic environment, time-consuming, environmentally-unfriendly, etc., and many preparation processes cannot realize the macro-quantitative production of the catalysts. Therefore, it is important to explore a new preparation process with low cost, high flux and non-toxic environment to obtain a cheap catalyst for oxygen evolution by electrolysis of water with excellent performance. On the other hand, most of the existing oxygen evolution catalysts with excellent performance are based on nickel-iron-based materials, and the oxygen evolution activity of cobalt-based materials is not improved all the time. How to obtain the cheap cobalt-based oxygen evolution catalyst which has the same activity as the nickel-iron-based oxygen evolution catalyst and is durable and stable in large current has important research significance. In the patent, aiming at meeting the factors of commercial catalyst efficiency, catalyst cost, environmental protection and the like, a high-efficiency low-cost electrolytic water oxygen evolution catalyst produced by a simple room-temperature chemical corrosion technology is designed, and the industrial large-scale hydrogen production application is hopefully realized. The catalyst is an excellent oxygen evolution electrocatalyst formed by a three-dimensional porous (Ni, Fe, Co) oxyhydroxide nanosheet array, and the main catalytic mechanism is derived from a FeOOH/M-OOH nanosheet array grown on foamed nickel-cobalt-iron. The alkaline water electrolyzer is constructed by matching the oxygen evolution catalyst with another strong catalyst for the water electrolysis hydrogen evolution reaction, so that the effective water electrolysis hydrogen production reaction is realized, and other forms of energy are converted into hydrogen chemical energy to be stored.
Disclosure of Invention
The invention aims to provide a preparation method of an amorphous oxyhydroxide oxygen evolution catalyst based on cheap transition metal elements such as nickel, cobalt, iron and the like and an electrolyzed water oxygen evolution reaction in an alkaline solution, wherein the catalyst obtained by a surface chemical corrosion method shows excellent catalytic oxygen production activity in an alkaline electrolyte. For example, the Fe-doped Co-based oxygen evolution catalyst synthesized by the method greatly reduces the overpotential of the electrolytic water oxygen evolution reaction, and the overpotential is 500 mA/cm at a large current2The overpotential of the catalyst only needs 281 mV, the performance of the overpotential is better than that of all cheap cobalt-based oxygen evolution catalysts reported at present and also better than that of most nickel-iron-based oxygen evolution catalysts, and the catalyst can be used for processing 5000 mA/cm at a larger current of 1500-2Stable operation and is hopeful to be utilized in commercial alkaline electrolytic cells.
The preparation method of the amorphous (hydroxyl) oxide oxygen evolution catalyst comprises the following steps: (taking a foamed cobalt substrate as an example).
Step 1: and cutting the foamed cobalt base substrate to obtain a cut area of 15 mm in length and 4 mm in width.
Step 2: the amorphous (hydroxy) oxide precursor is prepared by the following method: proportioning 0.755 g FeCl of substrate liquid3·6H2And O is fully dissolved in 5ml of ethanol, the mixture is subjected to ultrasonic mixing for about 10 minutes under the heating condition, the sheared foam cobalt is flattened and soaked in a chemical corrosion solution for a certain time, and the crushed foam cobalt is taken out and dried in the air, so that the electrolytic water oxygen evolution reaction with high catalytic performance can be obtained.
Compared with the existing electrocatalyst material, the invention has the characteristics that:
1. the invention synthesizes the amorphous (hydroxyl) oxide oxygen evolution catalyst based on the transition metal elements such as nickel, cobalt, iron and the like, has simple and convenient preparation process, low energy consumption at room temperature, no pollution, wide raw material sources, greenness, economy and suitability for macro-quantitative and large-size preparation.
2. The amorphous FeOOH/M-OOH of the electrocatalyst material has the advantage that the transition chalcogenide metal M and FeCl are creatively introduced3·6H2And carrying out surface oxidation-reduction reaction on the O at room temperature to synthesize an amorphous FeOOH/M-OOH nanosheet array. The unique synthesis path enables a nano porous structure with a high specific surface and COOOH and metal foam with good conductivity to be simultaneously integrated on the same catalyst, provides a comfortable path for effective transmission of charges and ions, and is favorable for accelerating hydroxyl (OH-]Adsorption and O2The desorption process is beneficial to the huge gain of oxygen production performance. The excellent structural characteristics also obviously reduce the contact resistance between the surface catalyst and the substrate, so that the series resistance of the catalyst is as low as about 1.2 omega, the transmission speed of electrons is greatly improved, and the overpotential of the catalyst in the electrocatalytic oxygen evolution reaction is obviously reduced. In particular, a large current density of 500 mA/cm is generated2Only an overpotential of around 280 mV is required. The amorphous FeOOH/M-OOH electrocatalyst material has the advantages that the catalyst has strong binding force with a substrate and no polymer adhesive exists between the catalyst and the substrate, so that the performance of the catalyst is kept lasting and stable in a long-time large-current catalytic oxygen evolution process; the preparation conditions are extremely mild, the phenomena of high temperature, high pressure and toxic gas release do not exist, and the prepared oxygen evolution catalyst has excellent catalytic performance.
3. The amorphous FeOOH/M-OOH nanosheet array of the electrocatalyst material has the advantage that in an alkaline environment of 1M KOH, the catalyst needs about 280 mV of overpotential to realize 500 mA/cm2High current density.
4. The preparation process is simple and energy-saving, any commercial metal substrate (cobalt, nickel, copper and the like) is adopted for surface corrosion treatment, the method is very compatible with the commercial alkaline electrolytic bath technology, and the industrial application is expected to be realized for large-scale hydrogen production by electrolyzing water.
Drawings
FIG. 1 is a graph of current-potential polarization of an amorphous FeOOH/CoOOH nanosheet array of catalyst material in an alkaline 1M KOH solution, initially and after 1000 CV cycles in example 1 of the present invention.
FIG. 2 is a graph showing the stability of the electrocatalytic oxygen evolution reaction of the catalyst material in example 1 of the present invention. It is clear that the catalyst is operated at a large current of 500 mA/cm2Has good stability.
FIG. 3 shows the AC impedance test performed on the catalyst material of example 1 of the present invention.
Fig. 4 is a Raman chart before and after the reaction of the catalyst material in example 1 of the present invention. It is clear that after prolonged testing, the Raman spectrum signals show that the sample surface is mainly composed of the metal oxyhydroxide MOOH, whereas the initial sample mainly exhibits the metal hydroxide M (OH)2The raman signal of (a).
FIG. 5 is a scanning electron micrograph of the catalyst material of example 1 of the present invention after being tested for oxygen evolution reaction. The left and right images represent the macroscopic and macroscopic topography images, respectively.
FIG. 6 is an image of the surface of a sample of each element after the cobalt-based oxygen evolution catalyst of example 1 of the present invention was tested.
FIG. 7 is a spectrum of the energy of each element after the oxygen evolution catalyst in example 1 of the present invention was tested. From this figure, it can be seen that the elemental ratio of Co to Fe to O is close to 0.76 to 0.4 to 2, indicating that the oxygen evolution active sites are likely to originate from iron-doped cobalt oxyhydroxide.
FIG. 8 is a comparison of the catalytic activity of oxygen evolution catalysts at different concentrations of iron trichloride etchant in example 3 of the present invention.
Detailed Description
The foregoing will provide further details of the invention in order to provide a better understanding of the nature of the patent, but is not to be construed as limiting the invention.
The scope of the present invention is not limited to the following examples, and any techniques based on the above implementations of the present invention are within the scope of the present invention.
An example of the preparation method of the oxygen evolution catalyst based on the amorphous (hydroxy) oxide of transition metal elements such as nickel, cobalt, iron and the like and the electrolytic water oxygen evolution reaction in the alkaline solution is as follows.
Example 1 preparation of amorphous FeOOH/M-OOH nanosheet array and electrochemical testing of oxygen evolution performance in a 1M KOH environment.
Step 1: the amorphous (hydroxyl) oxide precursor is prepared by mixing 0.755 g FeCl in substrate solution3·6H2And (3) fully dissolving O in 5ml of ethanol, performing ultrasonic treatment at a certain temperature for a certain time, and then putting the foam substrate cut in the step (1) into a substrate solution to soak for a period of time to obtain the catalyst with high oxygen evolution and electrolysis water performance.
The electrocatalytic oxygen evolution performance chemical testing device is an electrochemical workstation of a known brand GARY Reference 3000, and a standard three-electrode system is adopted for testing. The three-electrode system respectively has amorphous FeOOH/CoOOH as a working electrode, Hg/HgO electrodes imported by Gamry manufacturers as reference electrodes, platinum wires as counter electrodes, and 1M KOH solution as electrolyte solution, wherein the results of electrochemical tests are shown in fig. 1, 2, 3 and 4, the scanning electron microscope image of the amorphous FeOOH/CoOOH morphology test is shown in fig. 5, the imaging image of each element contained in the amorphous FeOOH/CoOOH on the sample surface is shown in fig. 6, and the energy spectrogram of each element contained in the amorphous FeOOH/CoOOH is shown in fig. 7.
Example 2 preparation of an amorphous FeOOH/M-OOH nanosheet array under different corrosive agent concentrations and application of electrochemical testing of oxygen evolution performance under a 1M KOH electrolyte environment.
Step 1: the preparation method of the amorphous (hydroxyl) oxide precursor comprises the following steps of proportioning substrate liquid with different concentrations: using 0.755 g, 0.5g and 0.25g FeCl respectively3·6H2And (3) fully dissolving O in 5ml of ethanol, ultrasonically mixing for a period of time under a heating condition to obtain a corrosion substrate agent, and then putting the foam substrate cut in the step (1) into the corrosion substrate solution to soak for a period of time to obtain the catalyst with high oxygen evolution electrolysis water performance.
The electrocatalytic oxygen evolution performance chemical testing device is an electrochemical workstation of a known brand GARY Reference 3000, and a standard three-electrode system is adopted for testing. The three-electrode system respectively uses amorphous FeOOH/CoOOH as a working electrode, an imported Hg/HgO electrode as a reference electrode, a platinum wire as a counter electrode, and a 1M KOH solution as an electrolyte solution, and the electrochemical test result is shown in FIG. 8.
The above examples illustrate the basic processes and applications of the present invention in the field of hydrogen production from electrolyzed water, and it will be understood by those skilled in the art that the present invention is not limited by the above examples, which are provided in the description for illustrating the principles and processes of the present invention, and that various changes and modifications may be made without departing from the scope of the principles and processes of the present invention and within the scope of the invention.
Claims (3)
1. The invention takes a room temperature method for preparing high-performance iron-doped cobalt-based amorphous hydroxide catalyst as an example to illustrate the preparation process of the cheap oxygen evolution catalyst material and the application research in the aspect of electrolytic water oxygen evolution reaction; a preparation method of an amorphous FeOOH/CoOOH nanosheet array oxygen evolution catalyst based on a cobalt-based material comprises the following steps:
step 1: firstly, FeCl with proper proportion is added3·6H2Dissolving O in 5mL of solvent, pouring the solution into a small beaker to serve as a precursor solution, and performing ultrasonic treatment for a period of time under the heating condition to serve as a surface chemical corrosive agent; step 2: soaking a pre-cleaned foamed cobalt substrate in a precursor solution; and step 3: and (3) drying the foamed cobalt sample soaked with the chemical corrosive in the air to obtain the catalyst material precursor with adjustable oxygen evolution performance.
2. The preparation method of the amorphous FeOOH/CoOOH nanosheet array oxygen evolution catalyst based on a cobalt-based material as claimed in claim 1 is as follows: it is characterized in that step 1' firstly FeCl with proper proportion3·6H2O dissolved in 5mL of solvent and poured into a small beaker as FeCl in the precursor solution3·6H2The amount of O can be 0.755 g, 0.5g, 0.25g, the solvent isEthanol, Dimethylformamide (DMF), methanol, isopropanol, acetone, and deionized water.
3. The preparation method of the amorphous FeOOH/CoOOH nanosheet array oxygen evolution catalyst based on a cobalt-based material as claimed in claim 1 is as follows: the method is characterized in that in the step 1, ultrasonic treatment is carried out for a period of time under the heating condition, and the ultrasonic treatment time is 10-20 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911039114.6A CN112808274A (en) | 2019-10-29 | 2019-10-29 | High-performance iron-doped nickel or cobalt-based amorphous oxyhydroxide catalyst prepared by room temperature method and research on efficient water electrolysis hydrogen production thereof |
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| CN113355682A (en) * | 2021-07-09 | 2021-09-07 | 苏州阳光氢能材料科技有限公司 | Iron-doped trifluoro cobaltate oxygen evolution electro-catalytic material, preparation method and application thereof |
| CN113385200A (en) * | 2021-07-07 | 2021-09-14 | 浙江大学 | Full spectrum oxygen production CeF without sacrificial agent3alpha-FeOOH photocatalyst and preparation method thereof |
| CN113684496A (en) * | 2021-08-17 | 2021-11-23 | 杭州兴态环保科技有限公司 | Non-noble metal anode material for electrolyzed water and preparation method and application thereof |
| CN113957456A (en) * | 2021-11-19 | 2022-01-21 | 江苏大学 | Nickel-based alkaline electrolytic water catalyst with co-doped combination heterostructure and preparation method thereof |
| CN115522223A (en) * | 2022-09-13 | 2022-12-27 | 华南理工大学 | Fluorine-doped non-noble metal electrocatalyst and preparation method and application thereof |
| CN117512676A (en) * | 2024-01-02 | 2024-02-06 | 洛阳理工学院 | Hierarchical iron doped nickel-carbon structure nanotube and preparation method and application thereof |
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| CN113957456A (en) * | 2021-11-19 | 2022-01-21 | 江苏大学 | Nickel-based alkaline electrolytic water catalyst with co-doped combination heterostructure and preparation method thereof |
| CN115522223A (en) * | 2022-09-13 | 2022-12-27 | 华南理工大学 | Fluorine-doped non-noble metal electrocatalyst and preparation method and application thereof |
| CN117512676A (en) * | 2024-01-02 | 2024-02-06 | 洛阳理工学院 | Hierarchical iron doped nickel-carbon structure nanotube and preparation method and application thereof |
| CN117512676B (en) * | 2024-01-02 | 2024-03-15 | 洛阳理工学院 | Hierarchical iron doped nickel-carbon structure nanotube and preparation method and application thereof |
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