Method for preparing sulfide heterogeneous foam carrier from foam metal and application

Abstract

The invention provides a method for preparing a sulfide heterogeneous foam carrier from foam metal and application, and the method comprises the following steps: placing a sulfur source in a porcelain boat, placing the foam metal in another porcelain boat, placing the two porcelain boats in a quartz tube, and placing the quartz tube in a tubular furnace, placing a porcelain boat filled with a sulfur source at the upstream, close to a gas inlet, of a tubular furnace, and placing a porcelain boat filled with foam metal at the center of the tubular furnace; sealing the tubular furnace, continuously introducing inert gas to keep inert atmosphere, and then heating the tubular furnace to 400-800 DEG C for reaction; and after the reaction is completed, continuously introducing inert gas, reducing the temperature of the tubular furnace to room temperature, and taking out a product, namely the sulfide heterogeneous foam carrier.

Description

Technical Field

[0001] The present disclosure belongs to the technical field of the preparation of self-supporting carriers, and relates to a method for preparing a sulfide heterogeneous foam carrier from a foam metal and its application. Background Art

[0002] With the intensification of energy problems, it has become an urgent task to develop clean and sustainable green energy. As a clean energy with high energy density, hydrogen energy has unlimited potential in replacing fossil fuels as a renewable energy source. Electrolysis of water is an extremely simple and effective method for hydrogen production, but it faces bottleneck problems such as high power consumption and high production costs. At the same time, high hydrogen evolution and oxygen evolution overpotentials are also obstacles restricting its large-scale industrial development. Noble metal platinum-based, ruthenium-based / iridium-based catalysts are respectively the benchmark catalysts for hydrogen evolution and oxygen evolution, which can drive the reaction with extremely low overpotentials. However, noble metals are costly and have low reserves on the earth. Therefore, it is of great significance to develop new, efficient, inexpensive, and stable transition metal-based catalysts whose catalytic activities can reach or even exceed those of noble metal-based catalysts.

[0003] In recent years, transition metal sulfides, as an electrolysis water catalyst, have been considered very promising catalyst materials due to their good electrical conductivity and high reaction activity. As a commercial material, foam metal has a good three-dimensional spatial structure and electrical conductivity, and is often used as a carrier material for preparing catalysts. Preparing transition metal sulfides on foam metal and using them for electrocatalytic water splitting is beneficial to reducing the reaction overpotential and thus reducing energy consumption. Traditional methods for preparing transition metal sulfides include the following: pre-in-situ growing metal hydroxides or metal complex precursors on a foam metal carrier, and then using sulfur powder as the sulfur source to anneal in an inert atmosphere; or using thiourea as the sulfur source and directly in-situ growing transition metal sulfides on the foam metal through a one-step hydrothermal reaction. However, for these traditional methods for preparing transition metal sulfides, the metal sources include foam metal and additional metal salts, and it is difficult to ensure and control the final phase purity, and the morphology of the transition metal sulfides is also difficult to be unified. In addition, due to the limited activity of the foam metal carrier itself, the activity of the obtained metal sulfides still has a large gap compared with noble metal materials. Summary of the Invention

[0004] The present disclosure provides a method for preparing a sulfide heterogeneous foam carrier from a foam metal and its application, which can effectively solve the above problems.

[0005] The present disclosure is implemented as follows:

[0006] On the one hand, the present disclosure provides a method for preparing a sulfide heterogeneous foam carrier from a foam metal, including the following steps:

[0007] Place the sulfur source in a porcelain boat, place the foam metal in another porcelain boat, after putting the two porcelain boats into a quartz tube, place the quartz tube in a tube furnace, wherein, place the porcelain boat containing the sulfur source upstream near the inlet of the tube furnace, and place the porcelain boat containing the foam metal in the center of the tube furnace;

[0008] Seal the tube furnace, continuously introduce an inert gas to maintain an inert atmosphere, and then heat up the tube furnace for reaction;

[0009] After the reaction is completed, continue to introduce the inert gas, cool the temperature of the tube furnace to room temperature, and take out the product, which is the sulfide heterogeneous foam carrier.

[0010] On the other hand, the present disclosure provides the sulfide heterogeneous foam carrier prepared by the above method.

[0011] On yet another aspect, the present disclosure provides the application of the above sulfide heterogeneous foam carrier in catalytic electrolytic water hydrogen evolution and oxygen evolution reactions.

[0012] The beneficial effects of the present disclosure are:

[0013] The present disclosure provides a method for preparing a sulfide heterogeneous foam carrier from foam metal. A sulfide heterogeneous foam material can be obtained by a simple one-step annealing method, that is, the foam metal skeleton is completely sulfided through medium-temperature heat treatment in a tube furnace to obtain a sulfide heterogeneous structure. The prepared sulfide heterogeneous foam carrier significantly improves the electrochemistry reaction kinetic performance through the interfacial electron synergy effect and the three-dimensional porous structure.

[0014] Furthermore, the sulfide heterogeneous foam carrier exhibits excellent hydrogen evolution and oxygen evolution performance in an alkaline electrolyte, realizing low-energy-consumption and high-efficiency electrochemistry reactions, and is suitable for large-scale industrial electrolytic water hydrogen production. Description of the Drawings

[0015] In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the following will briefly introduce the drawings required to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the present disclosure, and therefore should not be regarded as limiting the scope. For those of ordinary skill in the art, other related drawings can be obtained based on these drawings without creative efforts.

[0016] Figure 1 It is the X-ray diffraction pattern and scanning electron microscope image of the nickel sulfide heterogeneous foam prepared in Example 1 of the present disclosure.

[0017] Figure 2 It is the X-ray photoelectron spectroscopy image of the nickel sulfide heterogeneous foam prepared in Example 1 of the present disclosure.

[0018] Figure 3This is the electrocatalytic hydrogen evolution performance diagram of nickel sulfide heterogeneous foam prepared in Example 1 of the present disclosure under alkaline conditions.

[0019] Figure 4 This is the electrocatalytic oxygen evolution performance diagram of nickel sulfide heterogeneous foam prepared in Example 1 of the present disclosure under alkaline conditions. Detailed implementation manners

[0020] To make the objectives, technical solutions, and advantages of the embodiments of the present disclosure clearer, the technical solutions in the embodiments of the present disclosure will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present disclosure. Apparently, the described embodiments are some, but not all, of the embodiments of the present disclosure. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present disclosure without creative efforts fall within the scope of protection of the present disclosure. Therefore, the following detailed description of the embodiments of the present disclosure provided in the drawings is not intended to limit the scope of the present disclosure claimed, but merely represents selected embodiments of the present disclosure. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present disclosure without creative efforts fall within the scope of protection of the present disclosure.

[0021] The embodiments of the present disclosure provide a method for preparing a sulfide heterogeneous foam carrier from a foam metal, including the following steps:

[0022] S1. Place the sulfur source in a porcelain boat, place the foam metal in another porcelain boat, after putting the two porcelain boats into a quartz tube, place the quartz tube in a tube furnace. Among them, place the porcelain boat containing the sulfur source upstream near the gas inlet of the tube furnace, and place the porcelain boat containing the foam metal in the center of the tube furnace;

[0023] S2. Seal the tube furnace, continuously introduce an inert gas to maintain an inert atmosphere, and then heat the tube furnace to 400 - 800 °C for reaction;

[0024] S3. After the reaction is completed, continue to introduce the inert gas, cool the temperature of the tube furnace to room temperature, and take out the product, which is the sulfide heterogeneous foam carrier.

[0025] In step S1, a porcelain boat is used because it has high temperature resistance (>1000 °C), chemical inertness (does not react with the sulfur source), and a smooth surface, which is convenient for spreading and cleaning the sulfur source.

[0026] In some embodiments, in step S1, the sulfur source is evenly spread on the porcelain boat.

[0027] Specifically, the sulfur source is evenly spread on the porcelain boat by oscillation.

[0028] The sulfur source sublimes or decomposes into gaseous sulfur during the heating process (such as S x) Tilting can increase the contact area between the sulfur source and the heat source, accelerate the generation rate of gaseous sulfur, form a stable and continuous gaseous sulfur flow, and be transported to the downstream foamed metal with the inert gas, providing sufficient reactants for the subsequent sulfidation reaction. Moreover, it can avoid the local overheating caused by the accumulation of the sulfur source and ensure the uniform sublimation or decomposition of the sulfur source.

[0029] A uniform supply of gaseous sulfur can enable the foamed metal to form a uniform sulfide heterostructure and avoid local morphological differences.

[0030] In some embodiments, in step S1, the foamed metal is leaned against the wall of another porcelain boat.

[0031] Leaning placement can fully expose the three-dimensional porous skeleton of the foamed metal to the gas flow, enabling the inert gas and gaseous sulfur to flow more smoothly through the pores of the foamed metal, increasing the contact area between gaseous sulfur and the metal skeleton, promoting uniform sulfides, and enhancing the mass transfer efficiency. If placed flat, the bottom layer of the foamed metal may hinder the penetration of gaseous sulfur due to contact with the bottom of the porcelain boat, resulting in non-uniform sulfides.

[0032] In step S1, a foamed metal with a certain geometric area is cut.

[0033] Due to the high specific surface area of the foamed metal and the open pores of the three-dimensional porous skeleton, compared with the area, the thickness has a smaller impact on the reaction effect.

[0034] In some embodiments, the dosage ratio of the sulfur source to the foamed metal is: 1 g : 2 - 5 cm 2 .

[0035] In some embodiments, the dosage ratio of the sulfur source to the foamed metal is: 1 g : 3 cm 2 .

[0036] In some embodiments, the dosage ratio of the sulfur source to the foamed metal is: 2 g : 2 cm × 3 cm.

[0037] If the sulfur source is in excess, the unreacted gaseous sulfur will flow out of the quartz tube with the inert gas and be wasted.

[0038] Moreover, in order to form a monosulfide-disulfide heterostructure, it is necessary to avoid an excessive sulfur source, as all the metal being overly converted to disulfide will result in the loss of the interface synergistic effect and a decrease in catalytic activity.

[0039] If the sulfur source is insufficient, it cannot provide sufficient gaseous sulfur, which will cause some areas on the foamed metal to still not participate in the sulfidation reaction or the reaction to be incomplete. The catalytic performance of these areas will not meet the expectations, thereby reducing the overall catalytic performance of the product.

[0040] In some embodiments, in step S1, the sulfur source includes one or more of sublimed sulfur, thiourea, and thioacetamide.

[0041] In some embodiments, in step S1, the metal foam includes one or more of nickel foam, copper foam, iron foam, aluminum foam, magnesium foam, cobalt foam, nickel iron foam, iron aluminum foam, nickel copper foam, and nickel chromium foam.

[0042] The raw materials have a wide selection range, are inexpensive, non-toxic, and harmless. There is no need to use organic solvents or other toxic reagents during the preparation process.

[0043] In some embodiments, in step S2, the inert gas is a high-purity inert gas.

[0044] The inert gas is used to exclude air in the quartz tube and maintain an inert atmosphere inside the tube.

[0045] In some embodiments, in step S2, the inert gas is one or both of nitrogen and argon.

[0046] In some embodiments, in step S2, the flow rate of the inert gas is 150 mL / min.

[0047] In some embodiments, in step S2, the heating rate is 5 °C / min.

[0048] In some embodiments, it is held at 400 - 800 °C for 1 - 3 h to fully vaporize the sulfur source and allow the gaseous sulfur to fully react with the foam metal by sulfidation reaction.

[0049] In step S2, one-step annealing is used to fully sulfide the foam metal to form a sulfide heterogeneous foam structure, and the sulfide heterogeneous structure directly replaces the original metal skeleton.

[0050] Under the protection of an inert gas, the foam metal and the sulfur source are co-placed in a tube furnace, and the metal is completely converted into sulfide by medium-temperature annealing (400 - 800 °C) to form a monosulfide-disulfide heterogeneous structure.

[0051] An internal electric field can be formed at the interface between the monosulfide and the disulfide due to the work function difference, accelerating charge transfer and enhancing the catalytic activity of the material.

[0052] The monosulfide provides metal-sulfur bonds as adsorption sites, while the disulfide provides sulfur vacancies or edge sulfur atoms (S-) as catalytic centers.

[0053] The sulfide heterogeneous structure includes at least one of nickel monosulfide-nickel disulfide, copper monosulfide-copper disulfide, iron monosulfide-iron disulfide, aluminum monosulfide-aluminum disulfide, magnesium monosulfide-magnesium disulfide, cobalt monosulfide-cobalt disulfide, nickel iron monosulfide-nickel iron disulfide, iron aluminum monosulfide-iron aluminum disulfide, nickel copper monosulfide-nickel copper disulfide, and nickel chromium monosulfide-nickel chromium disulfide.

[0054] The chemical general formula of the sulfide heterogeneous foam support is MS-MS2, where M represents the corresponding transition metal element. For example, nickel (Ni), copper (Cu), iron (Fe), aluminum (Al), magnesium (Mg), cobalt (Co), nickel-iron (NiFe), iron-aluminum (FeAl), nickel-copper (NiCu), nickel-chromium (NiCr), etc.

[0055] In some embodiments, in step S3, the temperature of the tube furnace naturally drops to room temperature.

[0056] The sulfide heterogeneous foam support is a self-supporting support without the need for an additional binder, reducing the interfacial resistance. Its structure is stable, and the three-dimensional porous skeleton of the foam metal is completely retained. Its high specific surface area and through pores can accelerate ion / electron transport and enhance the diffusion efficiency of reactants (such as OH - , H2O). The one-step annealing method directly converts the foam metal to generate a high binding strength between monosulfide and disulfide. The open pores of the three-dimensional porous skeleton can provide anchor points for sulfides, enhancing the mechanical interlocking effect.

[0057] The preparation method is simple, environmentally friendly, green and safe.

[0058] In some embodiments, the sulfide heterogeneous foam exhibits the morphology of nanospheres.

[0059] The embodiments of the present disclosure provide the sulfide heterogeneous foam support prepared by the above method.

[0060] The embodiments of the present disclosure provide the application of the above sulfide heterogeneous foam support in catalytic electrolytic water hydrogen evolution and oxygen evolution reactions.

[0061] The sulfide heterogeneous foam support is a self-supporting sulfide support with a heterogeneous structure. By directly fully sulfiding the foam metal, the reaction kinetic performance of the material is significantly improved, making it have extremely high catalytic activity and capable of driving hydrogen evolution and oxygen evolution reactions at a very low overpotential.

[0062] This material can simultaneously and efficiently catalyze the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), which can reduce the system cost.

[0063] The electron synergistic effect at the "monosulfide-disulfide" interface of this material can adjust the adsorption free energy of water (H2O), hydrogen (H), or oxygen intermediates (OH, O, OOH), making it close to the ideal value, thereby reducing the reaction energy barrier.

[0064] The open pore structure of the foam metal and the morphology of the nanospheres formed after sulfidation can significantly increase the electrochemically active surface area and expose more active sites.

[0065] The porous structure can promote the penetration of the electrolyte into the material interior, and at the same time accelerate the rapid escape of reaction products (such as H2 and O2 bubbles), reducing concentration polarization.

[0066] The sulfide heterogeneous foam carrier and its preparation method have strong reference significance for the design of highly active catalysts in other technical fields.

[0067] In some embodiments, the electrolyte is an alkaline aqueous solution.

[0068] Sulfide is chemically stable in a strong alkaline environment and is not easily oxidized or dissolved. The alkaline electrolyte can also form a stable passivation layer (such as NiOOH) on the surface of this material, inhibiting the loss of active substances.

[0069] The alkaline aqueous solution can also directly provide OH - as a reactant.

[0070] The sulfide heterogeneous foam carrier exhibits excellent hydrogen evolution and oxygen evolution performance in an alkaline electrolyte, realizing a low-energy-consumption and high-efficiency electrochemical reaction, and is applicable to large-scale industrial electrolytic water hydrogen production.

[0071] In some embodiments, the sulfide heterogeneous foam carrier serves as a working electrode.

[0072] Correspondingly, in this electrolytic water system, mercury / mercuric oxide serves as a reference electrode, a graphite rod serves as a counter electrode, and the electrolyte is an alkaline electrolyte.

[0073] In some embodiments, the alkaline electrolyte is a 1.0 M potassium hydroxide (KOH) solution.

[0074] The ionic conductivity of the 1.0 M KOH solution is close to the peak value, and it has a high enough OH - concentration to ensure the supply of hydrogen evolution and oxygen evolution reactants.

[0075] Example 1

[0076] The preparation of the nickel sulfide heterogeneous foam carrier specifically includes the following steps:

[0077] 1. Weigh 1 g of sublimed sulfur and place it in a porcelain boat, and oscillate it to make it evenly spread on the porcelain boat.

[0078] 2. Cut a 2 cm × 3 cm piece of nickel foam and place it in another porcelain boat, leaning against the wall of the porcelain boat obliquely.

[0079] 3. Put the porcelain boat containing the sulfur source in step 1 into a quartz tube, which is located upstream of the tube furnace and close to the air inlet.

[0080] 4. Put the porcelain boat containing the foam metal in step 2 into the quartz tube, which is located in the center of the tube furnace.

[0081] 5. Seal the quartz tube, continuously introduce high-purity nitrogen to remove the air in the quartz tube, and maintain an inert atmosphere inside the tube to prevent metal oxidation or side reactions of the sulfur source.

[0082] 6. Heat the tube furnace to 400 °C at a heating rate of 5 °C / min and hold for 1 h to carry out the sulfidation reaction.

[0083] 7. After the reaction is completed, continue to introduce the inert gas. After the temperature of the tube furnace drops to room temperature, take out the product, which is the nickel sulfide heterogeneous foam carrier for later use.

[0084] Figure 1 In a, it is the X-ray diffraction (XRD) pattern of the nickel sulfide heterogeneous foam carrier. It can be seen from the XRD pattern that by comparing with the standard card, the obtained product is nickel monosulfide - nickel disulfide.

[0085] Figure 1 In b - d, they are the scanning electron microscope (SEM) patterns of the nickel sulfide heterogeneous foam carrier. It can be seen from the SEM patterns that the nickel monosulfide - nickel disulfide heterogeneous material presents a nanosphere morphology, and the spherical structure in d is relatively uniform, indicating that stable spherical particles are formed at the nanoscale.

[0086] Furthermore, X-ray photoelectron spectroscopy analysis is adopted. Figure 2 It can be proved from a that the material contains elements such as Ni and S, and at the same time, there are peaks attributed to S 2- and S2 2- existing, indicating that the nickel monosulfide - nickel disulfide heterogeneous material has been successfully prepared.

[0087] Take the nickel sulfide heterogeneous foam carrier as the working electrode, mercury / mercuric oxide as the reference electrode, graphite rod as the counter electrode, and 1.0 M KOH solution as the electrolyte to establish an electrolytic water system, and test the electrocatalytic hydrogen evolution and oxygen evolution performance of this material.

[0088] Meanwhile, select nickel foam and platinum carbon (Pt / C) as the working electrodes respectively to establish an electrolytic water hydrogen evolution system for comparison.

[0089] Select nickel foam and iridium dioxide (IrO2) as the working electrodes respectively to establish an electrolytic water oxygen evolution system for comparison.

[0090] Figure 3 and Figure 4 The electrochemical test results in show that under alkaline conditions, the catalytic activity of this material is greatly improved compared with that of the foam metal, and it can drive the hydrogen evolution and oxygen evolution reactions with a very low overpotential.

[0091] Figure 3 In a and b show that when catalyzing the hydrogen evolution reaction, this material has a catalytic activity close to that of Pt / C.

[0092] Figure 4 Among them, a shows that the current density of this material begins to increase significantly when the potential is relatively low (less than 1.4 V), which is superior to IrO2, and it can reach the current density of IrO2 at a higher potential at a lower potential, indicating its excellent OER activity. b shows that the Tafel slope of this material is less than that of IrO2, indicating its excellent reaction kinetic performance.

[0093] Example 2

[0094] The difference between Example 2 and Example 1 is as follows:

[0095] In step 2, 2 cm × 3 cm copper foam is used to replace 2 cm × 3 cm nickel foam.

[0096] In step 6, the tubular furnace is heated to 600 °C at a heating rate of 5 °C / min and held for 2 h.

[0097] In step 7, the product is a copper sulfide heterogeneous foam carrier.

[0098] Example 3

[0099] The difference between Example 3 and Example 1 is as follows:

[0100] In step 2, 2 cm × 3 cm iron foam is used to replace 2 cm × 3 cm nickel foam.

[0101] In step 6, the tubular furnace is heated to 500 °C at a heating rate of 5 °C / min and held for 2 h.

[0102] In step 7, the product is an iron sulfide heterogeneous foam carrier.

[0103] Example 4

[0104] The difference between Example 4 and Example 1 is as follows:

[0105] In step 2, 2 cm × 3 cm aluminum foam is used to replace 2 cm × 3 cm nickel foam. In step 6, the tubular furnace is heated to 700 °C at a heating rate of 5 °C / min and held for 2 h. In step 7, the product is an aluminum sulfide heterogeneous foam carrier.

[0106] Example 5

[0107] The difference between Example 5 and Example 1 is as follows:

[0108] In step 2, 2 cm × 3 cm magnesium foam is used to replace 2 cm × 3 cm nickel foam. In step 6, the tubular furnace is heated to 400 °C at a heating rate of 5 °C / min and held for 1 h. In step 7, the product is a magnesium sulfide heterogeneous foam carrier.

[0109] Example 6

[0110] The difference between Example 6 and Example 1 is as follows:

[0111] In step 2, 2 cm × 3 cm cobalt foam is used to replace 2 cm × 3 cm nickel foam. In step 6, the tubular furnace is heated to 500 °C at a heating rate of 5 °C / min and held for 2 h. In step 7, the product is a cobalt sulfide heterogeneous foam carrier.

[0112] Example 7

[0113] The difference between Example 7 and Example 1 is as follows:

[0114] In step 2, 2 cm × 3 cm nickel-iron foam is used to replace 2 cm × 3 cm nickel foam. In step 6, the tubular furnace is heated to 500 °C at a heating rate of 5 °C / min and held for 3 h. In step 7, the product is a nickel-iron sulfide heterogeneous foam carrier.

[0115] Example 8

[0116] The difference between Example 8 and Example 1 is as follows:

[0117] In step 2, 2 cm × 3 cm iron-aluminum foam is used to replace 2 cm × 3 cm nickel foam. In step 6, the tubular furnace is heated to 700 °C at a heating rate of 5 °C / min and held for 3 h. In step 7, the product is an iron-aluminum sulfide heterogeneous foam carrier.

[0118] Example 9

[0119] The difference between Example 9 and Example 1 is as follows:

[0120] In step 2, 2 cm × 3 cm nickel-chromium foam is used to replace 2 cm × 3 cm nickel foam. In step 6, the tubular furnace is heated to 800 °C at a heating rate of 5 °C / min and held for 3 h. In step 7, the product is a nickel-chromium sulfide heterogeneous foam carrier.

[0121] Example 10

[0122] The difference between Example 10 and Example 1 is as follows:

[0123] In step 2, 2 cm × 3 cm nickel-copper foam is used to replace 2 cm × 3 cm nickel foam. In step 6, the tubular furnace is heated to 550 °C at a heating rate of 5 °C / min and held for 3 h. In step 7, the product is a nickel-copper sulfide heterogeneous foam carrier.

[0124] Example 11

[0125] The difference between Example 11 and Example 1 is as follows:

[0126] In Step 1, 1 g of thiourea is used to replace 1 g of sublimed sulfur.

[0127] Example 12

[0128] The difference between Example 12 and Example 2 is that:

[0129] In Step 1, 1 g of thiourea is used to replace 1 g of sublimed sulfur.

[0130] Example 13

[0131] The difference between Example 13 and Example 3 is that:

[0132] In Step 1, 1 g of thiourea is used to replace 1 g of sublimed sulfur.

[0133] Example 14

[0134] The difference between Example 14 and Example 4 is that:

[0135] In Step 1, 1 g of thiourea is used to replace 1 g of sublimed sulfur.

[0136] Example 15

[0137] The difference between Example 15 and Example 5 is that:

[0138] In Step 1, 1 g of thiourea is used to replace 1 g of sublimed sulfur.

[0139] Example 16

[0140] The difference between Example 16 and Example 6 is that:

[0141] In Step 1, 1 g of thiourea is used to replace 1 g of sublimed sulfur.

[0142] Example 17

[0143] The difference between Example 17 and Example 7 is that:

[0144] In Step 1, 1 g of thiourea is used to replace 1 g of sublimed sulfur.

[0145] Example 18

[0146] The difference between Example 18 and Example 8 is that:

[0147] In Step 1, 1 g of thiourea is used to replace 1 g of sublimed sulfur.

[0148] Example 19

[0149] The difference between Example 19 and Example 9 is that:

[0150] In Step 1, 1 g of thiourea is used to replace 1 g of sublimed sulfur.

[0151] Example 20

[0152] The difference between Example 20 and Example 10 is that:

[0153] In step 1, 1 g of thiourea is used to replace 1 g of sublimed sulfur.

[0154] Example 21

[0155] The difference between Example 21 and Example 1 is that:

[0156] In step 1, 1 g of thioacetamide is used to replace 1 g of sublimed sulfur.

[0157] Example 22

[0158] The difference between Example 22 and Example 2 is that:

[0159] In step 1, 1 g of thioacetamide is used to replace 1 g of sublimed sulfur.

[0160] Example 23

[0161] The difference between Example 23 and Example 3 is that:

[0162] In step 1, 1 g of thioacetamide is used to replace 1 g of sublimed sulfur.

[0163] Example 24

[0164] The difference between Example 24 and Example 4 is that:

[0165] In step 1, 1 g of thioacetamide is used to replace 1 g of sublimed sulfur.

[0166] Example 25

[0167] The difference between Example 25 and Example 5 is that:

[0168] In step 1, 1 g of thioacetamide is used to replace 1 g of sublimed sulfur.

[0169] Example 26

[0170] The difference between Example 26 and Example 6 is that:

[0171] In step 1, 1 g of thioacetamide is used to replace 1 g of sublimed sulfur.

[0172] Example 27

[0173] The difference between Example 27 and Example 7 is that:

[0174] In step 1, 1 g of thioacetamide is used to replace 1 g of sublimed sulfur.

[0175] Example 28

[0176] The difference between Example 28 and Example 8 is as follows:

[0177] In Step 1, 1 g of thioacetamide is used to replace 1 g of sublimed sulfur.

[0178] Example 29

[0179] The difference between Example 29 and Example 9 is as follows:

[0180] In Step 1, 1 g of thioacetamide is used to replace 1 g of sublimed sulfur.

[0181] Example 30

[0182] The difference between Example 30 and Example 10 is as follows:

[0183] In Step 1, 1 g of thioacetamide is used to replace 1 g of sublimed sulfur.

[0184] The sulfide heterogeneous foam carriers prepared in Examples 2 - 30 are used as the working electrode, mercury / mercuric oxide as the reference electrode, a graphite rod as the counter electrode, and 1.0 M KOH solution as the electrolyte to establish an electrolytic water system, and the electrocatalytic hydrogen evolution and oxygen evolution performances of the material are tested.

[0185] The test results all show that under alkaline conditions, this material is used for the electrochemical hydrogen evolution and oxygen evolution reactions, has extremely high catalytic activity, and can drive the hydrogen evolution and oxygen evolution reactions with a very low overpotential.

[0186] The above are only the preferred embodiments of the present disclosure and are not used to limit the present disclosure. For those skilled in the art, various changes and modifications can be made to the present disclosure. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present disclosure shall be included within the protection scope of the present disclosure.

Claims

1. A method for preparing a sulfide heterogeneous foam carrier from foam metal, characterized in that: It includes the following steps: Place the sulfur source in a porcelain boat, place the metal foam in another porcelain boat, after putting the two porcelain boats into a quartz tube, place the quartz tube in a tube furnace, wherein, place the porcelain boat containing the sulfur source upstream near the air inlet of the tube furnace, and place the porcelain boat containing the metal foam in the center of the tube furnace; Seal the tube furnace, continuously introduce an inert gas to maintain an inert atmosphere, and then heat the tube furnace to 400 - 800 °C for reaction; After the reaction is completed, continue to introduce the inert gas, cool the temperature of the tube furnace to room temperature, and take out the product, which is the sulfide heterogeneous foam carrier.

2. The method according to claim 1, characterized in that Evenly spread the sulfur source on the porcelain boat; Lean the metal foam against the wall of another porcelain boat.

3. The method according to claim 1, characterized in that The ratio of sulfur source to foam metal is: 1g: 2-5cm 2 .

4. The method according to claim 1, characterized in that: The metal foam includes one or more of nickel foam, copper foam, iron foam, aluminum foam, magnesium foam, cobalt foam, nickel-iron foam, iron-aluminum foam, nickel-copper foam, nickel-chromium foam.

5. The method according to claim 1, characterized in that The sulfur source includes one or more of sublimed sulfur, thiourea, thioacetamide.

6. The method according to claim 1, wherein The inert gas is one or both of nitrogen and argon.

7. The sulfide heterogeneous foam carrier prepared by the method according to any one of claims 1 - 6.

8. The application of the sulfide heterogeneous foam carrier according to claim 7 in the catalytic electrolytic water hydrogen evolution and oxygen evolution reactions.

9. The application according to claim 8, characterized in that, The electrolyte is an alkaline aqueous solution.

10. The application according to claim 8, characterized in that, The sulfide heterogeneous foam carrier serves as a working electrode.

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