CN109985642B - Ni-Te-S composite carbon material and preparation method and application thereof - Google Patents
Ni-Te-S composite carbon material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 36
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- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 28
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 23
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- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 16
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- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
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- 229910003069 TeO2 Inorganic materials 0.000 claims description 2
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011369 resultant mixture Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 29
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a Ni-Te-S composite carbon material and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) dispersing divalent nickel salt, thioacetamide and Te nano wires in a first solvent, then adding hydrazine hydrate, and carrying out heating reaction to obtain a Ni-Te-S composite material; (2) and (2) mixing and contacting the Ni-Te-S composite material prepared in the step (1) and a carbon source material in a second solvent to obtain the Ni-Te-S composite carbon material. The material has better catalytic activity and stability and good acid-base adaptability, and shows excellent catalytic activity and stability superior to that of a commercial platinum-based catalyst in a strong acid-base environment. Meanwhile, the preparation method is simple to synthesize, has lower cost, and can replace platinum group noble metals such as platinum and the like as a catalyst for hydrogen evolution reaction, so that the preparation method has wider application prospect.
Description
Technical Field
The invention relates to the field of electrochemistry, and in particular relates to a Ni-Te-S composite carbon material and a preparation method and application thereof.
Background
With the rapid development of science and technology and the continuous increase of social demands on the global scale, energy and environmental protection are gradually paid attention to, and attention is paid to clean technology and sustainable hydrogen energy protection. Coal, oil and natural gas have long been the main fossil fuels, and these fossil fuels are non-renewable resources, and the long-term use of the fossil fuels in large quantities not only causes the endangered shortage of resources, but also brings threat to the ecological environment. Therefore, it is imperative to develop a new, green and renewable energy source, and hydrogen energy, a green secondary energy source, is highly efficient, pollution-free and has a high calorific value (-142 KJ g)-1) The characteristics of the hydrogen energy are widely concerned, the hydrogen energy can be used as a raw material for chemical industry, food, pharmacy and other industries, metallurgy, electronic component production and the like, and more importantly, the hydrogen energy only releases water without hydrogen energyCO2Generation of (a): 2H2+O2→2H2And O. As a new energy source in the 21 st century worldwide, hydrogen energy is developed and utilized by various countries, and especially in some developed countries, the concept of hydrogen economy is put into the strategic position in energy planning, so that it seems that the hydrogen economy in the future is a rapidly developing economic industry, and the hydrogen energy will play an important role in the world stage.
Hydrogen energy is considered to be the most important secondary energy source in the world's energy arena in the 21 st century. Although hydrogen is the most abundant substance in the universe, hydrogen mainly forms a compound with other substances and exists in a simple substance state, so that the development of various hydrogen production technologies is of great significance. Wherein, the water electrolysis hydrogen production technology is the most efficient and extensive method for all hydrogen evolution at present. The basic reaction equation is 2H2O＝2H2↑+O2℃,. according to the method, the reaction can be carried out at normal temperature and normal pressure, the production amount of hydrogen in the reaction is 2 times of that of oxygen, but a large amount of electric energy is consumed, so that the method is restricted, and therefore, the research of a novel cathode hydrogen evolution material with low energy consumption is urgent.
Precious metal (e.g., platinum group metals) based materials are the most performing hydrogen evolution catalysts, and their rarity and associated high cost alone impose severe limitations on the global use of precious metal based materials. Finding inexpensive alternatives has been a goal of chemists and material scientists.
Disclosure of Invention
The invention aims to provide a composite material which is used as a catalyst for hydrogen evolution reaction instead of platinum group noble metals such as platinum and the like, and has better catalytic activity and stability and good acid-base adaptability. Moreover, the preparation method is simple and the cost is lower.
In order to achieve the above object, the present invention provides a method for preparing a Ni-Te-S composite carbon material, comprising the steps of: (1) dispersing divalent nickel salt, thioacetamide and Te nano wires in a first solvent, then adding hydrazine hydrate, and carrying out heating reaction to obtain a Ni-Te-S composite material; (2) and (2) mixing and contacting the Ni-Te-S composite material prepared in the step (1) and a carbon source material in a second solvent to obtain the Ni-Te-S composite carbon material.
The invention also provides the Ni-Te-S composite carbon material prepared by the preparation method.
Furthermore, the invention also provides an application of the Ni-Te-S composite carbon material in hydrogen evolution catalytic reaction.
Through the technical scheme, the method comprises the steps of dispersing the divalent nickel salt, thioacetamide and Te nano wires in a first solvent, then adding hydrazine hydrate, and carrying out heating reaction to obtain the Ni-Te-S composite material; mixing and contacting the Ni-Te-S composite material prepared in the step (1) and a carbon source material in a second solvent to obtain a Ni-Te-S composite carbon material; the material has better catalytic activity and stability and good acid-base adaptability, and shows excellent catalytic activity and stability superior to that of a commercial platinum-based catalyst in a strong acid-base environment. The inventors speculate that the mechanism for realizing the invention is as follows: transition metal Ni is used as a coordination center, a sulfur source and a tellurium source are introduced in situ to improve the conductivity of the material and increase active sites, and the corrosion of an acid-base environment to the material is reduced while the conductivity of the material is changed by adding a carbon material, so that the material has better catalytic activity. Meanwhile, the preparation method is simple to synthesize, has lower cost, and can replace platinum group noble metals such as platinum and the like as a catalyst for hydrogen evolution reaction, so that the preparation method has wider application prospect.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a representation result diagram of a scanning electron microscope of a Ni-Te-S composite carbon material B1;
FIG. 2 is a representation result of a scanning electron microscope of the Ni-Te-S composite material C1;
FIG. 3 is a representation result of a scanning electron microscope of the Ni-S composite material C2;
FIG. 4 is a representation result of the Ni-Te composite material C3 by scanning electron microscope;
FIG. 5 is a graph showing the results of transmission electron microscopy characterization of the Ni-Te-S composite carbon material B1;
FIG. 6 is a graph showing the results of XPS characterization of Ni-Te-S composite carbon material B1;
FIG. 7 is a graph showing the LSV test results of Ni-Te-S composite carbon material B1;
FIG. 8 is a graph of the results of CV test post-treatment of B1, C1, C2, C3;
fig. 9 is a graph of the results of the impedance tests of B1, C1, C2, and C3.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In order to achieve the above object, the present invention provides a method for preparing a Ni-Te-S composite carbon material, comprising the steps of: (1) dispersing divalent nickel salt, thioacetamide and Te nano wires in a first solvent, then adding hydrazine hydrate, and carrying out heating reaction to obtain a Ni-Te-S composite material; (2) and (2) mixing and contacting the Ni-Te-S composite material prepared in the step (1) and a carbon source material in a second solvent to obtain the Ni-Te-S composite carbon material.
Through the technical scheme, the method comprises the steps of dispersing the divalent nickel salt, thioacetamide and Te nano wires in a first solvent, then adding hydrazine hydrate, and carrying out heating reaction to obtain the Ni-Te-S composite material; mixing and contacting the Ni-Te-S composite material prepared in the step (1) and a carbon source material in a second solvent to obtain a Ni-Te-S composite carbon material; the material has better catalytic activity and stability and good acid-base adaptability, and shows excellent catalytic activity and stability superior to that of a commercial platinum-based catalyst in a strong acid-base environment. The inventors speculate that the mechanism for realizing the invention is as follows: transition metal Ni is used as a coordination center, a sulfur source and a tellurium source are introduced in situ to improve the conductivity of the material and increase active sites, and the corrosion of an acid-base environment to the material is reduced while the conductivity of the material is changed by adding a carbon material, so that the material has better catalytic activity. Meanwhile, the preparation method is simple to synthesize, has lower cost, and can replace platinum group noble metals such as platinum and the like as a catalyst for hydrogen evolution reaction, so that the preparation method has wider application prospect.
In the present invention, conventional technical means in the art, such as stirring, shaking, ultrasound, etc., can be selected for mixing or dispersing, and the present invention can be implemented as long as the mixture can be uniformly mixed, which is not described herein again.
In the step (1), the amounts of the divalent nickel salt, thioacetamide, Te nanowire and hydrazine hydrate may be selected within a wide range, but in order to further improve the yield and catalytic performance of the resulting Ni — Te — S composite material, it is preferable that the ratio of the amounts of the divalent nickel salt, thioacetamide, Te nanowire and hydrazine hydrate in the step (1) is 1 mmol: 0.15-0.35 g: 0.35-0.55 g: 3-7 mL.
The conditions for the heating reaction in step (1) may be selected within a wide range, but in order to further improve the yield and catalytic performance of the Ni-Te-S composite material obtained, it is preferable that the reaction temperature is 170-190 ℃.
The conditions for the heating reaction in step (1) may be selected within a wide range, but in order to further improve the yield and catalytic properties of the Ni-Te-S composite material obtained, it is preferable that the reaction time is from 1 to 10 hours.
In the step (2), the mass ratio of the Ni-Te-S composite material prepared in the step (1) to the carbon source material can be selected within a wide range, but in order to further improve the yield and the catalytic performance of the prepared Ni-Te-S composite material, it is preferable that in the step (2), the mass ratio of the Ni-Te-S composite material prepared in the step (1) to the carbon source material is 6:4 to 9: 1.
In the step (2), the conditions of the mixing contact may be selected within a wide range, but in order to further improve the yield and catalytic performance of the Ni — Te — S composite material produced, it is preferable that in the step (2), the conditions of the mixing contact include: the temperature is 10-60 ℃.
In the step (2), the conditions of the mixing contact may be selected within a wide range, but in order to further improve the yield and catalytic performance of the Ni-Te-S composite material obtained, it is preferable that the time of the mixing contact is 1 to 3 hours.
The specific kind of the divalent nickel salt may be selected within a wide range as long as it is soluble in the organic solvent, but in order to further improve the yield and catalytic performance of the resulting Ni — Te — S composite material, preferably, the divalent nickel salt is selected from at least one of nickel chloride hexahydrate, nickel acetate tetrahydrate, and nickel nitrate hexahydrate.
The carbon source material may be selected within a wide range, but in order to further improve the yield and catalytic performance of the prepared Ni-Te-S composite material, it is preferable that the carbon source material is selected from at least one of carbon nanotubes, acetylene black, and nitrogen-doped graphene.
The first solvent may be selected within a wide range, but in order to further improve the yield and catalytic performance of the Ni — Te — S composite material produced, it is preferable that the first solvent is selected from a mixture of at least two of ethylene glycol, anhydrous ethanol, and water. Furthermore, in order to further improve the yield and the catalytic performance of the prepared Ni-Te-S composite material, the first solvent is a mixed solution formed by water and absolute ethyl alcohol in a volume ratio of 2-5: 3.
The second solvent may be selected within a wide range, but in order to further improve the yield and catalytic performance of the produced Ni — Te — S composite material, preferably, the second solvent is selected from at least one of ethylene glycol, anhydrous ethanol, and water.
The Te nano-wire can be prepared by various methods, and in the invention, in order to further improve the yield and better appearance of the prepared tellurium nano-wire, the prepared tellurium nano-wire is further improvedThe invention optimizes the preparation method of the Te nanowire, and the Te nanowire is prepared by the following method: in a third solvent, polyvinylpyrrolidone and TeO2The heating reaction is carried out in the presence of hydrazine hydrate to obtain black powder.
The amount of each material can be selected in a wide range, but in order to further improve the yield and better morphology of the prepared tellurium nanowires, the amount of hydrazine hydrate is preferably 3-5 mL.
The conditions of the heating reaction of the prepared tellurium nanowires can be selected within a wide range, but in order to further improve the yield and better morphology of the prepared tellurium nanowires, preferably, the heating reaction satisfies the following conditions: the reaction time is 1h, and the reaction temperature is 120-200 ℃.
The specific kind of the third solvent for the prepared tellurium nanowires can be selected within a wide range, but in order to further improve the yield and better morphology of the prepared tellurium nanowires, preferably, the third solvent is selected from at least one of ethylene glycol, anhydrous ethanol and water.
In order to further improve the purity of the prepared tellurium nanowires, preferably, after the heating reaction, the preparation method further comprises: the reaction was centrifuged to remove the solvent, followed by drying. In the above embodiment, the conditions for drying may be selected within a wide range, but in order to improve the drying effect, it is preferable that the drying satisfies the following conditions: the drying temperature is 50-70 deg.C, and the drying time is 12-24 h.
The invention also provides the Ni-Te-S composite carbon material prepared by the preparation method.
Furthermore, the invention also provides an application of the Ni-Te-S composite carbon material in hydrogen evolution catalytic reaction.
Through the technical scheme, the method comprises the steps of dispersing the divalent nickel salt, thioacetamide and Te nano wires in a first solvent, then adding hydrazine hydrate, and carrying out heating reaction to obtain the Ni-Te-S composite material; mixing and contacting the Ni-Te-S composite material prepared in the step (1) and a carbon source material in a second solvent to obtain a Ni-Te-S composite carbon material; the material has better catalytic activity and stability and good acid-base adaptability, and shows excellent catalytic activity and stability superior to that of a commercial platinum-based catalyst in a strong acid-base environment. The inventors speculate that the mechanism for realizing the invention is as follows: transition metal Ni is used as a coordination center, a sulfur source and a tellurium source are introduced in situ to improve the conductivity of the material and increase active sites, and the corrosion of an acid-base environment to the material is reduced while the conductivity of the material is changed by adding a carbon material, so that the material has better catalytic activity. Meanwhile, the preparation method is simple to synthesize, has lower cost, and can replace platinum group noble metals such as platinum and the like as a catalyst for hydrogen evolution reaction, so that the preparation method has wider application prospect.
The present invention will be described in detail below by way of examples. Electrochemical detection is carried out on a chemical workstation of Shanghai Chenghua apparatus company with the model number of CHI 6211E; x-ray photoelectron spectroscopy characterization (XPS) obtained by Al Ka radiation from Thermo Fisher Scientific, USA, thermocouple ESCALAB250XI spectrometer; the transmission electron microscope characterization is carried out on a transmission electron microscope with a Japanese Hitachi company model number of JEOL-2010; scanning electron microscopy characterization was performed using a Regulus-8100 scanning electron microscope.
Nickel acetate tetrahydrate and polyvinylpyrrolidone (PVP) are commercially available products of chemical reagents of national drug group; solvents: hydrazine hydrate 85%, ethylene glycol, absolute ethyl alcohol are the products sold by the national pharmaceutical group chemical reagent limited company; tellurium dioxide is a product sold in the Aladdin reagent company; thioacetamide is a commercially available product of welan chemicals ltd.
Preparation example 1
Respectively dissolving 3mmol of tellurium dioxide and 0.6g of polyvinylpyrrolidone in 50mL of ethylene glycol, then placing the solution in a round-bottom flask, heating by adopting an oil bath pot, keeping condensation reflux, quickly adding 4mL of hydrazine hydrate when the temperature is increased to 160 ℃, stopping heating after keeping the temperature for 60min, naturally cooling, taking out the solution, centrifugally washing by using a high-speed centrifuge, washing for three times by adopting secondary distilled water and absolute ethyl alcohol respectively, and drying for 18h at 60 ℃ to obtain black pink, namely tellurium nanowires; designated as a 1.
Preparation example 2
Tellurium nanowires, designated A2, were prepared according to the method of preparation example 1; except that the amount of hydrazine hydrate was 3mL and the reaction temperature was 200 ℃.
Preparation example 3
Tellurium nanowires, designated A3, were prepared according to the method of preparation example 1; except that the amount of hydrazine hydrate was 5mL and the reaction temperature was 120 ℃.
Example 1
1) 0.24884g of nickel acetate tetrahydrate (1mmol), 0.2552g of tellurium nanowire A1(2mmol) obtained in preparation example 1 and 0.45g of thioacetamide are weighed, dissolved in a mixed solution of 40mL of redistilled water and 30mL of absolute ethyl alcohol respectively at room temperature, subjected to ultrasonic dispersion, added with 5mL of hydrazine hydrate after dispersion, transferred into a high-pressure reaction kettle, and the reaction temperature is set to 180 ℃ and the reaction time is 2 hours.
And after the temperature of the reaction kettle is reduced to room temperature, centrifugally washing, and vacuum drying at 60 ℃ for 18 hours.
2) 80mg of the product and 20mg of acetylene black are weighed, dissolved in 50mL of absolute ethyl alcohol at room temperature, and ultrasonically dispersed for 2 hours. The resulting mixture was washed by centrifugation and dried under vacuum at 60 ℃ for 18 hours to obtain a Ni-Te-S composite carbon material designated as B1.
Example 2
1) 0.24884g of nickel acetate tetrahydrate (1mmol), 0.15g of tellurium nanowire A2(2mmol) obtained in preparation example 2 and 0.55g of thioacetamide are weighed, dissolved in a mixed solution of 40mL of redistilled water and 30mL of absolute ethyl alcohol respectively at room temperature, ultrasonically dispersed, 5mL of hydrazine hydrate is added after dispersion, the mixture is transferred to a high-pressure reaction kettle, the reaction temperature is set to 190 ℃, and the reaction time is 1 h.
And after the temperature of the reaction kettle is reduced to room temperature, centrifugally washing, and vacuum drying at 60 ℃ for 18 hours.
2) 60mg of the product and 40mg of the carbon nano tube are weighed, dissolved in 50mL of absolute ethyl alcohol at room temperature, and ultrasonically dispersed for 2 hours. The resulting mixture was washed by centrifugation and dried under vacuum at 60 ℃ for 18 hours to obtain a Ni-Te-S composite carbon material designated as B2.
Example 3
1) 0.24884g of nickel acetate tetrahydrate (1mmol), 0.35g of tellurium nanowire A1(2mmol) obtained in preparation example 1 and 0.35g of thioacetamide are weighed, dissolved in a mixed solution of 40mL of redistilled water and 30mL of absolute ethyl alcohol respectively at room temperature, ultrasonically dispersed, 5mL of hydrazine hydrate is added after dispersion, the mixture is transferred to a high-pressure reaction kettle, the reaction temperature is set to be 170 ℃, and the reaction time is 10 hours.
And after the temperature of the reaction kettle is reduced to room temperature, centrifugally washing, and vacuum drying at 60 ℃ for 18 hours.
2) Weighing 90mg of the product and 10mg of nitrogen-doped graphene, dissolving in 50mL of absolute ethyl alcohol at room temperature, and performing ultrasonic dispersion for 2 hours. The resulting mixture was washed by centrifugation and dried under vacuum at 60 ℃ for 18 hours to obtain a Ni-Te-S composite carbon material designated as B3.
Example 4
A Ni-Te-S composite carbon material was produced in the same manner as in example 1, except that the tellurium nanowire A1 was replaced with a tellurium nanowire A3.
Comparative example 1
0.24884g of nickel acetate tetrahydrate (1mmol), 0.35g of tellurium nanowire A1(2mmol) and 0.35g of thioacetamide are weighed, dissolved in a mixed solution of 40mL of redistilled water and 30mL of absolute ethyl alcohol at room temperature respectively, subjected to ultrasonic dispersion, added with 5mL of hydrazine hydrate after being dispersed, transferred into a high-pressure reaction kettle, the reaction temperature is set to be 180 ℃, and the reaction time is 10 hours.
And after the temperature of the reaction kettle is reduced to room temperature, centrifugally washing, and vacuum drying at 60 ℃ for 18 hours. A Ni- -Te- -S composite material was obtained, designated as C1.
Comparative example 2
0.24884g of nickel acetate tetrahydrate (1mmol) and 0.45g of thioacetamide are weighed, respectively dissolved in a mixed solution of 40mL of redistilled water and 30mL of absolute ethyl alcohol at room temperature, ultrasonic dispersion is carried out, 5mL of hydrazine hydrate is added after dispersion, the mixture is transferred to a high-pressure reaction kettle, the reaction temperature is set to be 180 ℃, and the reaction time is 2 hours.
And after the temperature of the reaction kettle is reduced to room temperature, centrifugally washing, and vacuum drying at 60 ℃ for 18 hours. A Ni-S composite material was obtained and designated C2.
Comparative example 3
0.24884g of nickel acetate tetrahydrate (1mmol) and 0.2552g of tellurium nanowire A1(2mmol) are weighed, dissolved in a mixed solution of 40mL of redistilled water and 30mL of absolute ethyl alcohol at room temperature respectively, subjected to ultrasonic dispersion, 5mL of hydrazine hydrate is added after dispersion, the mixture is transferred to a high-pressure reaction kettle, the reaction temperature is set to be 180 ℃, and the reaction time is 2 hours.
And after the temperature of the reaction kettle is reduced to room temperature, centrifugally washing, and vacuum drying at 60 ℃ for 18 hours. A Ni-Te composite material was obtained, and was designated as C3.
Detection example 1
The morphology of the Ni-Te-S composite carbon material B1 in example 1 was characterized by a JEOLJSM-6700F scanning electron microscope, and the specific results are shown in FIG. 1; the Ni-Te-S composite material C1 is subjected to shape characterization, and the specific result is shown in figure 2; carrying out morphology characterization on the Ni-S composite material C2, wherein the specific result is shown in figure 3; the Ni-Te composite material C3 is subjected to morphology characterization, and specific results are shown in a figure 4.
The morphology of B1 was characterized by a transmission electron microscope of JEOL-2010, Hitachi, Japan, and the specific results are shown in FIG. 5.
X-ray photoelectron spectroscopy (XPS) characterization of B1 was obtained by Al Ka radiation from Thermo Fisher Scientific, USA, thermocouple ESCALAB250XI spectrometer, as shown in FIG. 6.
FIG. 1 is a scanning topography characterization chart of Ni-Te-S composite carbon material B1, and compared with FIG. 2, it can be seen that there is some more black material, which is mechanically mixed acetylene black. FIG. 3 shows that the Ni-S composite material C2 has a sheet-like structure, and FIG. 4 shows that the Ni-Te composite material has a linear structure. While the scan of the Ni-Te-S composite material C1 in FIG. 2 has both a sheet-like structure and a wire-like structure and the sizes are equivalent, which shows that the Ni-Te compound and the Ni-S compound coexist in the in-situ synthesized Ni-Te-S composite material.
FIG. 5 shows that the Ni-Te-S composite carbon material has uniformly distributed flaky and linear structures, and both are hollow structures, and in the reaction process, the Ni-Te-S composite carbon material can expose multiple active sites after being compounded.
And the XPS analysis and characterization of figure 6 are combined, so that the prepared composite material contains elements Ni, Te, S, O and C, and further proves that the Ni-Te-S composite carbon material is successfully prepared in the invention.
The products of examples 2-4 were characterized according to the same method, with results substantially identical to those of example 1; the products of preparation examples 2 to 3 were characterized in the same manner, and the results were substantially identical to those of preparation example 1.
Application example 1
The glassy carbon modified electrodes modified by B1, C1, C2 and C3 are correspondingly marked as B1 ', C1', C2 'and C3';
preparing a modified electrode:
the glassy carbon rotary disk electrode needs to be carefully cleaned before use, is polished on wet polishing cloth by using alumina powder, and is then subjected to ultrasonic treatment in secondary distilled water and absolute ethyl alcohol in sequence to achieve thorough cleaning.
5mg of the final sample was added to the mixture (Nafion: 2-propanol: water in a volume ratio of 5:200: 800) to prepare a catalyst suspension having a concentration of 5 mg/mL. 10 microliter (5 microliter each time) is respectively taken to be put on a glassy carbon rotating disk electrode with the diameter of 5mm to prepare the glassy carbon modified electrode.
Taking 1mol/L KOH solution as electrolyte, selecting a platinum electrode as a counter electrode, a calomel electrode as a reference electrode, and taking B1 ', C1', C2 'and C3' as working electrodes, carrying out LSV test on B1 ', C1', C2 'and C3' in a three-electrode test system, wherein the rotating speed of a rotating disc electrode is 1600 rpm. And introducing nitrogen into the electrolyte for 30-40min, and carrying out LSV test. In the LSV test described above, the potential was selected from-2 to 0.8V and the scan rate was 5 mV/s. The LSV curve obtained by the test is shown in FIG. 7; in fig. 7, the abscissa Potential (V vs. RHE) represents the voltage of the Reversible Hydrogen Electrode (RHE) in terms of nernst equation ERHE ═ ESCE +0.242+0.0591 · pH; ordinate j (mA/cm)2) The current density is indicated.
A1 mol/L KOH solution is used as an electrolyte, a platinum electrode is selected as a counter electrode, a calomel electrode is selected as a reference electrode, B1 ', C1', C2 'and C3' are used as working electrodes, CV test is carried out on B1 ', C1', C2 'and C3' in a three-electrode test system, and the rotating speed of a rotating disc electrode is 1600 rpm. Introducing nitrogen into the electrolyte for 30-40min, and performing CV test at different sweep speeds. CV curve obtained by testingThe graph is shown in FIG. 8 after a series of conversions; in FIG. 8, the abscissa Scan Rate (V/s) represents the sweep Rate; ordinate Δ j (mA/cm)2) The current density difference at the same potential is shown.
A1 mol/L KOH solution is used as an electrolyte, a platinum electrode is selected as a counter electrode, a calomel electrode is selected as a reference electrode, B1 ', C1', C2 'and C3' are used as working electrodes, and B1 ', C1', C2 'and C3' are subjected to impedance test in a three-electrode test system. And introducing nitrogen into the electrolyte for 30-40min, and carrying out impedance test. In the impedance test, the potential was selected to be-1.40V (vs. SCE), the high frequency was 100000Hz, and the low frequency was 0.01 Hz. The impedance profile obtained from the test is shown in fig. 9 after a series of treatments.
Overpotential is the applied voltage at which the reaction occurs at a rate of 10mA cm-2The overpotential of (c) is an important parameter for the evaluation of HER catalytic activity. The ideal catalyst is capable of producing relatively high current densities at lower overpotentials. As can be seen from FIG. 7, the overpotential of C3 is significantly lower than that of B1, C1 and C2, and has the best hydrogen evolution catalytic performance.
The electrochemically active surface area can be indirectly characterized by the electric double layer capacitance (Cdl) of the solid-liquid interface, and the larger the Cdl value, the more surface active sites are exposed. To a certain extent, the more active sites, the better hydrogen evolution catalytic performance of the material is proved. As can be seen from FIG. 8, Cdl value of C3 is significantly greater than that of B1, C1 and C2, and the most surface active sites are exposed.
Electrochemical Impedance (EIS) was used to evaluate HER kinetics and electrode electrolyte interface reactions. The charge transfer resistance (Rct) is related to the electrode interface charge transfer and can be characterized by the semicircular diameter of a high-frequency region, and the smaller the diameter, the smaller the resistance. As can be seen from fig. 9, the EIS value of C3 is significantly smaller than that of B1, C1 and C2, and the doped carbon material has good conductivity.
As can be seen from fig. 7-9: compared with the hydrogen evolution catalytic performances of B1, C1, C2 and C3, the Ni-Te-S composite carbon material is obviously seen to have the optimal catalytic activity, lower catalytic potential, better conductivity and larger current density and electrochemical active area.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (7)
1. A preparation method of a Ni-Te-S composite carbon material is characterized by comprising the following steps:
(1) dispersing divalent nickel salt, thioacetamide and Te nano wires in a first solvent, then adding hydrazine hydrate, and carrying out heating reaction to obtain a Ni-Te-S composite material;
(2) mixing and contacting the Ni-Te-S composite material prepared in the step (1) and a carbon source material in a second solvent to obtain a Ni-Te-S composite carbon material;
wherein in the step (1), the dosage ratio of the divalent nickel salt, thioacetamide, Te nano wire and hydrazine hydrate is 1 mmol: 0.15-0.35 g: 0.35-0.55 g: 3-7 mL; the heating reaction conditions in the step (1) comprise: the reaction temperature is 170-190 ℃; and/or the reaction time is 1-10 h; in the step (2), the mass ratio of the Ni-Te-S composite material prepared in the step (1) to the carbon source material is 6: 4-9: 1; in the step (2), the conditions of the mixing contact comprise: the temperature is 10-60 ℃; and/or the mixing contact time is 1-3 h.
2. The production method according to claim 1, wherein the Te nanowire is produced by: in a third solvent, polyvinylpyrrolidone and TeO2The heating reaction is carried out in the presence of hydrazine hydrate,obtaining black powder;
wherein the third solvent is at least one of ethylene glycol, absolute ethyl alcohol and water.
3. The production method according to claim 1, wherein a divalent nickel salt is selected from at least one of nickel chloride hexahydrate, nickel acetate tetrahydrate, and nickel nitrate hexahydrate;
and/or the carbon source material is at least one selected from carbon nano tubes, acetylene black and nitrogen-doped graphene;
and/or, the first solvent is selected from a mixture of at least two of ethylene glycol, absolute ethanol and water;
and/or, the second solvent is selected from at least one of ethylene glycol, anhydrous ethanol, and water.
4. The method according to claim 3, wherein the first solvent is a mixture of water and absolute ethyl alcohol at a volume ratio of 2-5: 3.
5. The production method according to any one of claims 1 to 4, further comprising, after the heating reaction in step (1), a step of centrifuging the resultant mixture to retain the precipitate, and washing and drying the precipitate;
and/or, after the heating reaction in the step (2), the method further comprises the steps of centrifuging the obtained mixture to retain the precipitate, washing and drying the precipitate.
6. A Ni-Te-S composite carbon material produced by the production method according to any one of claims 1 to 5.
7. Use of the Ni-Te-S composite carbon material according to claim 6 for hydrogen evolution catalytic reactions.
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