Preparation method of ruthenium cluster alkene catalyst, ruthenium cluster alkene catalyst and application of ruthenium cluster alkene catalyst

Abstract

The invention provides a preparation method of a ruthenium cluster alkene catalyst, the ruthenium cluster alkene catalyst and application of the ruthenium cluster alkene catalyst, and relates to the technical field of carbon-supported catalysts. The preparation method of the ruthenium cluster alkene catalyst comprises the following steps: (1) mixing an organic noble metal ruthenium source, inorganic salt of alkali metal and a carbon carrier, and grinding to obtain a mixture; and (2) calcining the mixture obtained in the step (1), washing and drying to obtain the ruthenium cluster alkene catalyst. The preparation method of the ruthenium cluster alkene catalyst has the advantages of being green and simple, and large-scale synthesis of the catalyst can be achieved. In a hydrogen evolution reaction, the obtained catalyst shows the electrocatalytic activity superior to that of commercial platinum carbon and commercial ruthenium carbon; in anionic membrane alkaline electrolyzers, the catalyst also exhibits superior device activity over existing membrane electrode assemblies and maintains stability over long periods of time at high current densities.

Description

Technical Field

[0001] The present invention relates to the technical field of the preparation of novel carbon-supported catalysts, and particularly to a preparation method of a ruthenium cluster ene catalyst, a ruthenium cluster ene catalyst and its application, and more particularly to a preparation method of a ruthenium cluster ene catalyst, a ruthenium cluster ene catalyst and its application as an efficient hydrogen evolution catalyst in anionic membrane alkaline water electrolysis. Background Art

[0002] As a kind of inexpensive noble metal material expected to replace commercial platinum-carbon, ruthenium-based catalysts have received extensive attention in the field of electrocatalysis in recent years. Especially under the promotion of the "dual carbon" strategic goal, the application of ruthenium-based catalysts has developed rapidly. In the interfacial catalytic reaction, the particle size of noble metal catalysts is inversely proportional to their utilization rate. However, the preparation of sub-nanoscale catalysts often requires harsh conditions, and due to their high surface energy, it is easy to cause unstable structures. Therefore, it is of important application value to develop a scalable synthesis method and develop a sub-nanoscale ruthenium-based catalyst with high electrocatalytic stability.

[0003] CN117512641A - A carbon-supported ruthenium gallium intermetallic compound, a preparation method and its application. The preparation method includes: (1) dispersing ruthenium salt, gallium salt and a carbon carrier in a solvent and ultrasonically stirring, heating to evaporate the solvent, further drying the obtained sample and then grinding to obtain a precursor solid powder; (2) reducing the precursor solid powder in a reducing atmosphere to obtain a carbon-supported ruthenium gallium intermetallic compound. This preparation method cannot obtain a catalyst with a low-crystallinity and small-size cluster ene structure. The obtained carbon-supported ruthenium gallium intermetallic compound has an ordered structure and strong crystallinity; and during the calcination process, it needs to be carried out in a reducing atmosphere and at a high temperature of 600-800 °C to avoid the appearance of oxidation states on the surface of ruthenium gallium metal. The conditions are harsh, not suitable for large-scale production, and the differences in the structures of the obtained catalysts are not significant.

[0004] Research shows that when noble metal materials are at the nanometer particle, cluster or single atom scale, their utilization efficiency in electrocatalytic reactions is significantly improved. Currently, sub-nanoscale catalysts are usually synthesized by harsh conditions such as high-temperature calcination and post-treatment peeling. These catalysts have shown ultra-high mass activity in electrochemical tests, proving the application potential of sub-nanomaterials in devices. However, these methods are not suitable for large-scale production, and the differences in the structures of the obtained catalysts are not significant, resulting in the convergence of their electrochemical properties.

[0005] In view of this, the present invention is particularly proposed. Summary of the Invention

[0006] The object of the present invention is to provide a preparation method of a ruthenium cluster olefin catalyst, the ruthenium cluster olefin catalyst and its application. The preparation method of the present invention uses inorganic salts to regulate the migration behavior of ruthenium species during the growth process. The obtained catalyst realizes olefin-like properties on the carbon carrier, exhibits high hydrogen evolution activity, and shows ultra-long stability at high current densities.

[0007] In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:

[0008] In the first aspect, the present invention provides a preparation method of a ruthenium cluster olefin catalyst, and the preparation method of the ruthenium cluster olefin catalyst includes:

[0009] (1) Mix an organic noble metal ruthenium source, an inorganic salt of an alkali metal, and a carbon carrier, and grind to obtain a mixture;

[0010] (2) Calcinate the mixture obtained in step (1), and then wash and dry to obtain the ruthenium cluster olefin catalyst.

[0011] Preferably, in step (1), the organic noble metal ruthenium source is ruthenium acetylacetonate.

[0012] Preferably, in step (1), the inorganic salt of the alkali metal is selected from any one or a combination of at least two of the halides of the alkali metal.

[0013] Preferably, the alkali metal is selected from any one of lithium, sodium, or potassium.

[0014] Preferably, the halide is selected from any one of chlorides, bromides, or iodides.

[0015] Preferably, in step (1), the carbon carrier is selected from any one or a combination of at least two of carbon nanotubes, XC-72, Ketjenblack 300, Ketjenblack 600, or graphene.

[0016] Preferably, in step (1), the mass ratio of the organic noble metal ruthenium source, the inorganic salt of the alkali metal, and the carbon carrier is 10:(50 - 500):(5 - 20).

[0017] Preferably, in step (1), the rotation speed of the grinding is 50 - 200 rpm, and the grinding time is 60 - 120 min.

[0018] Preferably, in step (1), the particle size of the obtained mixture is 1 - 2 μm.

[0019] Preferably, in step (2), the calcination is carried out in a muffle furnace.

[0020] Preferably, in step (2), the heating rate of the calcination is 5-10 °C / min; the temperature of the calcination is 200-270 °C; the time of the calcination is 0.5-2 h.

[0021] Preferably, in step (2), the washing is carried out with pure water.

[0022] Preferably, in step (2), the drying temperature is 40-60 °C; the drying time is 2-4 h.

[0023] In a second aspect, the present invention provides a ruthenium cluster-ene catalyst, which is prepared by the preparation method of the ruthenium cluster-ene catalyst as described in the first aspect.

[0024] In a third aspect, the present invention provides an application of the ruthenium cluster-ene catalyst as described in the second aspect as an efficient hydrogen evolution catalyst in the preparation of an anion exchange membrane alkaline electrolytic water tank.

[0025] In a fourth aspect, the present invention provides a cathode for an anion exchange membrane alkaline electrolytic water tank, which comprises a diffusion layer and a catalyst layer; wherein, the catalyst layer comprises the ruthenium cluster-ene catalyst as described in the second aspect.

[0026] Preferably, the loading amount of the ruthenium cluster-ene catalyst is 0.1-0.5 mg·cm -2 .

[0027] Preferably, the diffusion layer is carbon paper.

[0028] In a fifth aspect, the present invention provides an anion exchange membrane alkaline electrolytic water tank, which comprises the cathode for an anion exchange membrane alkaline electrolytic water tank as described in the fourth aspect.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] (1) The preparation method of the ruthenium cluster-ene catalyst of the present invention is prepared by a solid-phase method, avoiding solvent pollution and meeting the requirements of green environmental protection;

[0031] (2) The preparation method of the ruthenium cluster-ene catalyst of the present invention adopts a low-temperature heat treatment process (200-270 °C), which can significantly save energy consumption;

[0032] (3) The synthesis process adopted by the preparation method of the ruthenium cluster-ene catalyst of the present invention is simple and efficient. It adopts a one-step calcination process and does not require harsh post-treatment conditions, having the advantage of large-scale preparation;

[0033] (4) The catalyst prepared by the preparation method of the ruthenium cluster-ene catalyst of the present invention is different from conventional sub-nanomaterials, has an enelike property, and has a stable structure;

[0034] (5) The synthesis process adopted in the preparation method of the ruthenium cluster ene catalyst of the present invention is stable, not easily affected by environmental factors, and the prepared hydrogen evolution catalyst has excellent performance. Description of the Drawings

[0035] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for use in the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0036] Figure 1 It is the transmission electron microscope image (TEM) and X-ray diffraction pattern (XRD) of the inorganic salt-regulated ruthenium cluster ene catalyst prepared in Example 1 of the present invention.

[0037] Figure 2 It is the transmission electron microscope image (TEM) of the inorganic salt-regulated ruthenium cluster ene catalyst prepared in Example 2 of the present invention.

[0038] Figure 3 It is the transmission electron microscope image (TEM) of the inorganic salt-regulated ruthenium cluster ene catalyst prepared in Example 3 of the present invention.

[0039] Figure 4 It is the X-ray diffraction pattern (XRD) of the inorganic salt-regulated ruthenium cluster ene catalyst prepared in Example 4 of the present invention.

[0040] Figure 5 It is the X-ray diffraction pattern (XRD) of the inorganic salt-regulated ruthenium cluster ene catalyst prepared in Example 5 of the present invention.

[0041] Figure 6 It is the linear sweep voltammogram (LSV) of the inorganic salt-regulated ruthenium cluster ene catalyst prepared in Example 1 of the present invention tested on a three-electrode system.

[0042] Figure 7 It is the activity curve of the inorganic salt-regulated ruthenium cluster ene catalyst prepared in Example 1 of the present invention in an anion exchange membrane alkaline electrolyzer.

[0043] Figure 8 It is the stability curve of the inorganic salt-regulated ruthenium cluster ene catalyst prepared in Example 1 of the present invention at a current density of 1 A·cm -2 in an anion exchange membrane alkaline electrolyzer.

[0044] Figure 9The stability curve of the inorganic salt-regulated ruthenium cluster-ene catalyst prepared in Example 1 of the present invention at a current density of 2 A·cm -2 in an anion exchange membrane alkaline electrolyzer.

[0045] Figure 10 The stability curve of the inorganic salt-regulated ruthenium cluster-ene catalyst prepared in Example 1 of the present invention at a current density of 3 A·cm -2 in an anion exchange membrane alkaline electrolyzer.

[0046] Figure 11 The X-ray diffraction pattern (XRD) of the inorganic salt-regulated ruthenium cluster-ene catalyst prepared in Example 1 of the present invention after 10-fold scale-up production.

[0047] Figure 12 The activity curves of the inorganic salt-regulated ruthenium cluster-ene catalyst prepared in Example 1 of the present invention in an anion exchange membrane alkaline electrolyzer after 10-fold and 50-fold scale-up production. Detailed implementation manners

[0048] Unless otherwise defined herein, scientific and technical terms used in conjunction with the present invention shall have the meanings commonly understood by those of ordinary skill in the art. The meanings and scopes of the terms should be clear. However, in any case of potential ambiguity, the definitions provided herein shall prevail over any dictionary or extrinsic definition. In this application, unless otherwise specified, the use of "or" means "and / or". In addition, the use of the term "comprising" and other forms is non-limiting.

[0049] It should be noted that specific details are set forth in the following description to facilitate a thorough understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar generalizations without departing from the spirit of the present invention. Therefore, the present invention is not limited by the specific implementation manners disclosed below.

[0050] The embodiments of the present invention will be described in detail below in conjunction with the implementation manners and examples. However, those skilled in the art will understand that the following implementation manners and examples are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention. All other examples obtained by those of ordinary skill in the art based on the examples of the present invention without creative efforts fall within the scope of protection of the present invention. Those not specifying specific conditions are carried out under conventional conditions or conditions recommended by the manufacturer. Those reagents or instruments not indicating the manufacturer can be obtained as conventional products commercially available.

[0051] In a first aspect, the present invention provides a method for preparing a ruthenium cluster-ene catalyst, and the method for preparing the ruthenium cluster-ene catalyst includes:

[0052] (1) Mix an organic noble metal ruthenium source, an inorganic salt of an alkali metal, and a carbon support, and grind them to obtain a mixture;

[0053] (2) Calcinate the mixture obtained in step (1), then wash and dry it to obtain the ruthenium cluster ene catalyst.

[0054] It should be noted that under the calcination conditions of the present invention, the set temperature is below the melting point of the inorganic salt of the alkali metal, and the inorganic salt of the alkali metal does not change at all, ensuring that the inorganic salt does not undergo a phase change and remains in a solid state, that is, it continuously absorbs the heat of the entire system during the calcination process but has not changed yet. Based on this, directly adding the inorganic salt of the alkali metal in the one-step calcination synthesis of the present invention can affect the migration characteristics of ruthenium species during the growth process by regulating the thermodynamics behavior of ruthenium species, thereby preparing a catalyst with a low crystallinity and small size cluster ene structure. In addition, according to the above scheme, the obtained catalyst realizes an ene-like property on the carbon support; and the catalyst obtained in the present invention only needs to be washed with water and does not need to go through harsh post-treatment steps.

[0055] As an optional implementation manner, in step (1), the organic noble metal ruthenium source is ruthenium acetylacetonate.

[0056] As an optional implementation manner, in step (1), the inorganic salt of the alkali metal is selected from any one or a combination of at least two of the halides of the alkali metal.

[0057] As an optional implementation manner, the alkali metal is selected from any one of lithium, sodium, or potassium.

[0058] As an optional implementation manner, the halide is selected from any one of chlorides, bromides, or iodides.

[0059] As an optional implementation manner, the inorganic salt of the alkali metal is selected from any one or a combination of at least two of lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, potassium bromide, lithium iodide, sodium iodide, or potassium iodide.

[0060] As an optional implementation manner, in step (1), the carbon support is selected from any one or a combination of at least two of carbon nanotubes, XC-72, Ketjenblack 300, Ketjenblack 600, or graphene.

[0061] As an optional implementation manner, in step (1), the mass ratio of the organic noble metal ruthenium source, the inorganic salt of the alkali metal, and the carbon support is 10:(50 - 500):(5 - 20);

[0062] Among them, "50 - 500" can be, for example, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, etc.;

[0063] Among them, "5 to 20" can be, for example, 5, 6, 8, 10, 12, 14, 15, 16, 18, 20, etc.

[0064] As an alternative embodiment, in step (1), the rotation speed of the grinding is 50 to 200 rpm, which can be, for example, 50 rpm, 60 rpm, 80 rpm, 100 rpm, 120 rpm, 140 rpm, 150 rpm, 160 rpm, 180 rpm, 200 rpm, etc., and the grinding time is 60 to 120 min, which can be, for example, 60 rpm, 70 rpm, 80 rpm, 90 rpm, 100 rpm, 110 rpm, 120 rpm, etc.

[0065] As an alternative embodiment, in step (1), the particle size of the mixture obtained by grinding is 1 to 2 μm, which can be, for example, 1 μm, 1.2 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.8 μm, 2 μm, etc.

[0066] As an alternative embodiment, in step (2), the calcination is carried out in a muffle furnace.

[0067] As an alternative embodiment, in step (2), the heating rate of the calcination is 5 to 10 °C / min, which can be, for example, 5 °C / min, 6 °C / min, 7 °C / min, 8 °C / min, 9 °C / min, 10 °C / min, etc.

[0068] As an alternative embodiment, in step (2), the temperature of the calcination is 200 to 270 °C, which can be, for example, 200 °C, 210 °C, 220 °C, 230 °C, 240 °C, 250 °C, 260 °C, 270 °C, etc.

[0069] As an alternative embodiment, in step (2), the time of the calcination is 0.5 to 2 h, which can be, for example, 0.5 h, 0.6 h, 0.8 h, 1 h, 1.2 h, 1.4 h, 1.5 h, 1.6 h, 1.8 h, 2 h, etc.

[0070] As an alternative embodiment, in step (2), the washing is carried out with pure water.

[0071] As an alternative embodiment, in step (2), the drying temperature is 40 to 60 °C, which can be, for example, 40 °C, 42 °C, 44 °C, 45 °C, 46 °C, 48 °C, 50 °C, 52 °C, 54 °C, 55 °C, 56 °C, 58 °C, 60 °C, etc.; the drying time is 2 to 4 h, which can be, for example, 2 h, 2.2 h, 2.4 h, 2.6 h, 2.8 h, 3 h, 3.2 h, 3.4 h, 3.6 h, 3.8 h, 4 h, etc.

[0072] In a second aspect, the present invention provides a ruthenium cluster olefin catalyst, which is prepared by the preparation method of the ruthenium cluster olefin catalyst as described in the first aspect.

[0073] In a third aspect, the present invention provides an application of the ruthenium cluster olefin catalyst as described in the second aspect as an efficient hydrogen evolution catalyst in the preparation of an anion exchange membrane alkaline electrolytic water tank.

[0074] In the present invention, the catalyst can be applied to the hydrogen evolution reaction and the anion exchange membrane alkaline electrolytic water tank, which has strong reference significance. Especially in the design and synthesis of sub-nanometer catalysts that can be prepared on a large scale, have high activity, high utilization efficiency and high stability, it provides an important reference.

[0075] In a fourth aspect, the present invention provides a cathode for an anion exchange membrane alkaline electrolytic water tank, which includes a diffusion layer and a catalyst layer; wherein, the catalyst layer includes the ruthenium cluster olefin catalyst as described in the second aspect.

[0076] As an optional embodiment, the noble metal loading of the ruthenium cluster olefin catalyst is 0.1 - 0.5 mg·cm -2 , for example, 0.1 mg·cm -2 , 0.15 mg·cm -2 , 0.2 mg·cm -2 , 0.25 mg·cm -2 , 0.3 mg·cm -2 , 0.35 mg·cm -2 , 0.4 mg·cm -2 , 0.45 mg·cm -2 , 0.5 mg·cm -2 and so on.

[0077] It should be noted that the loading mentioned in the present invention refers to the noble metal loading, that is, the weight of the noble metal sprayed on the carbon paper in the catalyst layer.

[0078] As an optional embodiment, the diffusion layer is carbon paper.

[0079] In a fifth aspect, the present invention provides an anion exchange membrane alkaline electrolytic water tank, which includes the cathode for an anion exchange membrane alkaline electrolytic water tank as described in the fourth aspect.

[0080] The present invention will be further described below through specific examples and comparative examples. However, it should be understood that these examples are only for more detailed description and should not be construed as limiting the present invention in any form.

[0081] Example 1

[0082] This embodiment provides a method for preparing a ruthenium cluster-ene catalyst. The method for preparing the ruthenium cluster-ene catalyst includes the following steps:

[0083] (1) Mix 10 mg of ruthenium acetylacetonate, 200 mg of sodium chloride, and 5 mg of XC-72, and grind them uniformly at a rotation speed of 200 rpm for 60 min to obtain a mixture with a particle size of 1 μm;

[0084] (2) Put the mixture obtained in step (1) into a muffle furnace. Under an air atmosphere, heat it to 250 °C at a rate of 5 °C / min and keep it warm for 2 h; then wash the obtained powder with pure water and dry it at 50 °C for 3 h to obtain the ruthenium cluster-ene catalyst.

[0085] Among them, Figure 1 are the transmission electron microscope image (TEM) and X-ray diffraction pattern (XRD) of the inorganic salt-regulated ruthenium cluster-ene catalyst prepared in Example 1 of the present invention. It can be seen from the transmission electron microscope image that the obtained ruthenium species are distributed in a cluster-ene-like manner on the carbon spheres, without obvious particle or cluster characteristics, and the unit area of the cluster-ene is small (≤2 nm). No strong peaks appear in the diffraction information of the XRD pattern, which proves the cluster-ene characteristics of the obtained catalyst.

[0086] Example 2

[0087] This embodiment provides a method for preparing a ruthenium cluster-ene catalyst. The method for preparing the ruthenium cluster-ene catalyst includes the following steps:

[0088] (1) Mix 10 mg of ruthenium acetylacetonate, 200 mg of sodium chloride, and 5 mg of carbon nanotubes, and grind them uniformly at a rotation speed of 200 rpm for 60 min to obtain a mixture with a particle size of 1 μm;

[0089] (2) Put the mixture obtained in step (1) into a muffle furnace. Under an air atmosphere, heat it to 250 °C at a rate of 5 °C / min and keep it warm for 2 h; then wash the obtained powder with pure water and dry it at 50 °C for 3 h to obtain the ruthenium cluster-ene catalyst.

[0090] Among them, Figure 2 is the transmission electron microscope image of the inorganic salt-regulated ruthenium cluster-ene catalyst provided in Example 2. It can be seen from the transmission electron microscope image that the obtained ruthenium species are distributed in a cluster-ene-like manner on the carbon nanotubes, without obvious particle or cluster characteristics, and the unit area of the cluster-ene is small (≤2 nm).

[0091] Example 3

[0092] This embodiment provides a method for preparing a ruthenium cluster-ene catalyst. The method for preparing the ruthenium cluster-ene catalyst includes the following steps:

[0093] (1) Mix 10 mg of ruthenium acetylacetonate, 200 mg of sodium chloride, and 5 mg of graphene, and conduct uniform grinding at a rotation speed of 200 rpm for 60 min to obtain a mixture with a particle size of 1 μm;

[0094] (2) Put the mixture obtained in step (1) into a muffle furnace. Under an air atmosphere, heat it to 250 °C at a rate of 5 °C / min and keep it warm for 2 h; then wash the obtained powder with pure water and dry it at 50 °C for 3 h to obtain the ruthenium cluster-ene catalyst.

[0095] Among them, Figure 3 is the transmission electron microscopy image of the inorganic salt-regulated ruthenium cluster-ene catalyst provided in Example 3. It can be seen from the transmission electron microscopy image that the obtained ruthenium species are distributed in an ene-like shape on graphene, without obvious particle or cluster characteristics, and the unit area of the ene is relatively small (≤2 nm).

[0096] Example 4

[0097] This example provides a preparation method of a ruthenium cluster-ene catalyst. The preparation method of the ruthenium cluster-ene catalyst includes the following steps:

[0098] (1) Mix 10 mg of ruthenium acetylacetonate, 200 mg of sodium chloride, and 5 mg of Ketjenblack 300, and conduct uniform grinding at a rotation speed of 200 rpm for 60 min to obtain a mixture with a particle size of 1 μm;

[0099] (2) Put the mixture obtained in step (1) into a muffle furnace. Under an air atmosphere, heat it to 250 °C at a rate of 5 °C / min and keep it warm for 2 h; then wash the obtained powder with pure water and dry it at 50 °C for 3 h to obtain the ruthenium cluster-ene catalyst.

[0100] Example 5

[0101] This example provides a preparation method of a ruthenium cluster-ene catalyst. The preparation method of the ruthenium cluster-ene catalyst includes the following steps:

[0102] (1) Mix 10 mg of ruthenium acetylacetonate, 200 mg of sodium chloride, and 5 mg of Ketjenblack 600, and conduct uniform grinding at a rotation speed of 200 rpm for 60 min to obtain a mixture with a particle size of 1 μm;

[0103] (2) Put the mixture obtained in step (1) into a muffle furnace. Under an air atmosphere, heat it to 250 °C at a rate of 5 °C / min and keep it warm for 2 h; then wash the obtained powder with pure water and dry it at 50 °C for 3 h to obtain the ruthenium cluster-ene catalyst.

[0104] Example 6

[0105] This embodiment provides a preparation method of a ruthenium cluster olefin catalyst. The preparation method of the ruthenium cluster olefin catalyst includes the following steps:

[0106] (1) Mix 10 mg of ruthenium acetylacetonate, 200 mg of lithium chloride, and 5 mg of carbon powder, and uniformly grind them at a rotation speed of 200 rpm for 60 min to obtain a mixture with a particle size of 1 μm;

[0107] (2) Put the mixture obtained in step (1) into a muffle furnace. Under an air atmosphere, heat it to 250 °C at a rate of 5 °C / min and keep it warm for 2 h; then wash the obtained powder with pure water and dry it at 50 °C for 3 h to obtain the ruthenium cluster olefin catalyst.

[0108] Among them, Figure 4 is the XRD pattern of the inorganic salt-regulated ruthenium cluster olefin catalyst provided in Example 6. The obtained catalyst has no obvious diffraction peaks, which proves the role of the inorganic salt in regulating the migration behavior of ruthenium species.

[0109] Example 7

[0110] This embodiment provides a preparation method of a ruthenium cluster olefin catalyst. The preparation method of the ruthenium cluster olefin catalyst includes the following steps:

[0111] (1) Mix 10 mg of ruthenium acetylacetonate, 200 mg of potassium chloride, and 5 mg of carbon powder, and uniformly grind them at a rotation speed of 200 rpm for 60 min to obtain a mixture with a particle size of 1 μm;

[0112] (2) Put the mixture obtained in step (1) into a muffle furnace. Under an air atmosphere, heat it to 250 °C at a rate of 5 °C / min and keep it warm for 2 h; then wash the obtained powder with pure water and dry it at 50 °C for 3 h to obtain the ruthenium cluster olefin catalyst.

[0113] Among them, Figure 5 is the XRD pattern of the inorganic salt-regulated ruthenium cluster olefin catalyst provided in Example 7. The obtained catalyst has no obvious diffraction peaks, which proves the role of the inorganic salt in regulating the migration behavior of ruthenium species.

[0114] Example 8

[0115] This embodiment provides a preparation method of a ruthenium cluster olefin catalyst. The preparation method of the ruthenium cluster olefin catalyst includes the following steps:

[0116] (1) Mix 10 mg of ruthenium acetylacetonate, 200 mg of sodium fluoride, and 5 mg of carbon powder, and uniformly grind them at a rotation speed of 200 rpm for 60 min to obtain a mixture with a particle size of 1 μm;

[0117] (2) Put the mixture obtained in step (1) into a muffle furnace. Under an air atmosphere, heat it to 250 °C at a rate of 5 °C / min and hold for 2 h. Subsequently, wash the resulting powder with pure water and dry it at 50 °C for 3 h to obtain the ruthenium cluster ene catalyst.

[0118] Example 9

[0119] This example provides a method for preparing a ruthenium cluster ene catalyst. The method for preparing the ruthenium cluster ene catalyst includes the following steps:

[0120] (1) Mix 10 mg of ruthenium acetylacetonate, 200 mg of sodium bromide, and 5 mg of carbon powder, and uniformly grind them at a rotation speed of 200 rpm for 60 min to obtain a mixture with a particle size of 1 μm;

[0121] (2) Put the mixture obtained in step (1) into a muffle furnace. Under an air atmosphere, heat it to 250 °C at a rate of 5 °C / min and hold for 2 h. Subsequently, wash the resulting powder with pure water and dry it at 50 °C for 3 h to obtain the ruthenium cluster ene catalyst.

[0122] Example 10

[0123] This example provides a method for preparing a ruthenium cluster ene catalyst. The method for preparing the ruthenium cluster ene catalyst includes the following steps:

[0124] (1) Mix 10 mg of ruthenium acetylacetonate, 200 mg of sodium iodide, and 5 mg of carbon powder, and uniformly grind them at a rotation speed of 200 rpm for 60 min to obtain a mixture with a particle size of 1 μm;

[0125] (2) Put the mixture obtained in step (1) into a muffle furnace. Under an air atmosphere, heat it to 250 °C at a rate of 5 °C / min and hold for 2 h. Subsequently, wash the resulting powder with pure water and dry it at 50 °C for 3 h to obtain the ruthenium cluster ene catalyst.

[0126] Example 11

[0127] This example provides a method for preparing a ruthenium cluster ene catalyst. The method for preparing the ruthenium cluster ene catalyst includes the following steps:

[0128] (1) Mix 10 mg of ruthenium acetylacetonate, 200 mg of potassium bromide, and 5 mg of carbon powder, and uniformly grind them at a rotation speed of 200 rpm for 60 min to obtain a mixture with a particle size of 1 μm;

[0129] (2) Put the mixture obtained in step (1) into a muffle furnace. Under an air atmosphere, heat it to 250 °C at a rate of 5 °C / min and hold for 2 h. Subsequently, wash the obtained powder with pure water and dry it at 50 °C for 3 h to obtain the ruthenium cluster ene catalyst.

[0130] Example 12

[0131] This example provides a preparation method of a ruthenium cluster ene catalyst. The preparation method of the ruthenium cluster ene catalyst includes the following steps:

[0132] (1) Mix 10 mg of ruthenium acetylacetonate, 200 mg of potassium iodide, and 5 mg of carbon powder, and grind them uniformly at a rotation speed of 200 rpm for 60 min to obtain a mixture with a particle size of 1 μm.

[0133] (2) Put the mixture obtained in step (1) into a muffle furnace. Under an air atmosphere, heat it to 250 °C at a rate of 5 °C / min and hold for 2 h. Subsequently, wash the obtained powder with pure water and dry it at 50 °C for 3 h to obtain the ruthenium cluster ene catalyst.

[0134] Comparative Example 1

[0135] This comparative example provides a preparation method of a ruthenium catalyst. The difference from Example 1 is only that sodium chloride is not added, and other steps are exactly the same as those in Example 1.

[0136] Comparative Example 2

[0137] This comparative example provides a preparation method of a ruthenium catalyst. The difference from Example 1 is only that the content of sodium chloride is reduced to 100 mg, and other steps are exactly the same as those in Example 1.

[0138] Comparative Example 3

[0139] This comparative example provides a preparation method of a ruthenium catalyst. The difference from Example 1 is only that the content of sodium chloride is increased to 500 mg, and other steps are exactly the same as those in Example 1.

[0140] Comparative Example 4

[0141] This comparative example provides a preparation method of a ruthenium catalyst. The difference from Example 1 is only that sodium chloride is replaced with an equal mass of ammonium chloride, and other steps are exactly the same as those in Example 1.

[0142] Comparative Example 5

[0143] This comparative example provides a preparation method of a ruthenium catalyst. The difference from Example 1 is only that ruthenium acetylacetonate is replaced with an equal mass of ruthenium chloride, and other steps are exactly the same as those in Example 1.

[0144] Comparative Example 6

[0145] This comparative example provides a method for preparing a ruthenium catalyst, which is only different from Example 1 in that the temperature is raised to 200 °C and held for 3 h, and the other steps are exactly the same as those in Example 1.

[0146] Comparative Example 7

[0147] This comparative example provides a method for preparing a ruthenium catalyst, which is only different from Example 1 in that the temperature is raised to 300 °C and held for 30 min, and the other steps are exactly the same as those in Example 1.

[0148] Test Example 1

[0149] Hydrogen evolution performance test

[0150] Test samples: The ruthenium cluster-ene catalysts provided in Examples 1, 6, 7, and 9, commercial platinum-carbon, commercial ruthenium-carbon, and the ruthenium catalysts provided in Comparative Examples 1-7.

[0151] Test method: Take each of the above catalyst samples as the working electrode and perform cyclic voltammetry scanning in the scanning range of -0.95 to -1.3 V (vs. SCE) at 100 mV·s -1 to achieve electrochemical activation, and then perform linear sweep voltammetry measurement at 5 mV·s in the same range -1 to test its hydrogen evolution performance.

[0152] The specific test results are shown in Table 1 below and Figure 6 as follows:

[0153] Table 1

[0154]

[0155] As shown in Table 1 and Figure 6 as can be seen, the inorganic salt-regulated ruthenium cluster-ene provided by the present invention has a significant activity improvement compared with commercial platinum-carbon and commercial ruthenium-carbon catalysts, and can drive the hydrogen evolution reaction to occur at a lower overpotential.

[0156] Application Example 1

[0157] This application example provides a cathode and an anion exchange membrane alkaline electrolytic cell containing the same. The anion exchange membrane alkaline electrolytic cell includes a cathode, an anode, and an electrolyte; wherein, the method for preparing the cathode is as follows: Prepare a slurry from the ruthenium cluster-ene catalyst prepared in Example 1, spray it on the carbon paper with an air gun, the spraying area is 1×1 cm, and the spraying loading is 0.1 mg Ru ·cm -2 , and use this as the cathode; the electrolyte is 1 M KOH.

[0158] Comparative Application Example 1

[0159] This comparative application example provides a cathode and an anion membrane alkaline electrolysis tank containing the cathode, which differs from Application Example 1 only in that the ruthenium cluster olefin catalyst prepared in Example 1 is replaced by the ruthenium particle catalyst prepared in Comparative Example 1, and the other settings are exactly the same as those in Application Example 1.

[0160] Test Example 2

[0161] Device activity and stability testing

[0162] Test samples: anion membrane alkaline electrolysis water tank provided in Application Example 1, and anion membrane alkaline electrolysis water tank provided in Comparative Application Example 1.

[0163] Test method:

[0164] (1) Device activity: Assemble the carbon paper sprayed with the application example sample, the homemade anode, the anion exchange membrane, and the polytetrafluoroethylene gasket of the corresponding thickness into a membrane electrode and install the electrolytic cell. Use a peristaltic pump to circulate the liquid at the liquid inlet. After the peristaltic pump runs for 10 minutes to ensure that the electrodes are wetted and there is no leakage, the electrolytic cell can be connected to a DC power supply. Set the current value in the operating software (set a measurement point every 0.2A until 7A), set the temperature control device to 80℃, and start the test when the temperature reaches 80℃. The software system will give a voltage response according to the set current value and record the real-time numerical value;

[0165] (2) Device stability: The electrolytic cell installation method is the same as above. First, set the operating current to 0.5A. During this process, turn on the temperature rise. When the temperature reaches 80°C, change the operating current to 1A, 2A or 3A for stability testing. The software background will record the real-time response voltage.

[0166] The specific test results are shown in Tables 2 and 3, and Figures 7 to 10 As shown:

[0167] Table 2

[0168]

[0169] Table 3

[0170]

[0171] From Table 2 and Figure 7 As shown in Table 3, the ruthenium cluster ene cathode regulated by inorganic salts has higher device activity than the commercial platinum carbon cathode. Figures 8 to 10 As mentioned above, ruthenium cluster ene also shows device stability at high current density.

[0172] Furthermore, step (1) in Example 1 is amplified 10 times year-on-year. Figure 11The transmission electron microscopy image and XRD pattern of the ruthenium cluster-ene catalyst regulated by inorganic salts after magnification are shown. It can be seen that the structure remains consistent. Further, the catalyst prepared by magnifying the above by 10 times is used for the activity operation in an anion exchange membrane alkaline electrolytic water cell. Figure 12 The activity of the magnified catalyst in an anion exchange membrane alkaline electrolytic water cell is shown. It can be seen that the performance remains consistent. Further, the steps in (1) are magnified by 50 times on a year-on-year basis, and the obtained catalyst is used for the activity operation in an anion exchange membrane alkaline electrolytic water cell. Figure 12 The activity of the magnified catalyst in an anion exchange membrane alkaline electrolytic water cell is shown. It can be seen that the performance remains consistent.

[0173] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a ruthenium cluster olefin catalyst, characterized in that: The preparation method of the ruthenium cluster olefin catalyst comprises: (1) mixing an organic noble metal ruthenium source, an inorganic salt of an alkali metal and a carbon support, and grinding the mixture to obtain a mixture; (2) calcining the mixture obtained in step (1), washing and drying the mixture to obtain the ruthenium cluster olefin catalyst.

2. The method for preparing a ruthenium cluster olefin catalyst according to claim 1, characterized in that: In step (1), the organic noble metal ruthenium source is ruthenium acetylacetonate.

3. The method for preparing a ruthenium cluster olefin catalyst according to claim 1, characterized in that: In step (1), the inorganic salt of the alkali metal is selected from any one or a combination of at least two of the halides of the alkali metal; Preferably, the alkali metal is selected from any one of lithium, sodium or potassium; Preferably, the halide is selected from any one of chloride, bromide and iodide.

4. The method for preparing a ruthenium cluster olefin catalyst according to claim 1, characterized in that: In step (1), the carbon carrier is selected from any one of carbon nanotubes, XC-72, Ketjen Black 300, Ketjen Black 600 or graphene, or a combination of at least two thereof.

5. The method for preparing a ruthenium cluster olefin catalyst according to claim 1, characterized in that: In step (1), the mass ratio of the organic noble metal ruthenium source, the inorganic salt of the alkali metal and the carbon support is 10:(50-500):(5-20); Preferably, in step (1), the grinding speed is 50 to 200 rpm, and the grinding time is 60 to 120 min; Preferably, in step (1), the particle size of the mixture obtained by grinding is 1 to 2 μm.

6. The method for preparing a ruthenium cluster olefin catalyst according to claim 1, characterized in that: In step (2), the calcination is carried out in a muffle furnace; Preferably, in step (2), the heating rate of the calcination is 5 to 10°C / min; the calcination temperature is 200 to 270°C; and the calcination time is 0.5 to 2h; Preferably, in step (2), the washing is carried out using pure water; Preferably, in step (2), the drying temperature is 40 to 60° C. and the drying time is 2 to 4 hours.

7. A ruthenium cluster olefin catalyst, characterized in that: The ruthenium cluster olefin catalyst is prepared by the preparation method of the ruthenium cluster olefin catalyst according to any one of claims 1 to 6.

8. Use of the ruthenium cluster ene catalyst according to claim 7 as a high-efficiency hydrogen evolution catalyst in the preparation of an anion membrane alkaline water electrolysis tank.

9. A cathode for an anion membrane alkaline electrolysis water tank, characterized in that: The cathode for anion membrane alkaline water electrolysis tank comprises: a diffusion layer and a catalyst layer; wherein the catalyst layer comprises the ruthenium cluster ene catalyst as claimed in claim 7; Preferably, the loading amount of the ruthenium cluster olefin catalyst is 0.1 to 0.5 mg·cm -2 ; Preferably, the diffusion layer is carbon paper.

10. An anion membrane alkaline electrolysis water tank, characterized in that: The anion membrane alkaline water electrolysis tank comprises the cathode for anion membrane alkaline water electrolysis tank as claimed in claim 9.

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