CN113026032B

CN113026032B - Ruthenium atom-level loaded manganese oxide catalyst and preparation method and application thereof

Info

Publication number: CN113026032B
Application number: CN202110262336.5A
Authority: CN
Inventors: ***; 林超
Original assignee: Donghua University
Current assignee: Donghua University
Priority date: 2021-03-10
Filing date: 2021-03-10
Publication date: 2023-04-11
Anticipated expiration: 2041-03-10
Also published as: CN113026032A

Abstract

The invention provides a ruthenium atom-level loaded manganese oxide catalyst and a preparation method and application thereof. The preparation method comprises the following steps: 1) Carrying out hydrothermal reaction on the mixed solution, filtering, washing and drying to obtain a solid product; the mixed solution comprises manganese salt, an oxidant, a pore canal filler and water; 2) And (3) reacting the solid product with ruthenium salt in solvent water, filtering, washing, drying, roasting and cooling to obtain the catalyst. The ruthenium atomic-scale-loaded manganese oxide catalyst is obtained by the preparation method, the ruthenium element component which is uniformly dispersed in atomic scale is anchored on the outer surface of the manganese oxide nanowire which is stable in an acidic medium, the dispersion effect of the ruthenium metal active site is effectively improved, the charge distribution structure of the active site is optimized, and the intrinsic activity and stability of the active site are improved.

Description

Ruthenium atom-level loaded manganese oxide catalyst and preparation method and application thereof

Technical Field

The invention belongs to the technical field of nano materials and energy technology, relates to a ruthenium atomic-scale loaded manganese oxide catalyst, a preparation method and application thereof, and particularly relates to an acidic and stable oxygen evolution reaction catalytic material, namely an anode material for hydrogen production by water electrolysis, a preparation method and application thereof in the field of hydrogen production by water electrolysis.

Background

Renewable energy power generation such as wind energy, tidal energy and solar energy is becoming the cheapest power generation technology in recent years. The conversion of renewable energy sources into "fuels" is an important renewable energy strategy to cope with the exhaustion of fossil fuels and climate change in the future. The hydrogen production by electrolyzing water by using renewable energy is one of the most feasible large-scale renewable energy storage and utilization technologies at present. Among the numerous water electrolysis technologies, proton Exchange Membrane (PEM) water electrolysis technologies are of great interest. The electrocatalytic Oxygen Evolution Reaction (OER) is an important anode half-reaction in the electrocatalytic energy conversion technology. However, OER is kinetically slow and requires an efficient oxygen evolution electrocatalyst to lower the reaction energy barrier and thus accelerate the reaction. Despite the diligent efforts to develop a number of highly efficient and stable basic OER catalysts, little has been done in the development of acidic OER electrocatalysts. Because the electrocatalysis reaction in the acidic PEM electrolytic cell has the advantages of higher mass transfer speed, higher product purity, higher reaction efficiency and the like, the development of the high-efficiency acidic OER electrocatalyst has more important large-scale industrial application significance. To date, there is still a lack of highly active and stable acidic OER electrocatalysts, which greatly hampers the electrocatalytic energy sourceThe conversion reaction develops in an acidic medium. At present, although RuO ₂ The catalyst is an acidic oxygen evolution catalyst with the highest intrinsic activity, but the storage capacity is limited, the cost is high, and the utilization rate of the noble metal needs to be improved as much as possible in order to reduce the use amount of the noble metal and the cost of the catalyst. Increasing the active site density per unit area by maximizing the dispersion of the noble metal is the most effective method for reducing the noble metal materials and improving the utilization rate of the noble metal. A common strategy is to load noble metal nanoparticles on a corrosion-resistant conductive support with high specific surface area, such as RuO ₂ CNT and RuO ₂ Gr, but the interaction force between the active component and the carrier in the system is relatively weak, the dispersion degree of the active sites is limited, the agglomeration is easy, and the activity and the stability of the catalyst are not ideal.

Manganese oxide is the most common acidic and stable transition metal oxide, has low cost, is environment-friendly and harmless to human bodies, and is known as the most potential high-stability non-noble metal acidic OER catalyst. And the manganese oxide can realize the secondary deposition of manganese ions on the surface of the manganese oxide through a self-repairing mechanism under the acidic electrolytic oxygen evolution reaction environment, and the tolerance capability and the performance stability of the manganese oxide in an acidic reaction system are greatly improved through the mechanism. However, the single manganese oxide nanomaterial cannot meet the commercial demand due to the high OER reaction energy barrier of manganese oxide.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide a ruthenium atom-grade supported manganese oxide catalyst, and a preparation method and application thereof, so as to solve the problems of few types, low activity and poor stability of the existing acidic OER catalyst. The ruthenium atomic-scale-loaded manganese oxide catalyst obtained by the preparation method can anchor the ruthenium element component uniformly dispersed in atomic scale on the outer surface of the manganese oxide nanowire stable in an acidic medium, effectively improve the dispersion effect of ruthenium metal active sites, optimize the charge distribution structure of the active sites, improve the intrinsic activity and stability of the active sites, stably operate for a long period in an acidic electrolyte environment, solve the problem of poor stability of an anode material in the acidic electrolyte environment, and have long service life.

In order to achieve the above and other related objects, a first aspect of the present invention provides a method for preparing a ruthenium atom-scale supported manganese oxide catalyst, comprising the steps of:

1) Carrying out hydrothermal reaction on the mixed solution, filtering, washing and drying to obtain a solid product; the mixed solution comprises manganese salt, an oxidant, a pore filler and solvent water;

2) And (3) reacting the solid product with ruthenium salt in solvent water, filtering, washing, drying, roasting and cooling to obtain the catalyst.

Preferably, step 1) further comprises at least one of the following technical features:

1a) The manganese salt is selected from at least one of manganese sulfate, manganese acetate, manganese nitrate and manganese chloride;

1b) The oxidant is persulfate;

1c) The pore filler is selected from at least one of potassium salt, sodium salt and ammonium salt;

1d) The molar ratio of the manganese salt to the oxidant is 0.5-2:1, such as 0.5-0.99: 1. 0.99 to 1: 1. 1-1.02:1 or 1.02-2:1;

1e) The molar ratio of the manganese salt to the pore canal filler is 1:2 to 5, such as 1: 2-3, 1: 3-3.05, 1:3.05 to 3.07, 1:3.07 to 5;

1f) In the mixed solution, the concentration of the oxidant is 0.1-2.0mol/l, such as 0.1-0.28mol/l, 0.28-0.6mol/l or 0.6-2.0mol/l.

More preferably, at least one of the following technical characteristics is also included:

1b1) The feature 1 b) is that the persulfate is at least one selected from the group consisting of ammonium persulfate, potassium persulfate, and sodium persulfate;

1c1) In the feature 1 c), the potassium salt is at least one selected from potassium sulfate, potassium acetate, potassium nitrate and potassium chloride;

1c2) In the feature 1 c), the sodium salt is at least one selected from the group consisting of sodium sulfate, sodium acetate, sodium nitrate and sodium chloride;

1c3) In the feature 1 c), the ammonium salt is at least one selected from the group consisting of ammonium sulfate, ammonium acetate, ammonium nitrate and ammonium chloride;

1d1) In feature 1 d), the molar ratio of the manganese salt to the oxidizing agent is 0.5 to 1.5:1;

1e1) Characteristic 1 e), the molar ratio of the manganese salt to the pore filler is 1:2.5 to 3.5;

1f1) In feature 1 f), the concentration of the oxidizing agent is 0.2 to 1.0mol/l.

1h) The reaction temperature of the hydrothermal reaction is 100-180 ℃, such as 100-140 ℃ or 140-180 ℃;

1i) The reaction time of the hydrothermal reaction is 0.5-24h, such as 0.5-12h or 12-24h;

1j) The hydrothermal reaction is carried out in a hydrothermal kettle;

1k) After the hydrothermal reaction, carrying out filtration treatment in a suction filtration mode;

1 l) the washing is one or more times with deionized water and/or ethanol;

1 m) the drying temperature is 60-100 ℃, such as 60-80 ℃ or 80-100 ℃;

1 n) the drying time is 1-24h, such as 1-12h or 12-24h.

Preferably, step 2) further comprises at least one of the following technical features:

2a) The solid product is in MnO ₂ The ratio of the calculated molar amount to the molar amount of the ruthenium salt is 1:1 to 50, such as 1:1 to 3.21, 1:3.21 to 6.43, 1: 6.43-12.85, 1: 12.85-25.71 or 1:25.71 to 50;

2b) The concentration of the ruthenium salt is 1 to 15mol/L, such as 1 to 1.205mol/L, 1.205 to 2.41mol/L, 2.41 to 4.82mol/L, 4.82 to 9.64mol/L, or 9.64 to 15mol/L, based on the total amount of the solid product, the ruthenium salt, and the solvent water;

2c) The ruthenium salt is selected from one or more of ruthenium acetate, ruthenium nitrate and ruthenium chloride;

2d) The reaction time is 1-24h, such as 1-12h or 12-24h;

2e) The reaction is a stirring reaction at room temperature; the room temperature is 20-30 ℃;

2f) The filtration mode is suction filtration;

2g) Washing is carried out after the filtration, and the washing is carried out for one time or multiple times by adopting water;

2h) The drying temperature is 50-80 deg.C, such as 50-70 deg.C or 70-80 deg.C;

2i) The drying time is 2-24h, such as 2-12h or 12-24h;

2j) The roasting temperature is 150-250 deg.C, such as 150-200 deg.C or 200-250 deg.C;

2k) The roasting time is 1-5h;

2 l) the roasting atmosphere is air atmosphere;

2 m) the cooling is natural cooling to room temperature; the room temperature is 20-30 ℃;

2 n) mixing the solid product and part of solvent water in an ultrasonic dispersion mode to obtain a first solution; mixing the ruthenium salt and the residual solvent water to obtain a second solution; and mixing the first solution and the second solution for reaction.

2a1) In feature 2 a), the solid product is in the form of MnO ₂ The ratio of the calculated molar amount to the molar amount of the ruthenium salt is 1:3 to 30 percent;

2b1) In the feature 2 b), the concentration of the ruthenium salt is 2 to 20mol/L;

2d1) In the characteristic 2 d), the reaction time is 10-24h;

2n 1) feature 2 n), the ultrasonic time of the ultrasonic dispersion is 10-60min;

2n 2) feature 2 n), the ruthenium salt concentration of the second solution is 2 to 30mol/L, such as 2 to 2.41mol/L, 2.41 to 4.82mol/L, 4.82 to 9.64mol/L, 9.64 to 19.28mol/L, or 19.28 to 30mol/L.

2j1) In the characteristic 2 j), the roasting temperature is 150-230 ℃;

2k1) In the characteristic 2 k), the roasting time is 1-3h.

The invention provides a manganese oxide catalyst loaded on a ruthenium atom scale, which is prepared by the preparation method.

Preferably, the method comprises atomically dispersed ruthenium element multi-center active sites and manganese oxide nanowires.

In a third aspect, the invention provides the use of the ruthenium atom-scale-supported manganese oxide catalyst as an anode material for an acidic aqueous solution electrolytic cell.

As mentioned above, the ruthenium atom-level supported manganese oxide catalyst, the preparation method and the application thereof provided by the invention have the following beneficial effects:

(1) According to the ruthenium atomic-level loaded manganese oxide catalyst, the ruthenium element components uniformly dispersed at the atomic level are anchored on the outer surface of the manganese oxide nanowire stable in an acidic medium, so that the dispersion effect of ruthenium metal active sites is effectively improved, the charge distribution structure of the active sites is optimized, and the intrinsic activity and stability of the active sites are improved.

(2) The ruthenium atom-level loaded manganese oxide catalyst can be used as a high-performance acidic oxygen evolution reaction electrocatalyst, can stably and efficiently perform Oxygen Evolution Reaction (OER) in an acidic electrolyte environment, can be used as an anode material for hydrogen production by water electrolysis, is used in a proton conduction polymer membrane electrolytic hydrogen production electrolytic cell, and solves the problems of few types, low performance and short service life of the existing acidic oxygen evolution catalyst.

Drawings

FIG. 1 shows Ru/MnO as described in examples and comparative examples ₂ X-ray diffraction patterns 1a and 1b for catalysts, where FIG. 1a is the Ru/MnO described in the examples ₂ X-ray diffraction Pattern of the catalyst, FIG. 1b shows Ru/MnO as described in example 4 and comparative examples 1# and 2# ₂ X-ray diffraction pattern of the catalyst.

FIG. 2 shows Ru/MnO as described in scanning example of scanning Electron microscopy ₂ Image obtained from the catalyst.

FIG. 3 shows Ru/MnO in example 4 ₂ Synchrotron radiation X-ray absorption fine structure spectrum of the catalyst.

FIG. 4 shows Ru/MnO ₂ Oxygen evolution polarization curve results for the catalyst.

FIG. 5 shows Ru/MnO ₂ The oxygen evolution catalytic performance of the catalyst is compared with that of the reported acidic OER catalyst.

FIG. 6 shows Ru/MnO ₂ The catalyst (example 4) at a current density of 10mAcm ^-2 Next, long cycle stability test results.

FIG. 7 shows Ru/MnO before and after electrocatalytic reaction for scanning by a high angle annular dark field scanning transmission electron microscope after spherical aberration correction ₂ Images 7a, 7b obtained with the catalyst (example 4), where FIG. 7a is Ru/MnO ₂ Electron microscope images before catalyst reaction; FIG. 7b is Ru/MnO ₂ Electron microscope images after catalyst reaction.

FIG. 8 shows Ru/MnO before and after reaction ₂ Catalyst energy scattering

X-ray spectra

8a, 8b, where FIG. 8a is Ru/MnO ₂ Energy scattering X-ray spectroscopy before catalyst reaction; FIG. 8b shows Ru/MnO ₂ The energy after the catalyst reaction scatters the X-ray spectrum.

Detailed Description

The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.

The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.

It should be understood that the processing equipment or devices not specifically mentioned in the following examples are conventional in the art; all pressure values and ranges refer to relative pressures.

Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.

Example 1

0.02mol of manganese sulfate and 0.06mol of potassium sulfate are added into 70ml of ammonium persulfate aqueous solution with the concentration of 0.28mol/l, and a mixed solution is obtained after complete dissolution. And (3) putting the mixed solution into a hydrothermal kettle, carrying out hydrothermal reaction for 12h at the temperature of 140 ℃, washing for multiple times by using deionized water, and drying for 12h at the temperature of 80 ℃ to obtain a solid product A.

Ultrasonically dispersing 15mmol of solid product A in 20mL of deionized water, and adding 20mL of RuCl with the concentration of 2.41mol/l in one portion ₃ The aqueous solution is vigorously stirred and reacts for 1 hour, the solution is filtered until solid precipitate is completely dried, a large amount of deionized water is adopted for washing for many times, the solid precipitate is dried for 12 hours at the temperature of 80 ℃, the solid precipitate is roasted for 1 hour in the air atmosphere at the temperature of 200 ℃, and the solid precipitate is naturally cooled to room temperature to obtain Ru/MnO ₂ Catalyst sample # 1.

Example 2

0.014mol of manganese nitrate and 0.043mol of potassium nitrate were added to 50ml of an aqueous ammonium persulfate solution having a concentration of 0.28mol/l, and completely dissolved to obtain a mixed solution. And (3) putting the mixed solution into a hydrothermal kettle, carrying out hydrothermal reaction for 12h at the temperature of 140 ℃, washing for multiple times by using deionized water, and drying for 12h at the temperature of 80 ℃ to obtain a solid product A.

Ultrasonically dispersing 15mmol of solid product A in 20ml of deionized water, and adding 20ml of RuCl with the concentration of 4.82mol/l in one step ₃ Stirring the aqueous solution vigorously for reacting for 1h, filtering until the solid precipitate is completely dried, washing with a large amount of deionized water, drying at 80 deg.C for 8h, and calcining at 200 deg.C in air atmosphereNaturally cooling to room temperature for 1h to obtain Ru/MnO ₂ Catalyst sample # 2.

Example 3

0.028mol of manganese nitrate and 0.086mol of potassium nitrate were added to 100ml of an aqueous ammonium persulfate solution having a concentration of 0.28mol/l, and the mixture was completely dissolved to obtain a mixed solution. And (3) putting the mixed solution into a hydrothermal kettle, carrying out hydrothermal reaction for 12h at the temperature of 140 ℃, washing for multiple times by using deionized water, and drying for 12h at the temperature of 80 ℃ to obtain a solid product A.

Ultrasonically dispersing 15mmol of solid product A in 20ml of deionized water, and adding 20ml of RuCl with the concentration of 9.64mol/l in one step ₃ The aqueous solution is violently stirred and reacts for 1 hour, then is filtered until solid precipitate is completely dried, is washed by a large amount of deionized water for many times, is dried for 12 hours at 70 ℃, is roasted for 1 hour in air atmosphere at the temperature of 200 ℃, and is naturally cooled to room temperature to obtain Ru/MnO ₂ Catalyst sample # 3.

Example 4

0.021mol of manganese nitrate and 0.064mol of potassium nitrate were added to 75ml of an aqueous ammonium persulfate solution having a concentration of 0.28mol/l, and the mixture was completely dissolved to obtain a mixed solution. And (3) putting the mixed solution into a hydrothermal kettle, carrying out hydrothermal reaction for 12h at the temperature of 140 ℃, washing for multiple times by using deionized water, and drying for 12h at the temperature of 80 ℃ to obtain a solid product A.

30mmol of solid product A are dispersed ultrasonically in 40ml of deionized water, 40ml of RuCl with the concentration of 19.28mol/l are added in one portion ₃ The aqueous solution is vigorously stirred and reacts for 12 hours, then is filtered until solid precipitate is completely dried, is washed by a large amount of deionized water for a plurality of times, is dried for 12 hours at 80 ℃, is roasted for 1 hour in the air atmosphere at the temperature of 200 ℃, and is naturally cooled to room temperature to obtain Ru/MnO ₂ Catalyst sample # 4.

Example 5

0.028mol of manganese nitrate and 0.086mol of potassium nitrate were added to 14ml of an aqueous ammonium persulfate solution having a concentration of 2.0mol/l, and a mixed solution was obtained after complete dissolution. And (3) putting the mixed solution into a hydrothermal kettle, carrying out hydrothermal reaction for 12h at the temperature of 140 ℃, washing for multiple times by using deionized water, and drying for 12h at the temperature of 80 ℃ to obtain a solid product A.

30mmol of solid product A are dispersed ultrasonically in 40ml of deionized water, 40ml of RuCl with the concentration of 19.28mol/l are added in one portion ₃ The aqueous solution is vigorously stirred and reacts for 12 hours, then is filtered until solid precipitate is completely dried, is washed by a large amount of deionized water for a plurality of times, is dried for 12 hours at 80 ℃, is roasted for 1 hour in the air atmosphere at the temperature of 200 ℃, and is naturally cooled to room temperature to obtain Ru/MnO ₂ Catalyst sample # 5.

Example 6

0.028mol of manganese nitrate and 0.086mol of potassium sulfate are added into 47ml of 0.6mol/l ammonium persulfate aqueous solution, and a mixed solution is obtained after complete dissolution. And (3) putting the mixed solution into a hydrothermal kettle, carrying out hydrothermal reaction for 12h at the temperature of 140 ℃, washing for multiple times by using deionized water, and drying for 12h at the temperature of 80 ℃ to obtain a solid product A.

30mmol of solid product A are dispersed ultrasonically in 40ml of deionized water, 40ml of RuCl with the concentration of 19.28mol/l are added in one portion ₃ The aqueous solution is vigorously stirred and reacts for 12 hours, then is filtered until solid precipitate is completely dried, is washed by a large amount of deionized water for a plurality of times, is dried for 12 hours at 80 ℃, is roasted for 1 hour in the air atmosphere at the temperature of 200 ℃, and is naturally cooled to room temperature to obtain Ru/MnO ₂ Catalyst sample # 6.

Ru/MnO obtained in examples 1-6 ₂ Catalyst samples # 1-6 were subjected to X-ray testing and the results are shown in FIG. 1. As can be seen from fig. 1a and 1b, the support in the catalyst is alpha-phase manganese oxide, and no characteristic peak corresponding to ruthenium and its oxide is found, which indicates that the ruthenium element of the sample prepared in the example is uniformly dispersed and no agglomeration occurs. From FIG. 1b, when MnO was changed ₂ Nanowire preparation conditions, mnO ₂ The peak intensity of the corresponding characteristic peak is obviously changed, which indicates that the MnO is improved by the high manganese ion concentration ₂ The crystallinity of (a).

Ru/MnO obtained in examples 1 to 4 ₂ Catalyst samples # 1-4, were scanned by scanning electron microscopy and the results are shown in figure 2. As can be seen from FIG. 2, the catalysts described in examples 1-4 are all of nanowire structure, and the surface roughness gradually increases with the increase of the loading amount of the ruthenium element, which indicates that the ruthenium element can be effectively negatively charged through the cation exchange reactionLoaded on the surface of the manganese oxide carrier.

Ru/MnO obtained in example 4 ₂ And 4# catalyst sample, performing synchrotron radiation X-ray absorption spectrum fine structure analysis, and obtaining a test result shown in figure 3. From the fitting results of the curve of FIG. 3, ru/MnO ₂ In the catalyst, the coordination number of the Ru-O bond is 6, and the coordination number of the Ru-Ru bond is 2.7, which shows that the Ru active sites in the catalyst are of a multi-center atomic-level dispersed structure connected by the Ru-O bond, and the active sites can effectively cooperate with each other, thereby providing a structural basis for realizing the oxygen evolution reaction depending on an oxide path, and being beneficial to accelerating the promotion of the catalytic process of the oxygen evolution reaction on the premise of not influencing the stability of the material.

Ru/MnO obtained in examples 1 to 4 was measured ₂ Catalyst samples 1-4# at 0.1M HClO ₄ The catalytic activity of the oxygen evolution reaction in aqueous solution is shown in fig. 4 and 5. As can be seen from FIGS. 4 and 5, the optimized Ru/MnO ₂ The catalyst shows excellent OER catalytic performance of an acid electrolyte system, 10mAcm ^-2 The overpotential is only 161mV, which is superior to RuO ₂ Catalysts, and other noble metal acidic OER catalysts have been reported.

Ru/MnO obtained in example 4 ₂ And 4# catalyst sample, carrying out a constant current oxygen evolution reaction stability test, and the test result is shown in figure 6. As can be seen from FIG. 6, ru/MnO ₂ The catalyst can effectively carry out OER reaction for more than 100h, has no obvious performance attenuation, and fully proves the stability of the catalytic performance. Scanning of the Ru/MnO obtained in example 4 with a high angle annular dark field scanning transmission electron microscope after spherical aberration correction ₂ The images of catalyst sample 4# before and after the oxygen evolution reaction stability test are shown in fig. 7. As can be seen from FIG. 7a, the Ru/MnO was prior to the OER reaction ₂ Orderly arranged bright spots were observed on the surface of the catalyst, and Ru/MnO after the reaction was observed from FIG. 7b ₂ The catalyst surface is enriched with more obvious ordered bright spots arranged in an array manner. As can be seen from the results of the energy scattering X-ray spectrum of fig. 8, the ordered bright spots in the sample before and after the reaction correspond to Ru atoms. The Ru element can self-assemble to form an ordered array structure in the OER reaction process, and the single-atom-layer and multi-center cooperative ruthenium atom structure is beneficial to the OER reactionThe catalyst relies on a metal oxide mechanism to efficiently and stably drive the electrolytic oxygen generation reaction to proceed.

In conclusion, the invention provides a preparation method and application of a high-performance oxygen evolution reaction catalyst suitable for an acidic electrolyte system, and prepared Ru/MnO ₂ The catalyst can be used as an anode material of an electrolytic cell for producing hydrogen by electrolyzing water, solves the problems of few types, low performance and short service life of the existing acidic electrolyte system oxygen evolution reaction catalyst, and prepares the Ru/MnO ₂ The catalyst shows excellent oxygen evolution reaction activity and long-period stability under an acidic system, and is far superior to most of reported related catalysts. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.

The above examples are intended to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, various modifications of the methods and compositions set forth herein, as well as variations of the methods and compositions of the present invention, will be apparent to those skilled in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the above-described embodiments which are obvious to those skilled in the art to which the invention pertains are intended to be covered by the scope of the present invention.

Claims

1. A preparation method of a ruthenium atom-level loaded manganese oxide catalyst is characterized by comprising the following steps:

2) Carrying out cation exchange reaction on the solid product and ruthenium salt in solvent water at room temperature, filtering, washing, drying, roasting and cooling to obtain a catalyst, wherein ruthenium atoms in the manganese oxide catalyst are orderly arranged in an atomic chain and are loaded on the surface of manganese oxide;

in the step 1), the molar ratio of the manganese salt to the oxidant is 0.5-2: 1; the molar ratio of the manganese salt to the pore canal filler is 1:2 to 5;

in step 2), the solid product is mixed with MnO ₂ The ratio of the calculated molar weight to the molar weight of the ruthenium salt is 1:1 to 50; the drying temperature is 50-80 ℃; the roasting temperature is 150-250 ℃.

2. The method for preparing the ruthenium atom-based supported manganese oxide catalyst according to claim 1, wherein the step 1) further comprises at least one of the following technical characteristics:

1b) The oxidant is persulfate;

1c) The pore canal filling agent is selected from at least one of potassium salt, sodium salt and ammonium salt;

1f) In the mixed solution, the concentration of the oxidant is 0.1-2.0mol/l.

3. The method for preparing a ruthenium atom-scale supported manganese oxide catalyst according to claim 1, wherein the molar ratio of the manganese salt to the oxidizing agent is 0.5 to 1.5:1.

4. the method of preparing a ruthenium atomic scale supported manganese oxide catalyst according to claim 1, wherein the molar ratio of said manganese salt to said channel filler is 1:2.5 to 3.5.

5. The method for preparing the ruthenium atomic scale supported manganese oxide catalyst according to claim 2, further comprising at least one of the following technical features:

6. The method for preparing the ruthenium atom-based supported manganese oxide catalyst according to claim 1, wherein the step 1) further comprises at least one of the following technical characteristics:

1h) The reaction temperature of the hydrothermal reaction is 100-180 ℃;

1i) The reaction time of the hydrothermal reaction is 0.5-24h;

1j) The hydrothermal reaction is carried out in a hydrothermal kettle;

1 l) the washing is one or more times with deionized water and/or ethanol;

1 m) the drying temperature is 60-100 ℃;

1 n) the drying time is 1-24h.

7. The method of claim 1, wherein the solid product is in the form of MnO ₂ The ratio of the calculated molar amount to the molar amount of the ruthenium salt is 1:3 to 30.

8. The method for preparing the ruthenium atom-based supported manganese oxide catalyst according to claim 1, wherein the step 2) further comprises at least one of the following technical characteristics:

2b) The concentration of the ruthenium salt is 1 to 15mol/L based on the total amount of the solid product, the ruthenium salt and the solvent water;

2d) The reaction time is 1-24h;

2e) The reaction is carried out under stirring conditions;

2f) The filtration mode is suction filtration;

2i) The drying time is 2-24h;

2k) The roasting time is 1-5h;

2 l) the roasting atmosphere is air atmosphere;

2 m) the cooling is natural cooling to room temperature;

9. The method of claim 8, further comprising at least one of the following features:

2d1) In the characteristic 2 d), the reaction time is 10-24h;

2n 2) feature 2 n), the ruthenium salt concentration of the second solution is 2 to 30mol/L.

10. The method of claim 8, further comprising at least one of the following features:

2j1) In the characteristic 2 j), the roasting temperature is 150-230 ℃;

2k1) In the characteristic 2 k), the roasting time is 1-3h.

11. A ruthenium atom-scale supported manganese oxide catalyst, characterized by being obtained by the production method according to any one of claims 1 to 10.

12. The ruthenium atomically supported manganese oxide catalyst of claim 11 comprising atomically dispersed multicenter active sites of ruthenium element and manganese oxide nanowires.

13. Use of a ruthenium atom scale supported manganese oxide catalyst as claimed in claim 11 or 12 as anode material for an acidic aqueous solution electrolysis cell.