CN113058619B - Efficient non-noble metal electrolytic water catalytic material and preparation method and application thereof - Google Patents

Efficient non-noble metal electrolytic water catalytic material and preparation method and application thereof Download PDF

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CN113058619B
CN113058619B CN201911285634.5A CN201911285634A CN113058619B CN 113058619 B CN113058619 B CN 113058619B CN 201911285634 A CN201911285634 A CN 201911285634A CN 113058619 B CN113058619 B CN 113058619B
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electrolytic water
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CN113058619A (en
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邓德会
郑智龙
胡景庭
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Dalian Institute of Chemical Physics of CAS
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
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Abstract

The invention provides a high-efficiency non-noble metal electrolytic water catalytic material, and a preparation method and application thereof, and mainly solves the problems that the price of the current commercial platinum-based catalyst is high, the current catalyst can only realize smaller current density, and the stability is poor under the large current density of a working condition. According to the invention, a metal with excellent conductivity is selected as a substrate, and the three-dimensional honeycomb-shaped porous sulfide grows on the surface of the substrate to form the efficient integral electrode catalyst for electrolyzing water. The catalyst can simultaneously realize high-efficiency hydrogen and oxygen evolution of electrolyzed water, still keeps ultrahigh stability under the condition of high current density, and has good industrial application prospect and commercial value. The preparation method of the catalyst is a universal method for preparing the efficient electrolytic water catalytic material, and has the characteristics of simplicity, easiness in operation, high commercial application value of the prepared electrolytic water catalytic material and the like.

Description

Efficient non-noble metal electrolytic water catalytic material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a high-efficiency non-noble metal electrolytic water catalytic material.
Background
The hydrogen is an important clean energy carrier, has the advantages of no toxicity, no pollution, high heat value and the like, and is considered to be a novel energy carrier capable of replacing fossil energy. Among them, the electrolyzed water has been widely noticed as a method for cleanly preparing high-purity hydrogen. The electrolytic water reaction comprises two half reactions of cathodic Hydrogen Evolution Reaction (HER) and anodic Oxygen Evolution Reaction (OER), the current hydrogen evolution reaction mainly uses expensive commercial platinum-based catalyst, and the oxygen evolution reaction also mainly uses expensive IrO2And RuO2And the like. With the rise of graphene materials, other two-dimensional materials are also gradually favored by people. Among them, two-dimensional transition metal chalcogenides (TMDs) as graphene-like layered materials have great potential applications in electronic devices, inductors, energy sources, catalysis, and the like due to their unique electronic and structural properties. Especially in the field of electrolysis of water, TMDs is considered as a good alternative to expensive noble metal commercial catalysts because of its superior performance, environmental friendliness and huge earth reserves.
However, the current TMDS catalysts still have difficulty in comparison with commercial noble metal catalysts. Among them, TMDS is one kind in terms of conductivityThe conductivity of semiconductor materials has not been satisfactory. And with the gradual increase of the reaction current density, TMDs interacting by van der waals force are easily agglomerated and deactivated by themselves, resulting in difficulty in maintaining stability. Aiming at the problems of TMDs intrinsic conductivity and stability, a feasible scheme is to compound molybdenum disulfide and a material with good conductivity so as to improve the catalytic activity of the molybdenum disulfide. For example, after TMDs such as molybdenum disulfide and tungsten disulfide are compounded with graphene, the conductivity of the obtained material is significantly improved (y.li, h.dai et al.j.am.chem.soc.,133,7296 (2011)). Although the composite material with good conductivity is a good strategy, the powder catalyst still cannot bear the test of high current density along with the gradual increase of the current density, which greatly limits the popularization and application of the electrolytic water catalyst. Based on the above knowledge, it is necessary to develop a suitable conductive substrate on which TMDs are self-supported to form a monolithic electrode, so as to overcome the above difficulties. More importantly, it is considered that most TMDs (e.g. molybdenum disulphide) have their hydrogen evolution activity demonstrated to be mainly due to marginal sites, whereas the perfect large patch of in-plane sites are relatively inert (b.hinnemann, j.k).
Figure BDA0002317904950000011
et al.J.Am.chem.Soc.,127, 5308-. Therefore, the preparation strategy of how to satisfy the requirements of the catalytic material on stability and conductivity in the reaction and ensure that the molybdenum disulfide has rich and stable edges under the condition of self-support has a very challenging task.
Disclosure of Invention
Based on the background technology, the invention provides a design and preparation method of a high-efficiency non-noble metal electrolytic water catalytic material. The method selects the metal substrate with excellent conductivity, then grows the three-dimensional honeycomb-shaped porous sulfide on the surface of the metal substrate in a self-supporting way, can be simultaneously applied to the hydrogen evolution and oxygen evolution reactions of electrolyzed water, has excellent activity and stability, and can keep the stability under the condition of large current. The method is easy to operate, has wide application range, and can be used for preparing integral electrodes of other two-dimensional materials. The material has wide application prospect in the fields of electro-catalysis, energy storage and conversion and the like.
The technical scheme of the invention is as follows:
the invention provides a non-noble metal electrolytic water catalytic material, which comprises a substrate and three-dimensional honeycomb porous sulfides growing on the surface of at least one side of the substrate; the substrate is foamed nickel; the aperture of a single hole of the three-dimensional honeycomb-shaped porous sulfide is 10-400 nm, the hole wall is formed by combining sulfide nanosheet arrays, and holes of the three-dimensional honeycomb-shaped porous sulfide are distributed in a honeycomb shape; the growth amount of the three-dimensional honeycomb-shaped porous sulfide is 1-60mg/cm2
Based on the technical scheme, preferably, the sulfide is one or more of tungsten sulfide, cobalt sulfide, nickel sulfide, vanadium sulfide, molybdenum sulfide, tantalum sulfide, iron sulfide, copper sulfide and manganese sulfide.
The invention also provides a preparation method of the non-noble metal electrolytic water catalytic material, which comprises the following steps:
(1) sequentially placing foamed nickel in ultrapure water, acetone, hydrochloric acid and ultrapure water, respectively carrying out ultrasonic treatment for 10-60 min, and then drying at 25-100 ℃ for 4-24 h under vacuum; the concentration of the hydrochloric acid is 1-3M;
(2) mixing a metal cation salt, a sulfur source, alcohol, a pore template and a dispersing agent, ultrasonically dispersing for 0.5-6 h, and stirring for 1-48 h at 25-100 ℃ to obtain a load component precursor mixed solution;
(3) dripping the load component precursor mixed solution obtained in the step (2) on the foamed nickel treated in the step (1), placing the foamed nickel under an infrared lamp of 50-200W for 1-6 h, then carrying out vacuum drying at 25-100 ℃ for 4-24 h, and then keeping the dried product at 200-600 ℃ for 60-360 min in a reducing atmosphere to obtain a reaction product;
(4) and (4) transferring the reaction product obtained in the step (3) to a template agent removing solution, sealing and standing for 1-240 min, then washing, and carrying out vacuum drying at 25-150 ℃ for 6-24 h to obtain the non-noble metal electrolytic water catalytic material.
Based on the technical scheme, preferably, the porosity of the foamed nickel in the step (1) is 75-700 PPI; the thickness is 1-5 mm;
in the step (2), the metal in the metal cation salt is tungsten, cobalt, nickel, vanadium, molybdenum, tantalum, iron, copper and manganese; the metal cation salt is at least one of nitrate, sulfate, chloride and acetate of the metal;
the sulfur source in the step (2) is at least one of thiourea, thioacetamide, sodium sulfide, potassium sulfide, sodium sulfite and sulfur powder;
in the step (2), the pore template is at least one of polystyrene, nano alumina, silicon dioxide, carbon nano tube, titanium dioxide and molecular sieve;
in the step (2), the dispersant is at least one of water, acetone, toluene, acetonitrile, ethylenediamine, chloroform and diethyl ether;
in the step (2), the alcohol is at least one of methanol, ethanol, ethylene glycol or isopropanol;
based on the technical scheme, preferably, the size of the pore channel template in the step (2) is 10-400 nm;
the molar ratio of sulfur atoms in the sulfur source to metal atoms in the metal cation salt in the step (2) is 1: 10-500: 1;
the mass ratio of metal atoms in the metal cation salt in the step (2) to the pore channel template is 1: 1-100;
the mass ratio of the dispersing agent to the alcohol in the step (2) is 0.5-10: 1;
based on the technical scheme, preferably, the reducing gas in the step (3) comprises hydrogen and argon, the volume ratio of the hydrogen to the argon is 0-10: 10, and the flow rate of the mixed gas is 20-200 mL/min;
based on the technical scheme, preferably, the template removal solution in the step (4) is a mixed solution of a solution A and alcohol; the solution A is at least one of hydrofluoric acid solution, sodium hydroxide solution, potassium hydroxide solution, ammonia water solution, hydrochloric acid solution, sulfuric acid solution and nitric acid solution;
the concentration of the solution A is 5-70 wt.%;
the alcohol is at least one of methanol, ethanol, ethylene glycol or isopropanol;
in the mixed solution, the mass ratio of the solution A to the alcohol is 10: 1-50;
in the step (4), the washing is carried out in ultrapure water and ethanol until the solution is neutral.
The invention also provides an application of the non-noble metal water electrolysis catalytic material, and the non-noble metal catalytic material can be used as a water electrolysis hydrogen evolution catalyst and a water electrolysis oxygen evolution catalyst at the same time, namely can efficiently catalyze OH at the anode-Oxidizing to generate oxygen, and high-efficiency catalyzing H at cathode+Reduction produces hydrogen.
Advantageous effects
1. The prepared three-dimensional honeycomb porous sulfide has a large specific surface area of a three-dimensional honeycomb porous structure, is beneficial to full contact of electrolyte and the surface of a catalyst, and improves the mass transfer efficiency.
2. The three-dimensional cellular porous structure of the prepared three-dimensional cellular porous sulfide changes the surface thermodynamic property of the sulfide, and is more beneficial to the formation and exposure of the active edge of the sulfide.
3. The prepared electrolytic water material has the substrate of metallic nickel, is easy to form a compound with a carrier, can more firmly stabilize a load component, has good conductivity of the foamed nickel, and is beneficial to electrocatalytic reaction.
4. The prepared integral electrode has stable structure and various load components, and can adopt chalcogenide of different elements as the load components;
5. the catalyst disclosed by the invention does not use noble metal elements, is low in production cost, simple to operate, wide in precursor source, capable of realizing macro preparation and easy for large-scale production.
6. The prepared self-supporting three-dimensional honeycomb porous sulfide integral electrode can be simultaneously and efficiently applied to the electrolytic water hydrogen evolution and oxygen evolution reactions, has high catalytic activity and good stability, can bear the test of large current density, and keeps certain stability.
Drawings
FIG. 1 is an electron micrograph of a non-noble metal catalytic material prepared according to example 1; a is a Transmission Electron Microscope (TEM) image; b is a High Resolution Transmission Electron Microscopy (HRTEM) image;
fig. 2 is a Scanning Electron Microscope (SEM) image of the non-noble metal catalytic material prepared in example 1.
Detailed Description
The whole material preparation process is described in detail by the following examples, but the scope of the claims of the present invention is not limited by these examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, but do not mean that the conditions must be satisfied for achieving the purpose.
Example 1
1. Cutting foam nickel (1 x 1cm, 300PPI, 3mm) with certain size, sequentially placing in ultrapure water, acetone, hydrochloric acid (1M) and ultrapure water for ultrasonic treatment for 20min each time, and then placing in a vacuum oven for drying for 12 h;
2. dissolving 1.7mg of ammonium molybdate and 7mg of thiourea in 2mL of water, adding 50mg of silicon dioxide (100nm, 30 wt.%) and 0.5mL of ethanol, stirring, uniformly mixing, and performing ultrasonic treatment for 60 min;
3. directly dripping the mixed solution obtained in the step (2) on the foam nickel to enable the foam nickel to be uniformly loaded with the precursor, roasting for 3 hours under a 100W infrared lamp, then placing the foam nickel in vacuum drying for 10 hours, wherein the drying temperature is 60 ℃;
4. transferring the product obtained in the step (3) to a tube furnace, heating to 400 ℃ at a heating speed of 10 ℃/min in an argon atmosphere by a program, controlling the flow rate of the mixed gas to be 80mL/min, and then keeping the temperature for 240 min;
5. mixing 25mL of hydrofluoric acid, 25mL of ethanol and 125mL of water to obtain a mixed solution for removing the template agent, sealing and standing the product obtained in the step (4) in the mixed solution, keeping the mixed solution for 5min, taking out the product, washing the product for several times by using ultrapure water and ethanol until the washing solution is neutral, and drying the product at 80 ℃ for 12 hours to obtain the foam nickel-loaded three-dimensional porous molybdenum disulfide integral electrode (MP-MoS)2@Ni foam)；
The transmission electron microscope (see fig. 1a) shows that the obtained samples are all foam-shaped hole structures, wherein the hole structures can be clearly seen to be mainly composed of holes with the size of 100nm, the whole collapse phenomenon does not exist, and the high-resolution electron microscope (see fig. 1b) shows that the obtained samples are all composed of molybdenum disulfide nanosheet arrays, have rich edges and do not contain other impurities and clusters. In a scanning electron microscope (see figure 2), the growth of three-dimensional porous molybdenum disulfide on a foam nickel framework can be seen, the structure is stable, and the collapse phenomenon is avoided.
Example 2
1. Cutting foam nickel (1 x 1cm, 300PPI, 3mm) with certain size, sequentially placing in ultrapure water, acetone, hydrochloric acid (1M) and ultrapure water for ultrasonic treatment for 20min each time, and then placing in a vacuum oven for drying for 12 h;
2. dissolving 13.3mg of sodium tungstate and 7mg of thiourea in 2mL of water, adding 50mg of silicon dioxide (100nm, 30 wt.%) and 0.5mL of ethanol, stirring uniformly, and performing ultrasonic treatment for 60 min;
3. directly dripping the mixed solution obtained in the step (2) on the foamed nickel to enable the foamed nickel to be uniformly loaded with the precursor, roasting for 3 hours under a 100W infrared lamp, then placing in vacuum drying, and drying for 10 hours at the drying temperature of 60 ℃;
4. transferring the product obtained in the step (3) to a tube furnace, heating to 400 ℃ at a heating speed of 10 ℃/min in an argon atmosphere by a program, controlling the flow rate of the mixed gas to be 80mL/min, and then keeping the temperature for 240 min;
5. mixing 25mL of hydrofluoric acid, 25mL of ethanol and 125mL of water to obtain a mixed solution for removing the template agent, sealing and standing the product obtained in the step (4) in the mixed solution, keeping the mixed solution for 5min, taking out the product, washing the product for several times by using ultrapure water and ethanol until the washing solution is neutral, and drying the product at 80 ℃ for 12 hours to obtain the foam nickel-loaded three-dimensional porous tungsten disulfide integral electrode (MP-WS)2@Ni foam)；
The transmission electron microscope shows that the obtained samples are all foam-shaped hole structures, wherein the hole structures can be clearly seen to be mainly composed of holes with the size of 100nm, the whole structure has no collapse phenomenon, and the high-resolution electron microscope shows that the obtained samples are all composed of tungsten disulfide nanosheet arrays, have rich edges and have no other impurities or clusters. The scanning electron microscope can see that the three-dimensional porous tungsten disulfide grows on the foam nickel framework, the structure is stable, and the collapse phenomenon is avoided.
Example 3
1. Cutting foam nickel (1 x 1cm, 300PPI, 3mm) with certain size, sequentially placing in ultrapure water, acetone, hydrochloric acid (1M) and ultrapure water for ultrasonic treatment for 20min each time, and then placing in a vacuum oven for drying for 12 h;
2. dissolving 23.7mg of cobalt nitrate and 7mg of thiourea in 2mL of water, adding 50mg of silicon dioxide (100nm, 30 wt.%) and 1mL of ethanol, stirring, uniformly mixing, and performing ultrasonic treatment for 60 min;
3. directly dripping the mixed solution obtained in the step (2) on the foamed nickel to enable the foamed nickel to be uniformly loaded with the precursor, roasting for 3 hours under a 100W infrared lamp, and drying for 10 hours at the drying temperature of 60 ℃;
4. transferring the product obtained in the step (3) to a tube furnace, heating to 400 ℃ at a heating speed of 10 ℃/min in an argon atmosphere by a program, controlling the flow rate of the mixed gas to be 80ml/min, and then keeping the temperature for 240 min;
5. mixing 25mL of hydrofluoric acid, 25mL of ethanol and 125mL of water to obtain a mixed solution for removing the template agent, sealing and standing the product obtained in the step (4) in the mixed solution, keeping the mixed solution for 5min, taking out the product, washing the product for several times by using ultrapure water and ethanol until the washing solution is neutral, and drying the product at 80 ℃ for 12 hours to obtain the foam nickel-loaded three-dimensional porous cobalt sulfide monolithic electrode (MP-CoS)2@Ni foam)；
The transmission electron microscope shows that the obtained samples are all foam-shaped hole structures, wherein the hole structures can be clearly seen to be mainly composed of holes with the size of 100nm, the whole body has no collapse phenomenon, and other impurities and clusters do not exist. The scanning electron microscope can see that the three-dimensional porous cobalt sulfide grows on the foam nickel framework, the structure is stable, and the collapse phenomenon is avoided.
Example 4
1. Cutting foam nickel (1 x 1cm, 300PPI, 3mm) with certain size, sequentially placing in ultrapure water, acetone, hydrochloric acid (1M) and ultrapure water for ultrasonic treatment for 20min each time, and then placing in a vacuum oven for drying for 12 h;
2. dissolving 13.7mg of vanadium chloride and 7mg of thiourea in 2mL of water, adding 50mg of silicon dioxide (100nm, 30 wt.%) and 0.5mL of ethanol, stirring, uniformly mixing, and performing ultrasonic treatment for 60 min;
3. directly dripping the mixed solution obtained in the step (2) on the foamed nickel to enable the foamed nickel to be uniformly loaded with the precursor, roasting for 3 hours under a 100W infrared lamp, and drying for 10 hours at the drying temperature of 60 ℃;
4. transferring the product obtained in the step (3) into a tube furnace, heating to 400 ℃ at a heating speed of 10 ℃/min in an argon atmosphere, controlling the flow rate of the mixed gas to be 80ml/min, and then keeping the flow rate for 240 min;
5. mixing 25mL of hydrofluoric acid, 25mL of ethanol and 125mL of water to obtain a mixed solution for removing the template agent, sealing and standing the product obtained in the step (4) in the mixed solution, keeping the mixed solution for 5min, taking out the product, washing the product for several times by using ultrapure water and ethanol until the washing solution is neutral, and drying the product at 80 ℃ for 12 hours to obtain the foam nickel-loaded three-dimensional porous vanadium disulfide integral electrode (MP-VS)2@Ni foam)；
The transmission electron microscope shows that the obtained samples are all foam-shaped hole structures, wherein the hole structures can be clearly seen to be mainly composed of holes with the size of 100nm, the whole body has no collapse phenomenon, and other impurities and clusters do not exist. The scanning electron microscope can see that the three-dimensional porous vanadium disulfide grows on the foam nickel framework, the structure is stable, and the collapse phenomenon is avoided.
Example 5
1. Cutting foam nickel (1 x 1cm, 300PPI, 3mm) with certain size, sequentially placing in ultrapure water, acetone, hydrochloric acid (1M) and ultrapure water for ultrasonic treatment for 20min each time, and then placing in a vacuum oven for drying for 12 h;
2. dissolving 14.6mg of tantalum pentachloride and 7mg of thiourea in 2mL of water, adding 50mg of silicon dioxide (100nm, 30 wt.%) and 0.5mL of ethanol, stirring, uniformly mixing, and performing ultrasonic treatment for 60 min;
3. directly dripping the mixed solution obtained in the step (2) on the foamed nickel to enable the foamed nickel to be uniformly loaded with the precursor, roasting for 3 hours under a 100W infrared lamp, and drying for 10 hours at the drying temperature of 60 ℃;
4. transferring the product obtained in the step (3) to a tube furnace, heating to 400 ℃ at a heating speed of 10 ℃/min in an argon atmosphere by a program, controlling the flow rate of the mixed gas to be 80ml/min, and then keeping the temperature for 240 min;
5. 25mL of hydrofluoric acid, 25mL of ethanol and 125mL of water are mixed to remove the template agentSealing and standing the product obtained in the step (4) in the mixed solution, keeping the mixed solution for 5min, taking out the product, washing the product for a plurality of times by using ultrapure water and ethanol until the washing solution is neutral, and drying the product at the temperature of 80 ℃ for 12h to obtain the foamed nickel loaded three-dimensional porous tantalum disulfide integral electrode (MP-TaS)2@Ni foam)；
The transmission electron microscope shows that the obtained samples are all foam-shaped hole structures, wherein the hole structures can be clearly seen to be mainly composed of holes with the size of 100nm, the whole body has no collapse phenomenon, and other impurities and clusters do not exist. The scanning electron microscope can see that the three-dimensional porous tantalum disulfide grows on the foam nickel framework, the structure is stable, and the collapse phenomenon is avoided.
Example 6
1. Cutting foam nickel (1 x 1cm, 300PPI, 3mm) with certain size, sequentially placing in ultrapure water, acetone, hydrochloric acid (1M) and ultrapure water for ultrasonic treatment for 20min each time, and then placing in a vacuum oven for drying for 12 h;
2. dissolving 3.5mg of ammonium molybdate and 7mg of thiourea in 2mL of water, adding 50mg of silicon dioxide (20nm, 30 wt.%) and 0.5mL of ethanol, stirring, uniformly mixing, and performing ultrasonic treatment for 60 min;
3. directly dripping the mixed solution obtained in the step (2) on the foamed nickel to enable the foamed nickel to be uniformly loaded with the precursor, roasting for 3 hours under a 100W infrared lamp, and drying for 10 hours at the drying temperature of 60 ℃;
4. transferring the product obtained in the step (3) into a tube furnace, heating to 400 ℃ at a heating speed of 10 ℃/min in an argon atmosphere, controlling the flow rate of the mixed gas to be 80mL/min, and then keeping the flow rate for 240 min;
5. mixing 25mL of hydrofluoric acid, 25mL of ethanol and 125mL of water to obtain a mixed solution for removing the template agent, sealing and standing the product obtained in the step (4) in the mixed solution, keeping the mixed solution for 5min, taking out the product, washing the product for several times by using ultrapure water and ethanol until the washing solution is neutral, and drying the product at 80 ℃ for 12 hours to obtain the foam nickel-loaded three-dimensional porous molybdenum disulfide integral electrode (MP-MoS)2@Ni foam-2)；
The transmission electron microscope shows that the obtained samples are all in foam-shaped hole structures, wherein the hole structures can be clearly seen to be mainly composed of holes with the size of 20nm, the whole structure has no collapse phenomenon, and the high-resolution electron microscope shows that the obtained samples are all composed of molybdenum disulfide nanosheet arrays, have rich edges and have no other impurities or clusters. The scanning electron microscope can see that the three-dimensional porous molybdenum disulfide grows on the foam nickel framework, the structure is stable, and the collapse phenomenon is avoided.
Example 7
1. Cutting foam nickel (1 x 1cm, 300PPI, 3mm) with certain size, sequentially placing in ultrapure water, acetone, hydrochloric acid (1M) and ultrapure water for ultrasonic treatment for 20min each time, and then placing in a vacuum oven for drying for 12 h;
2. dissolving 5mg of sodium molybdate and 10mg of thioacetamide in 2mL of water, adding 50mg of silicon dioxide (100nm, 30 wt.%) and 0.5mL of ethanol, stirring, uniformly mixing, and performing ultrasonic treatment for 60 min;
3. directly dripping the mixed solution obtained in the step (2) on the foamed nickel to enable the foamed nickel to be uniformly loaded with the precursor, roasting for 3 hours under a 100W infrared lamp, and drying for 10 hours at the drying temperature of 60 ℃;
4. transferring the product obtained in the step (3) to a tube furnace, heating to 300 ℃ at a heating speed of 10 ℃/min by a program under the argon atmosphere, controlling the flow rate of the mixed gas to be 80mL/min, and then keeping the temperature for 240 min;
5. mixing 25mL of hydrofluoric acid, 25mL of ethanol and 125mL of water to form a mixed solution for removing the template agent, sealing and standing the product obtained in the step (4) in the mixed solution, keeping the mixed solution for 5min, taking out the mixed solution, washing the mixed solution for a plurality of times by using ultrapure water and ethanol until the washing solution is neutral, and drying the washed solution for 12 hours at 80 ℃ to obtain the foam nickel loaded three-dimensional porous molybdenum disulfide integral electrode (MP-MoS)2@Ni foam-3)；
The transmission electron microscope shows that the obtained samples are all foam-shaped hole structures, wherein the hole structures can be clearly seen to be mainly composed of holes with the size of 100nm, the whole structure has no collapse phenomenon, and the high-resolution electron microscope shows that the obtained samples are all composed of molybdenum disulfide nanosheet arrays, have rich edges and have no other impurities or clusters. The scanning electron microscope can see that the three-dimensional porous molybdenum disulfide grows on the foam nickel framework, the structure is stable, and the collapse phenomenon is avoided.
Example 8
1. Cutting foam nickel (1 x 1cm, 300PPI, 3mm) with certain size, sequentially placing in ultrapure water, acetone, hydrochloric acid (1M) and ultrapure water for ultrasonic treatment for 20min each time, and then placing in a vacuum oven for drying for 12 h;
2. dissolving 3.5mg of ammonium molybdate and 10mg of sodium sulfide in 2mL of water, adding 50mg of silicon dioxide (100nm, 30 wt.%) and 0.5mL of ethanol, stirring, uniformly mixing, and performing ultrasonic treatment for 60 min;
3. directly dripping the mixed solution obtained in the step (2) on the foamed nickel to enable the foamed nickel to be uniformly loaded with the precursor, roasting for 3 hours under a 100W infrared lamp, and drying for 10 hours at the drying temperature of 60 ℃;
4. transferring the product obtained in the step (3) to a tube furnace, heating to 400 ℃ at a heating speed of 10 ℃/min in an argon/hydrogen (9:1) atmosphere by a program, keeping the flow rate of the mixed gas at 80mL/min, and then keeping the temperature for 240 min;
5. mixing 25mL of hydrofluoric acid, 25mL of ethanol and 125mL of water to obtain a mixed solution for removing the template agent, sealing and standing the product obtained in the step (4) in the mixed solution, keeping the mixed solution for 5min, taking out the product, washing the product for several times by using ultrapure water and ethanol until the washing solution is neutral, and drying the product at 80 ℃ for 12 hours to obtain the foam nickel-loaded three-dimensional porous molybdenum disulfide integral electrode (MP-MoS)2@Ni foam-4)；
The transmission electron microscope shows that the obtained samples are all foam-shaped hole structures, wherein the hole structures can be clearly seen to be mainly composed of holes with the size of 100nm, the whole structure has no collapse phenomenon, and the high-resolution electron microscope shows that the obtained samples are all composed of molybdenum disulfide nanosheet arrays, have rich edges and have no other impurities or clusters. The scanning electron microscope can see that the three-dimensional porous molybdenum disulfide grows on the foam nickel framework, the structure is stable, and the collapse phenomenon is avoided.
Example 9
1. Cutting foam nickel (1 x 1cm, 300PPI, 3mm) with certain size, sequentially placing in ultrapure water, acetone, hydrochloric acid (1M) and ultrapure water for ultrasonic treatment for 20min each time, and then placing in a vacuum oven for drying for 12 h;
2. dissolving 10mg of ammonium tungstate and 20mg of thiourea in 2mL of water, adding 50mg of silicon dioxide (100nm, 30 wt.%) and 0.5mL of ethanol, stirring, uniformly mixing, and performing ultrasonic treatment for 60 min;
3. directly dripping the mixed solution obtained in the step (2) on the foamed nickel to enable the foamed nickel to be uniformly loaded with the precursor, roasting for 3 hours under a 100W infrared lamp, and drying for 10 hours at the drying temperature of 60 ℃;
4. transferring the product obtained in the step (3) to a tube furnace, heating to 400 ℃ at a heating speed of 10 ℃/min in an argon/hydrogen (9:1) atmosphere by a program, keeping the flow rate of the mixed gas at 80mL/min, and then keeping the temperature for 240 min;
5. 100mL of 6mol L are taken-1Continuously adding 25mL of ethanol into the potassium hydroxide solution to form a mixed solution for removing the template agent, sealing and standing the product obtained in the step (4) in the mixed solution, keeping the mixed solution for 120min, taking out the product, washing the product for several times by using ultrapure water and ethanol until the washing solution is neutral, and drying the product at 80 ℃ for 12 hours to obtain the foamed nickel loaded three-dimensional porous tungsten disulfide integral electrode (MP-WS)2@Ni foam-2)；
The transmission electron microscope shows that the obtained samples are all foam-shaped hole structures, wherein the hole structures can be clearly seen to be mainly composed of holes with the size of 100nm, the whole body has no collapse phenomenon, and other impurities and clusters do not exist. The scanning electron microscope can see that the three-dimensional porous tungsten disulfide grows on the foam nickel framework, the structure is stable, and the collapse phenomenon is avoided.
Comparative example 1
1. Cutting foam nickel (1 x 1cm, 300PPI, 3mm) with certain size, sequentially placing in ultrapure water, acetone, hydrochloric acid (1M) and ultrapure water for ultrasonic treatment for 20min each time, and then placing in a vacuum oven for drying for 12 h;
2. dissolving 1.7mg of ammonium molybdate and 7mg of thiourea in 2mL of water, then continuously adding 0.5mL of ethanol, stirring and uniformly mixing, and performing ultrasonic treatment for 60 min;
3. directly dripping the mixed solution obtained in the step (2) on the foamed nickel to enable the foamed nickel to be uniformly loaded with the precursor, roasting for 3 hours under a 100W infrared lamp, and drying for 10 hours at the drying temperature of 60 ℃;
4. transferring the product obtained in the step (3) to a tube furnace, heating to 400 ℃ at a heating speed of 10 ℃/min in an argon atmosphere by a program, controlling the flow rate of the mixed gas to be 80mL/min, and then keeping the temperature for 240 min;
5. mixing 25mL of hydrofluoric acid, 25mL of ethanol and 125mL of waterSynthesizing a mixed solution for removing the template agent, sealing and standing the product obtained in the step (4) in the mixed solution, keeping the mixed solution for 5min, taking out the product, washing the product for a plurality of times by using ultrapure water and ethanol until the washing solution is neutral, and drying the product at the temperature of 80 ℃ for 12h to obtain the foam nickel loaded two-dimensional molybdenum disulfide integral electrode (FL-MoS)2@Ni foam)；
Comparative example 2
1. Cutting foam nickel (1 x 1cm, 300PPI, 3mm) with certain size, sequentially placing in ultrapure water, acetone, hydrochloric acid (1M) and ultrapure water for ultrasonic treatment for 20min each time, and then placing in a vacuum oven for drying for 12 h;
2. dissolving 13.7mg of vanadium chloride and 7mg of thiourea in 2mL of water, then continuously adding 0.5mL of ethanol, stirring and uniformly mixing, and performing ultrasonic treatment for 60 min;
3. directly dripping the mixed solution obtained in the step (2) on the foamed nickel to enable the foamed nickel to be uniformly loaded with the precursor, roasting for 3 hours under a 100W infrared lamp, and drying for 10 hours at the drying temperature of 60 ℃;
4. transferring the product obtained in the step (3) to a tube furnace, heating to 400 ℃ at a heating speed of 10 ℃/min in an argon atmosphere by a program, controlling the flow rate of the mixed gas to be 80mL/min, and then keeping the temperature for 240 min;
5. mixing 25mL of hydrofluoric acid, 25mL of ethanol and 125mL of water to obtain a mixed solution for removing the template agent, sealing and standing the product obtained in the step (4) in the mixed solution, keeping the mixed solution for 5min, taking out the product, washing the product for several times by using ultrapure water and ethanol until the washing solution is neutral, and drying the product at 80 ℃ for 12 hours to obtain the foam nickel-loaded two-dimensional vanadium disulfide integral electrode (FL-VS)2@Ni foam)；
Application example 1
The catalysts obtained in examples 1 to 5 and comparative examples 1 and 2 were used as catalysts for alkaline electrocatalytic Hydrogen Evolution Reaction (HER), and the activity of the catalysts was evaluated.
1. The electrocatalytic hydrogen evolution performance evaluation method comprises the following steps: a three-electrode system is adopted to carry out a linear sweep voltammetry experiment, a reference electrode is an Hg/HgO electrode, a counter electrode is a carbon rod electrode, an electrolyte is an argon saturated 1M NaOH solution, and a synthesized catalytic material is directly used as a working electrode.
2. And (3) testing conditions are as follows: and (3) testing temperature: at 25 ℃.
3. There is template catalytic material MP-MoS2@ Ni foam and MP-VS2The @ Ni foam shows excellent electrocatalytic hydrogen evolution reaction activity in an alkaline medium, compared with a template-free catalytic material FL-MoS2@ Ni foam and FL-VS2The activity of the @ Ni foam is obviously improved, and compared with other catalysts, the hydrogen evolution activity is in the following order:
MP-MoS2@Ni foam>FL-MoS2@Ni foam；
MP-VS2@Ni foam>FL-VS2@Ni foam
MP-MoS2@Nifoam＞MP-CoS2@Ni foam>MP-WS2@Ni foam>MP-TaS2@Ni foam>MP-VS2@ Ni foam (see Table 1). Compared with a catalytic material without a template agent, the three-dimensional cellular sulfide electrolyzed water catalytic material has the advantages that the three-dimensional cellular structure can not be formed due to the absence of the template agent, the performance is inferior to that of the three-dimensional cellular sulfide electrolyzed water catalytic material, and meanwhile, different performances can be realized by regulating and controlling the types of sulfides.
Application example 2
The catalysts obtained in examples 1 to 5 and comparative examples 1 and 2 were used as catalysts for alkaline electrocatalytic Oxygen Evolution Reaction (OER) to evaluate the activity of the catalysts.
1. The electrocatalytic oxygen evolution performance evaluation method comprises the following steps: a three-electrode system is adopted to carry out a linear sweep voltammetry experiment, a reference electrode is an Hg/HgO electrode, a counter electrode is a carbon rod electrode, an electrolyte is an argon saturated 1M NaOH solution, and a synthesized catalytic material is directly used as a working electrode. .
2. And (3) testing conditions are as follows: and (3) testing temperature: at 25 ℃.
3. There is template catalysis material MP-MoS2@ Ni foam and MP-VS2The @ Ni foam shows excellent electrocatalytic oxygen evolution reaction activity in alkaline medium, compared with a template-free catalytic material FL-MoS2@ Ni foam and FL-VS2The activity of the @ Ni foam is obviously improved, and compared with other catalysts, the oxygen evolution activity is in the following order:
MP-MoS2@Ni foam>FL-MoS2@Ni foam；
MP-VS2@Ni foam>FL-VS2@Ni foam；
MP-MoS2@Ni foam>MP-TaS2@Ni foam>MP-WS2@Ni foam>MP-VS2@Ni foam>MP-CoS2@ Ni foam (see Table 1).
TABLE 1 evaluation results of catalyst Activity under alkalinity
Figure BDA0002317904950000111

Claims (7)

1. The preparation method of the non-noble metal electrolytic water catalytic material is characterized in that the non-noble metal electrolytic water catalytic material comprises a substrate and three-dimensional honeycomb-shaped porous sulfide growing on at least one side surface of the substrate; the substrate is foamed nickel; the aperture of a single hole of the three-dimensional honeycomb-shaped porous sulfide is 10-400 nm, and the hole wall is formed by combining sulfide nanosheet arrays; the holes of the three-dimensional honeycomb-shaped porous sulfide are distributed in a honeycomb shape; the growth amount of the three-dimensional honeycomb-shaped porous sulfide is 1-60mg/cm 2;
the preparation method of the non-noble metal electrolytic water catalytic material comprises the following steps:
(1) sequentially placing the foamed nickel in ultrapure water, acetone, hydrochloric acid and ultrapure water, respectively carrying out ultrasonic treatment for 10-60 min, and then drying at 25-100 ℃ for 4-24 h in vacuum; the concentration of the hydrochloric acid is 1-3M;
(2) mixing a metal cation salt, a sulfur source, alcohol, a pore template and a dispersing agent, ultrasonically dispersing for 0.5-6 h, and stirring for 1-48 h at 25-100 ℃ to obtain a load component precursor mixed solution;
(3) dropping the load component precursor mixed solution obtained in the step (2) on the foamed nickel treated in the step (1), placing the foamed nickel under an infrared lamp of 50-200W for 1-6 h, then carrying out vacuum drying at 25-100 ℃ for 4-24 h, and then keeping the dried product at 200-600 ℃ for 60-360 min under a reducing atmosphere to obtain a reaction product;
(4) transferring the reaction product obtained in the step (3) into a template agent removing solution, sealing and standing for 1-240 min, then washing, and carrying out vacuum drying at 25-150 ℃ for 6-24 h to obtain the non-noble metal electrolytic water catalytic material;
in the step (2), the pore channel template is silicon dioxide;
the template agent removing solution in the step (4) is a mixed solution of a solution A and alcohol; the solution A is at least one of hydrofluoric acid solution and potassium hydroxide solution.
2. The method of claim 1, wherein the sulfide is one or more of tungsten sulfide, cobalt sulfide, nickel sulfide, vanadium sulfide, molybdenum sulfide, tantalum sulfide, iron sulfide, copper sulfide, and manganese sulfide.
3. The production method according to claim 1,
the porosity of the foamed nickel in the step (1) is 75-700 PPI; the thickness is 1-5 mm;
in the step (2), the metal in the metal cation salt is tungsten, cobalt, nickel, vanadium, molybdenum, tantalum, iron, copper and manganese; the metal cation salt is at least one of nitrate, sulfate, chloride and acetate of the metal;
the sulfur source in the step (2) is at least one of thiourea, thioacetamide, sodium sulfide, potassium sulfide, sodium sulfite and sulfur powder;
in the step (2), the dispersant is at least one of water, acetone, toluene, acetonitrile, ethylenediamine, chloroform and diethyl ether;
in the step (2), the alcohol is at least one of methanol, ethanol, ethylene glycol or isopropanol.
4. The production method according to claim 1,
the size of the pore channel template in the step (2) is 10-400 nm;
the molar ratio of sulfur atoms in the sulfur source to metal atoms in the metal cation salt in the step (2) is 1: 10-500: 1;
the mass ratio of metal atoms in the metal cation salt in the step (2) to the pore channel template is 1: 1-100;
the mass ratio of the dispersing agent to the alcohol in the step (2) is 0.5-10: 1.
5. The method according to claim 1, wherein the reducing gas in the step (3) comprises hydrogen and argon, the volume ratio of hydrogen to argon is 0-10: 10, and the flow rate of the mixed gas is 20-200 mL/min.
6. The production method according to claim 1,
the concentration of the solution A is 5-70 wt.%;
the alcohol in the step (4) is at least one of methanol, ethanol, ethylene glycol or isopropanol;
in the mixed solution, the mass ratio of the solution A to the alcohol is 10: 1-50;
in the step (4), the washing is carried out in ultrapure water and ethanol until the solution is neutral.
7. The application of the non-noble metal electrolytic water catalytic material prepared by the preparation method of any one of claims 1 to 6 is characterized in that the non-noble metal catalytic material can be used as an electrolytic water hydrogen evolution catalyst and an electrolytic water oxygen evolution catalyst at the same time.
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