CN114540864B - Non-noble metal-based acidic electrolyzed water oxygen evolution reaction electrocatalyst and preparation method thereof - Google Patents

Non-noble metal-based acidic electrolyzed water oxygen evolution reaction electrocatalyst and preparation method thereof Download PDF

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CN114540864B
CN114540864B CN202210160867.8A CN202210160867A CN114540864B CN 114540864 B CN114540864 B CN 114540864B CN 202210160867 A CN202210160867 A CN 202210160867A CN 114540864 B CN114540864 B CN 114540864B
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manganese
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carbon cloth
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CN114540864A (en
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张晓丹
潘三江
张奇星
王满敬
赵颖
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Nankai University
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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    • 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
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    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention discloses a non-noble metal-based acidic electrolyzed water oxygen evolution reaction electrocatalyst and a preparation method thereof, wherein the electrocatalyst is a (Mn, O, br) novel manganese-based oxybromide material, and the specific components of the material are (Mn 7.5 O 10 Br 3 ) The preparation method comprises dissolving manganese-based halogen salt in water, mixing with manganese-based nitrate solution, uniformly dripping on conductive hydrophilic carbon cloth, and continuously heating. The invention solves the problems of poor catalytic activity and stability of the non-noble metal catalyst under the acidic condition and high cost caused by using the noble metal-based catalyst in the current industrial water electrolysis device. Meanwhile, the material has excellent acid oxygen evolution electrocatalytic activity and high stability, and is expected to be applied to PEM electrolytic tanks in industrial hydrogen production devices, so that the device cost is greatly reduced. Meanwhile, the preparation method is simple and easy to operate, and provides technical feasibility for large-scale hydrogen production.

Description

Non-noble metal-based acidic electrolyzed water oxygen evolution reaction electrocatalyst and preparation method thereof
Technical Field
The invention relates to a novel electrocatalyst material and a preparation method thereof, belongs to the field of electrocatalytic material application, and in particular relates to a non-noble metal-based electrocatalyst material for efficient and stable acid oxygen evolution reaction and a preparation method thereof.
Background
The electrocatalytic energy conversion technology such as electrocatalytic water decomposition hydrogen production, electrocatalytic carbon dioxide reduction, electrocatalytic nitrogen reduction and the like is an effective method for replacing fossil energy, reducing carbon emission and obtaining renewable fuel. However, the water oxidation or Oxygen Evolution Reaction (OER) is the bonding of two oxygen atoms in two water molecules and the release of one oxygen molecule, which plays a key role by providing protons and electrons required for hydrogen generation, electrochemical carbon dioxide reduction and nitrogen fixation. The multiple electron transfer OER process involves multiple reaction intermediates, requiring higher overpotential to overcome the slow kinetics.
PEM electrolyzers have similar designs to PEM fuel cells, with greater advantages over alkaline electrolyzers, such as a more compact system design and lower ohmic losses, higher current density and gas purity, a larger part load range, and faster system response. However, PEMs such as perfluorosulfonic acid membranes create a local acidic environment in water at pH 0-3, which requires corrosion resistant components, is costly, and has very limited choice of anode catalyst. While a large amount of noble and non-noble metal-based catalysts exhibit high activity and stability only in alkaline electrolytes. Expensive and non-scalable iridium oxide and ruthenium-based materials are the only electrocatalysts currently known to have a balance of activity and stability in acidic electrolytes. Thus, the development of non-noble metal OER catalysts with high activity and durability in acidic media directly affects the efficiency and cost effectiveness of PEM devices.
In nature, oxidation of water occurs in Mn in photosystem II 4 CaO 5 A cluster complex. In the case of heterogeneous electrocatalysts, many theories and experimental achievements have been reported regarding the use of manganese oxides in acidic OER. Oxides of manganese exist in a variety of oxidation states and crystalline phases. The surface electrochemistry of oxides of manganese is very complex, and often different electrolyte pH and application potentials cause phase changes at the surface and near-surface regions of the catalyst material. Research on OER electrocatalytic mechanism by related manganese transition metal compounds shows that Mn 3+ Disproportionation occurs in systems with pH < 9, which results in poor oxygen evolution activity of the material. Currently, both oxides of manganese and doped modified oxides of manganese show a stabilizing prospect for acidic OER, but their activity still needs to be further improved compared to noble metal catalysts.
On the other hand, the surface self-reconstruction effect of the electrochemical oxygen evolution process of the material is effectively controlled under the acidic condition, and the stability of the material is not sacrificed in the process of optimizing the catalytic activity. The manganese-based catalyst is used as a candidate material which is hopefully used for replacing an oxygen evolution catalyst under the acidic condition of noble metal, and the main problem is that the catalytic performance is a certain gap compared with that of noble metal, so that the energy consumption of electrolysis water is higher. Therefore, the efficient and stable manganese-based catalyst and the simple and easy preparation method are found, and the method has great significance for the practical application of the non-noble metal-based acidic oxygen evolution reaction electrocatalyst in the field of industrial acidic electrolyzed water.
Disclosure of Invention
The invention aims to solve the problems that the existing manganese-based catalyst has poor catalytic activity and stability under an acidic condition and high energy consumption, and the cost is high due to the use of a noble metal-based catalyst, and provides a novel non-noble metal-based acidic electrolytic water oxygen precipitation reaction electrocatalyst which is a manganese-based oxybromide material; the invention also provides a preparation method of the manganese-based oxybromide.
The technical scheme of the invention is as follows:
a novel non-noble metal-based acidic electrolyzed water oxygen evolution reaction electrocatalyst, which is manganese-based oxybromide with a polycrystalline surface crystal structure, wherein manganese elements in a microstructure of a material have various coordination modes; the manganese-based oxybromide is directly supported on conductive hydrophilic carbon cloth in the preparation process, wherein the content ratio of Mn, O and Br elements is 7.5:10:3, and the chemical formula is Mn 7.5 O 10 Br 3 。
The electrocatalytic activity of the manganese-based oxybromide material reaches 10mA/cm in an acidic medium at ph=0 2 The overpotential range required by the catalytic current density is 290-330 mV; the manganese-based oxybromide material is at 10mA/cm 2 The stable operation time under the current density condition exceeds 450 hours, and the over-potential rising rate is in the range of 0.2-0.3 mV/h.
The invention also provides a preparation method of the non-noble metal-based acidic electrolyzed water oxygen evolution reaction electrocatalyst, which comprises the following preparation steps:
dissolving manganese-based bromine salt in water, adding the prepared manganese-based nitrate solution into the solution, mixing, ensuring that the dosage mole ratio of the manganese-based nitrate solution to the solution is 1:4, mixing to obtain a precursor solution, uniformly dripping the precursor solution on conductive hydrophilic carbon cloth, continuously heating the precursor solution for 3-5 hours at 200-300 ℃, cooling, ultrasonically cleaning the obtained product with deionized water, and then drying to obtain the electrocatalyst.
The manganese-based bromine salt is tetrahydrate manganese bromide or manganese bromide;
the manganese-based nitrate is tetrahydrate manganese nitrate or manganese nitrate;
the mixing is that after ultrasonic dissolution, the mechanical oscillation is fully carried out;
the conductive hydrophilic carbon cloth needs to be pretreated, and the method comprises the following steps: the commercial conductive carbon cloth is soaked in acetone for 15-30 minutes, washed three times by deionized water and absolute ethyl alcohol respectively, and dried. Placing the cleaned and dried carbon in nitric acid with the concentration of 40%, and oxidizing for 30-50 min under ultrasonic conditions.
In one embodiment, the resulting precursor is added dropwise to an area of 2.5 x 2.5cm after the mixing 2 The amounts of the precursor solutions are respectively 100ul,200ul,300ul,400ul and 500ul, wherein 300ul is the optimal dropping amount.
The electrochemical performance test of the novel non-noble metal-based acidic electrolyzed water oxygen precipitation reaction electrocatalyst comprises the following steps:
1) Cutting the carbon cloth loaded with the catalyst into a certain area, then uniformly smearing waterproof silica gel, leaving a part for clamping the electrode and a part with a certain area to contact with water, and naturally airing overnight to solidify the silica gel;
2) Evaluating the electrochemical measurements in a three-electrode device with an Ag/AgCl electrode as reference electrode and a graphite electrode as counter electrode, using a platinum sheet electrode clamp as working electrode;
3) Potential reference Reversible Hydrogen Electrode (RHE): e (E) RHE ＝E Ag/AgCl +0.098+0.059×pH(0.5M H 2 SO 4 A solution). The overpotential (η) is calculated according to the following equation: η=e RHE -1.23V. At a scan rate of 1mV/s at saturated 0.5. 0.5M H 2 SO 4 Linear Sweep Voltammetry (LSV) was recorded in solution to obtain a polarization curve. All electrode potential data were 100% voltage drop compensated.
The invention has the following advantages and effects:
the novel non-noble metal-based acidic electrolyzed water oxygen precipitation reaction electrocatalyst adopts low-cost and easily-obtained manganese-based halide and manganese-based nitrate as manganese sources, and synthesizes the catalyst with multiple active sites and high stability through a high-temperature calcination one-step methodAn acidic non-noble metal catalyst of (a); the electrocatalyst material is simple and easy to prepare and suitable for mass production. The electrocatalyst can significantly reduce the overpotential (relative to gamma-MnO without halogen) when applied to oxygen evolution reaction in an acidic environment 2 Catalyst), 10mA cm -2 Only 295mV for overpotential at current density, the Tafil slope is 68mV dec -1 Is the non-noble metal electrocatalyst for oxygen precipitation reaction with highest activity in an acidic environment. Meanwhile, the prepared electrocatalyst has excellent stability in acid electrolyte and is 10mA cm -2 Is stable for more than 450 hours at a current density of (c). The high performance can be attributed to the change in material structure caused by the introduction of halogen atoms, and the halogen atoms have higher electron density, which improves the conductivity of the overall material. Meanwhile, the material undergoes interfacial self-reconstruction at the interface in the oxygen evolution process to form close-packed MnO x The structure can effectively optimize the binding energy of the oxygen evolution reaction intermediate, thereby improving the activity of the material. This new discovery can provide theoretical guidance for the design of non-noble metal catalysts under acidic conditions, and at the same time, makes the discovery of non-noble metal electrochemical water-splitting oxygen precipitation catalysts of great practical significance.
Drawings
FIG. 1 shows the composition of example 1 (Mn) 7.5 O 10 Br 3 ) A corresponding crystal structure diagram;
FIG. 2 shows the composition of example 1, comparative example 1 (Mn 8 O 10 Cl 3 ) And comparative example 2 (gamma-MnO) 2 ) The electrocatalyst prepared was prepared at a scan rate of 1mV/s at 0.5. 0.5M H 2 SO 4 Recording Linear Sweep Voltammetry (LSV) in the solution to obtain a polarization curve;
FIG. 3 shows the electrocatalyst according to example 1 of the invention at 10mA cm -2 A 450 hour stability test curve was maintained at constant current density with all electrode potential data being 100% iR compensated;
FIG. 4 shows XRD diffraction patterns of the electrocatalysts prepared in example 1 and comparative example 1 of the present invention;
FIG. 5 shows the results of Scanning Electron Microscope (SEM) test of the electrocatalyst prepared in example 1 of the invention supported on hydrophilic conductive carbon cloth;
FIG. 6 shows the results of TEM morphology testing of the electrocatalyst prepared in example 1 of the invention;
FIG. 7 shows the characteristic lattice 303 corresponding to the electrocatalyst HRTEM prepared in example 1 of the invention;
figure 8 shows the 213 characteristic lattices corresponding to the electrocatalyst HRTEM prepared in example 1 of the invention.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the attached drawings and specific embodiments.
Example 1:
firstly, fully dissolving 143.4 milligrams of manganese bromide tetrahydrate in 300 microliters of deionized water by ultrasonic waves; 500 microliters of the prepared 4M manganese nitrate solution is taken and placed in the solution, and mechanical oscillation ensures that the two are fully mixed. The heating plate is preheated to 250 ℃, the pretreated hydrophilic conductive carbon cloth is horizontally placed on the heating plate, 300 microliters of the mixed solution is dropwise added on the hydrophilic conductive carbon cloth, and the catalyst material is required to be uniformly loaded on the hydrophilic conductive carbon cloth in the dropping process. After the completion of the dropwise addition, the mixture was kept at 250℃for 5 hours. After heating, cooling the material to room temperature, carrying out ultrasonic treatment on the material in deionized water for 30 seconds, flushing the material three times, and drying the material in an oven at 65 ℃ overnight to obtain the electrocatalyst. The resulting electrocatalyst of example 1, according to the invention, is a manganese-based oxychloride with a specific crystal structure, see fig. 1.
Example 2:
firstly, fully dissolving 143.4 milligrams of manganese bromide tetrahydrate in 300 microliters of deionized water by ultrasonic waves; 500 microliters of the prepared 4M manganese nitrate solution is taken and placed in the solution, and mechanical oscillation ensures that the two are fully mixed. The heating plate is preheated to 250 ℃, the pretreated hydrophilic conductive carbon cloth is horizontally placed on the heating plate, 100 microliters of the mixed solution is added dropwise on the hydrophilic conductive carbon cloth, and the catalyst material is required to be uniformly loaded on the hydrophilic conductive carbon cloth in the dropping process. After the completion of the dropwise addition, the mixture was kept at 250℃for 5 hours. After heating, cooling the material to room temperature, carrying out ultrasonic treatment on the material in deionized water for 30 seconds, flushing the material three times, and drying the material in an oven at 65 ℃ overnight to obtain the electrocatalyst.
Example 3:
firstly, fully dissolving 143.4 milligrams of manganese bromide tetrahydrate in 300 microliters of deionized water by ultrasonic waves; 500 microliters of the prepared 4M manganese nitrate solution is taken and placed in the solution, and mechanical oscillation ensures that the two are fully mixed. The heating plate is preheated to 250 ℃, the pretreated hydrophilic conductive carbon cloth is horizontally placed on the heating plate, 200 microliters of the mixed solution is dropwise added on the hydrophilic conductive carbon cloth, and the catalyst material is required to be uniformly loaded on the hydrophilic conductive carbon cloth in the dropping process. After the completion of the dropwise addition, the mixture was kept at 250℃for 5 hours. After heating, cooling the material to room temperature, carrying out ultrasonic treatment on the material in deionized water for 30 seconds, flushing the material three times, and drying the material in an oven at 65 ℃ overnight to obtain the electrocatalyst.
Example 4:
firstly, fully dissolving 143.4 milligrams of manganese bromide tetrahydrate in 300 microliters of deionized water by ultrasonic waves; 500 microliters of the prepared 4M manganese nitrate solution is taken and placed in the solution, and mechanical oscillation ensures that the two are fully mixed. The heating plate is preheated to 250 ℃, the pretreated hydrophilic conductive carbon cloth is horizontally placed on the heating plate, 400 microliters of the mixed solution is added dropwise on the hydrophilic conductive carbon cloth, and the catalyst material is required to be uniformly loaded on the hydrophilic conductive carbon cloth in the dropping process. After the completion of the dropwise addition, the mixture was kept at 250℃for 5 hours. After heating, cooling the material to room temperature, carrying out ultrasonic treatment on the material in deionized water for 30 seconds, flushing the material three times, and drying the material in an oven at 65 ℃ overnight to obtain the electrocatalyst.
Example 5:
firstly, fully dissolving 143.4 milligrams of manganese bromide tetrahydrate in 300 microliters of deionized water by ultrasonic waves; 500 microliters of the prepared 4M manganese nitrate solution is taken and placed in the solution, and mechanical oscillation ensures that the two are fully mixed. The heating plate is preheated to 250 ℃, the pretreated hydrophilic conductive carbon cloth is horizontally placed on the heating plate, 500 microliters of the mixed solution is added dropwise on the hydrophilic conductive carbon cloth, and the catalyst material is required to be uniformly loaded on the hydrophilic conductive carbon cloth in the dropping process. After the completion of the dropwise addition, the mixture was kept at 250℃for 5 hours. After heating, cooling the material to room temperature, carrying out ultrasonic treatment on the material in deionized water for 30 seconds, flushing the material three times, and drying the material in an oven at 65 ℃ overnight to obtain the electrocatalyst.
Example 6:
firstly, fully dissolving 143.4 milligrams of manganese bromide tetrahydrate in 300 microliters of deionized water by ultrasonic waves; 500 microliters of the prepared 4M manganese nitrate solution is taken and placed in the solution, and mechanical oscillation ensures that the two are fully mixed. The heating plate is preheated to 250 ℃, the pretreated hydrophilic conductive carbon cloth is horizontally placed on the heating plate, 300 microliters of the mixed solution is dropwise added on the hydrophilic conductive carbon cloth, and the catalyst material is required to be uniformly loaded on the hydrophilic conductive carbon cloth in the dropping process. After the completion of the dropwise addition, the mixture was kept at 200℃for 5 hours. After heating, cooling the material to room temperature, carrying out ultrasonic treatment on the material in deionized water for 30 seconds, flushing the material three times, and drying the material in an oven at 65 ℃ overnight to obtain the electrocatalyst.
Example 7:
firstly, fully dissolving 143.4 milligrams of manganese bromide tetrahydrate in 300 microliters of deionized water by ultrasonic waves; 500 microliters of the prepared 4M manganese nitrate solution is taken and placed in the solution, and mechanical oscillation ensures that the two are fully mixed. The heating plate is preheated to 250 ℃, the pretreated hydrophilic conductive carbon cloth is horizontally placed on the heating plate, 300 microliters of the mixed solution is dropwise added on the hydrophilic conductive carbon cloth, and the catalyst material is required to be uniformly loaded on the hydrophilic conductive carbon cloth in the dropping process. After the completion of the dropwise addition, the mixture was kept at 300℃for 5 hours. After heating, cooling the material to room temperature, carrying out ultrasonic treatment on the material in deionized water for 30 seconds, flushing the material three times, and drying the material in an oven at 65 ℃ overnight to obtain the electrocatalyst.
Example 8:
firstly, fully dissolving 143.4 milligrams of manganese bromide tetrahydrate in 300 microliters of deionized water by ultrasonic waves; 500 microliters of the prepared 4M manganese nitrate solution is taken and placed in the solution, and mechanical oscillation ensures that the two are fully mixed. The heating plate is preheated to 250 ℃, the pretreated hydrophilic conductive carbon cloth is horizontally placed on the heating plate, 300 microliters of the mixed solution is dropwise added on the hydrophilic conductive carbon cloth, and the catalyst material is required to be uniformly loaded on the hydrophilic conductive carbon cloth in the dropping process. After the completion of the dropwise addition, the mixture was kept at 300℃for 3 hours. After heating, cooling the material to room temperature, carrying out ultrasonic treatment on the material in deionized water for 30 seconds, flushing the material three times, and drying the material in an oven at 65 ℃ overnight to obtain the electrocatalyst.
Example 9:
firstly, fully dissolving 143.4 milligrams of manganese bromide tetrahydrate in 300 microliters of deionized water by ultrasonic waves; 500 microliters of the prepared 4M manganese nitrate solution is taken and placed in the solution, and mechanical oscillation ensures that the two are fully mixed. The heating plate is preheated to 250 ℃, the pretreated hydrophilic conductive carbon cloth is horizontally placed on the heating plate, 300 microliters of the mixed solution is dropwise added on the hydrophilic conductive carbon cloth, and the catalyst material is required to be uniformly loaded on the hydrophilic conductive carbon cloth in the dropping process. After the completion of the dropwise addition, the mixture was kept at 300℃for 4 hours. After heating, cooling the material to room temperature, carrying out ultrasonic treatment on the material in deionized water for 30 seconds, flushing the material three times, and drying the material in an oven at 65 ℃ overnight to obtain the electrocatalyst.
Example 10:
electrochemical performance test of electrocatalysts prepared in examples 1 to 9
(1) Cutting the carbon cloth loaded with the catalyst into a certain area, then uniformly smearing waterproof silica gel, leaving a part for clamping the electrode and a part with a certain area to contact with water, and naturally airing overnight to solidify the silica gel; evaluating electrochemical measurements in a three-electrode device with an Ag/AgCl electrode as reference electrode and a graphite electrode as counter electrode, using a platinum sheet electrode clamp as working electrode; potential reference Reversible Hydrogen Electrode (RHE): e (E) RHE ＝E Ag/AgCl +0.098+0.059×pH(0.5M H 2 SO 4 A solution). The overpotential (η) is calculated according to the following equation: η=e RHE -1.23V. At a scan rate of 1mV/s at saturated 0.5. 0.5M H 2 SO 4 Linear Sweep Voltammetry (LSV) was recorded in the solution to obtain a polarization curve, analysis revealed that the overpotential of example 1 was 295mV, see FIG. 2. Stability test at 10mAcm -2 The analysis shows that the overpotential rise rate of example 1 is 0.23mV/h, see fig. 3, for a stability test curve maintained at constant current density for 450 hours. All electrode potential data were 100% voltage drop compensated.
(2) An amount of the catalyst prepared in example 1 was weighed to test XRD having a polycrystalline structure, which was found by comparing PDF cards to be Mn 7.5 O 10 Br 3 See fig. 4.
(3) A small portion of the catalyst test SEM prepared in example 1, loaded on a hydrophilic conductive carbon cloth, see fig. 5, was cut.
(4) A quantity of the catalyst prepared in example 1 was weighed for test TEM, see fig. 6.
(5) A certain amount of the catalyst prepared in example 1 was weighed out to test HRTEM, see fig. 7, fig. 8.
Comparative example 1:
(1)Mn 8 O 10 Cl 3 is prepared from the following steps: firstly, fully dissolving 143.4 milligrams of manganese chloride tetrahydrate in 300 microliters of deionized water by ultrasonic waves; 500 microliters of the prepared 4M manganese nitrate solution is taken and placed in the solution, and mechanical oscillation ensures that the two are fully mixed. The heating plate is preheated to 250 ℃, the pretreated hydrophilic conductive carbon cloth is horizontally placed on the heating plate, 300 microliters of the mixed solution is dropwise added on the hydrophilic conductive carbon cloth, and the catalyst material is required to be uniformly loaded on the hydrophilic conductive carbon cloth in the dropping process. After the completion of the dropwise addition, the mixture was kept at 250℃for 5 hours. After heating, the material was cooled to room temperature, sonicated in deionized water for 30 seconds, rinsed three times, and dried in an oven at 65 ℃ overnight. The electrocatalyst obtained in comparative example 1, which is not according to the invention, is a manganese-based oxychloride.
(2) Cutting the carbon cloth loaded with the catalyst into a certain area, then uniformly smearing waterproof silica gel, leaving a part for clamping the electrode and a part with a specific area to contact with water, and naturally airing overnight to solidify the silica gel; evaluating electrochemical measurements in a three-electrode device with an Ag/AgCl electrode as reference electrode and a graphite electrode as counter electrode, using a platinum sheet electrode clamp as working electrode; potential reference Reversible Hydrogen Electrode (RHE): e (E) RHE ＝E Ag/AgCl +0.098+0.059×pH(0.5M H 2 SO 4 A solution). The overpotential (η) is calculated according to the following equation: η=e RHE -1.23V. At a scan rate of 1mV/s at saturated 0.5. 0.5M H 2 SO 4 Linear Sweep Voltammetry (LSV) was recorded in solution to obtain a polarization curve, see FIG. 2, and it was found that comparative example 1 had an overpotential increase of about 73mV for oxygen evolution catalysis under acidic conditions as compared to example 1. All ofThe electrode potential data were all 100% voltage drop compensated.
(3) Weighing a certain amount of the catalyst prepared in the step (1), testing XRD, wherein the catalyst has a polycrystalline structure, and comparing PDF cards to obtain the Mn-containing material 8 O 10 Cl 3 See fig. 4.
Comparative example 2:
(1)γ-MnO 2 is prepared from the following steps: the heating plate is preheated to 250 ℃, the pretreated hydrophilic conductive carbon cloth is horizontally placed on the heating plate, 500 microliters of prepared 4M manganese nitrate solution are dropwise added on the hydrophilic conductive carbon cloth, and the catalyst material is required to be uniformly loaded on the hydrophilic conductive carbon cloth in the dropwise adding process. After the completion of the dropwise addition, the mixture was kept at 250℃for 5 hours. After heating, the material was cooled to room temperature, sonicated in deionized water for 30 seconds, rinsed three times, and dried in an oven at 65 ℃ overnight. The resulting electrocatalyst of comparative example 2, which is not according to the invention, is a gamma-phase manganese-based oxide.
(2) Cutting the carbon cloth loaded with the catalyst into a certain area, then uniformly smearing waterproof silica gel, leaving a part for clamping the electrode and a part with a specific area to contact with water, and naturally airing overnight to solidify the silica gel; evaluating electrochemical measurements in a three-electrode device with an Ag/AgCl electrode as reference electrode and a graphite electrode as counter electrode, using a platinum sheet electrode clamp as working electrode; potential reference Reversible Hydrogen Electrode (RHE): e (E) RHE ＝E Ag/AgCl +0.098+0.059×pH(0.5M H 2 SO 4 A solution). The overpotential (η) is calculated according to the following equation: η=e RHE -1.23V. At a scan rate of 1mV/s at saturated 0.5. 0.5M H 2 SO 4 Linear Sweep Voltammetry (LSV) was recorded in solution to obtain a polarization curve, see FIG. 2, and it was found that comparative example 2 had an overpotential increase of about 118mV for oxygen evolution catalysis under acidic conditions as compared to example 1. All electrode potential data were 100% voltage drop compensated.
In summary, a novel non-noble metal-based acidic electrolytic water oxygen evolution reaction electrocatalyst and a preparation method thereof form a novel material structure by introducing halogen into manganese-based oxide and are suitable for catalyzing oxygen evolution reaction under acidic conditions. The activity of the catalyst material is obviously improved compared with that of a manganese-based oxide catalyst, and the stability of the catalyst is also well maintained.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims (6)

1. The application of the manganese-based bromine oxide as an acid electrolyzed water oxygen evolution reaction electrocatalyst is characterized in that the electrocatalyst is manganese-based bromine oxide, the manganese-based bromine oxide has a crystal structure with multiple crystal faces, wherein the content ratio of Mn, O and Br elements is 7.5:10:3, and the chemical formula is Mn 7.5 O 10 Br 3 。
2. The use according to claim 1, characterized in that the electrocatalytic activity of the manganese-based oxybromide material reaches 10mA/cm in an acidic medium at ph=0 2 The overpotential required for the catalytic current density ranges from 290 to 330mV.
3. The use according to claim 1, wherein the manganese-based oxybromide material is at 10mA/cm 2 The stable operation time under the current density condition exceeds 450 hours, and the over-potential rising rate ranges from 0.2 to 0.3mV/h.
4. The use according to claim 1, wherein the manganese-based oxybromide is prepared by the following method:
dissolving manganese-based bromine salt in water, adding prepared manganese-based nitrate into the solution, mixing the manganese-based nitrate and the solution at a molar ratio of 1:4 to obtain a precursor solution, uniformly dripping the precursor solution on conductive hydrophilic carbon cloth, continuously heating the precursor solution for 3-5 hours at 200-300 ℃, cooling the precursor solution, ultrasonically cleaning the obtained product with deionized water, and then drying the product to obtain the electrocatalyst.
5. The use according to claim 4, wherein the mixing is by ultrasonic dissolution followed by sufficient mechanical shaking.
6. The use according to claim 4, wherein the conductive hydrophilic carbon cloth is subjected to pretreatment by: soaking commercial conductive carbon cloth in acetone for 15-30 minutes by ultrasonic treatment, respectively washing with deionized water and absolute ethyl alcohol for three times, and drying; placing the cleaned and dried carbon in nitric acid with the concentration of 40%, and oxidizing for 30-50 min under ultrasonic conditions.
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SYNTHESIS AND STRUCTURAL STUDIES OF MANGANESE OXYHALIDES WITH A MULTISITE FRAMEWORK;P. EUZEN et. al.;《Mat. Res. Bull.,》;第27卷;1423-1430 *

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