CN113832492A - Nickel-cobalt-sulfur material, preparation method and application in electrocatalytic OER - Google Patents
Nickel-cobalt-sulfur material, preparation method and application in electrocatalytic OER Download PDFInfo
- Publication number
- CN113832492A CN113832492A CN202111090927.5A CN202111090927A CN113832492A CN 113832492 A CN113832492 A CN 113832492A CN 202111090927 A CN202111090927 A CN 202111090927A CN 113832492 A CN113832492 A CN 113832492A
- Authority
- CN
- China
- Prior art keywords
- nickel
- cobalt
- carbon cloth
- deionized water
- reaction kettle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/056—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of textile or non-woven fabric
-
- 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
- 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
-
- 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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- 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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention belongs to the field of electrocatalysis, and particularly relates to a nickel-cobalt-sulfur material, a preparation method and application thereof in electrocatalysis OER. The method takes cobalt nitrate hexahydrate, urea and nickel nitrate hexahydrate aqueous solutions with different molar weights as raw materials, prepares a nickel-cobalt hydroxide precursor through a first hydrothermal reaction, adds sodium sulfide nonahydrate to vulcanize the precursor through a second hydrothermal reaction, and successfully prepares the nickel-cobalt-sulfur catalyst for electrolyzing water to produce oxygen. The nickel cobalt sulfur nanometer materials synthesized by nickel nitrate hexahydrate with different molar weights have different morphologies and OER performances. The preparation process involved in the invention is simple and convenient, and has quite good application prospect in some battery fields.
Description
Technical Field
The invention belongs to the field of electrocatalysis, and particularly relates to a nickel-cobalt-sulfur nano material with specific nickel-cobalt molar ratio and starfish-shaped nanorod structure morphology, a preparation method thereof and application thereof in electrocatalysis OER.
Background
The ever-increasing demand for energy and fuels, coupled with the global depletion of fossil fuels and their associated negative environmental impacts, is driving the pursuit and intense research into a wide variety of high-efficiency, low-cost, sustainable energy conversion and storage technologies. The electrically driven water splitting to produce hydrogen and oxygen fuels is considered one of the most promising and valuable strategies for converting solar energy into electrical energy, and thus can overcome the shortage of fossil fuelsThe conversion and storage of solar energy now. The hydrogen produced by this technology is widely regarded as a sustainable and abundant energy carrier, and the electrocatalytic decomposition of water to produce hydrogen can solve the current energy crisis problem faced by mankind due to high energy density and no carbon emissions when stored and released. However, the cost required for hydrogen production by water electrolysis is much higher than that of hydrogen production by fossil fuel due to the slow kinetics of Oxygen Evolution Reaction (OER) occurring at the anode, the large overpotential, and the higher voltage required for hydrogen production by water electrolysis than the thermodynamic potential for water decomposition. Therefore, IrO is often required2And RuO2This noble metal material acts as a catalyst, but due to the high price and limited reserves of noble metals, its wide application in industry is limited. Therefore, it is of great significance to develop and design an OER electrocatalyst that can replace noble metals. In recent years, transition metal sulfides have attracted much attention as electrocatalytic OER catalyst materials. Among them, researchers have found various transition metal sulfides such as CoS2、Co3S4、Co9S8Etc., however, their OER performance is not ideal. As the OER performance of the single transition metal sulfide needs to be improved, another transition metal is introduced to form a bimetallic sulfide, the element valence state is adjusted through the synergistic effect of bimetallic, and the two metals have different molar ratios and different morphological properties. Research shows that the introduction of transition metal nickel into transition metal sulfide is a way to effectively improve the performance of OER. Therefore, the invention provides a simple and efficient method for synthesizing nickel-cobalt-sulfur nano materials with different proportions, so as to improve the performance of the electrocatalytic OER.
Disclosure of Invention
The invention aims to provide a preparation method of nickel-cobalt-sulfur nano materials with high OER performance and different morphologies, and aims to solve the problems.
The invention adopts the following specific technical scheme:
a preparation method of nickel cobalt sulfide for an electrocatalytic OER catalyst comprises the following steps:
(1) pretreatment of the carbon cloth: cutting the carbon cloth into blocks, wherein the size of each block is 3cm multiplied by 4 cm; and sequentially carrying out ultrasonic cleaning in acetone, distilled water and absolute ethyl alcohol for 30 min. The purpose is to remove impurities on the surface of the carbon cloth. And (3) placing the carbon cloth subjected to the cleaning treatment in a nitric acid solution, wherein the mass percentage concentration of the nitric acid solution is 40%, and carrying out oxidation treatment under an ultrasonic condition for 30 min. Aims to improve the wettability of the carbon cloth, reduce the contact angle and improve the surface energy of a matrix.
(2) The preparation method of the nickel cobalt hydroxide precursor comprises the following steps: respectively weighing cobalt nitrate hexahydrate, urea and nickel nitrate hexahydrate into a beaker, weighing deionized water by using a measuring cylinder, adding deionized water into the beaker, and uniformly dissolving the mixture by magnetic stirring at room temperature for 30min, wherein the ratio of the cobalt nitrate hexahydrate, the urea, the nickel nitrate hexahydrate and the deionized water is 5 mmol: 5 mmol: 0.5-2.5 mmol: 35 mL. And (3) transferring the mixed solution into a stainless steel high-pressure hydrothermal reaction kettle, soaking the carbon cloth processed in the step (1) in the reaction kettle, screwing a kettle cover, putting the stainless steel high-pressure hydrothermal reaction kettle into a drying oven, and reacting for 12 hours at 120 ℃ to obtain the carbon cloth loaded with the nickel-cobalt hydroxide precursor.
(3) After the reaction is finished, cooling the reaction kettle to room temperature, taking out the carbon cloth loaded with the product, washing the carbon cloth with deionized water and ethanol respectively for 3-5 times, and drying the carbon cloth in an oven for 6 hours at 60 ℃.
(4) Weighing sodium sulfide nonahydrate and dissolving in deionized water, wherein the ratio of the sodium sulfide nonahydrate to the cobalt nitrate hexahydrate in the step (2) to the deionized water is 8 mmol: 5 mmol: 40 mL. Magnetically stirring at room temperature to form a uniform clear solution, and magnetically stirring for 30 min.
(5) And (3) transferring the clear solution obtained in the step (4) to a stainless steel high-pressure reaction kettle, soaking the carbon cloth loaded with the nickel-cobalt hydroxide precursor prepared in the step (2) in the reaction kettle, and putting the reaction kettle into an oven to react for 4 hours at 120 ℃.
(6) After the reaction is finished, after the reaction kettle is cooled to room temperature, taking out the carbon cloth, respectively washing the carbon cloth for 3-5 times by using deionized water and ethanol, and drying the carbon cloth in air for 6 hours in an oven at the temperature of 60 ℃ to obtain the nickel-cobalt-sulfur nano material.
The nickel nitrate hexahydrate with different molar weights in the step (2) has different molar weights, different molar ratios of nickel and cobalt, and different morphologies and electrocatalytic OER properties.
The starfish-shaped nickel-cobalt-sulfur transition metal sulfide obtained in the invention has a unique morphology which is beneficial to electron transfer and is also beneficial to the release of a gas product, thereby improving the catalytic performance and the electrochemical stability, and complex means such as heat treatment and the like are not needed in the preparation process. In addition, the nickel-cobalt-sulfur nano material synthesized by the nickel-cobalt molar ratio is firstly used for OER catalytic reaction.
The molar ratio of nickel to cobalt obtained in the invention is 1:4, the nickel-cobalt-sulfur catalyst shows excellent electrochemical performance, and the current density of the catalyst reaches 10mA/cm in the test process through OER test2The overpotential at this time was only 215mV, far exceeding the OER performance of commercially available ruthenium oxide.
The raw materials used in the preparation process are wide in source, environment-friendly and green, and high in safety. The preparation method is simple and convenient, and the obtained product is nontoxic, has better OER catalytic performance and has better prospect in large-scale application of replacing commercial electrocatalyst for electric driving water to generate oxygen in the future.
Drawings
FIG. 1 is a NiCo preparation of example 12S4-1:10 SEM image.
FIG. 2 shows the NiCo nickel cobalt sulfide NiCo prepared in example 22S4-1: XRD pattern of 4
FIG. 3 shows the NiCo nickel cobalt sulfide NiCo prepared in example 22S4-1: SEM and TEM images of 4.
FIG. 4 shows the NiCo nickel cobalt sulfide NiCo prepared in example 32S4-1:2 SEM image.
FIG. 5 shows NiCo with different ratios of Ni and Co2S4Linear Scan (LSV) plot of Oxygen Evolution Reaction (OER) under alkaline electrolyte.
Detailed Description
Instruments and reagents: the reagents used in the invention are all analytically pure, and the reagents are directly applied without special instructions and without any special treatment.
Cobalt nitrate hexahydrate (Co (NO)3)2·6H2O), nickel nitrate hexahydrate (Ni (NO)3)2·6H2O), urea (CH)4N2O), sodium sulfide nonahydrate (Na)2S·9H2O), nitric acid (HNO)3) Acetone, absolute ethyl alcohol and potassium hydroxide (KOH) are analytically pure and purchased from chemical reagents of national drug group, Inc.; carbon cloth [ HCP330N (hydrophilic), 0.32. + -. 0.02mm]Purchased from shanghai and sen electric limited.
Analytical balance (Precisa, XJ220A), stainless steel high-pressure hydrothermal reaction kettle, air-blast drying oven (shanghai sperm macro, DFG-9076A), vacuum drying oven (shanghai sperm macro, DZF-6090), electrochemical workstation (shanghai chenhua, CHI 760E).
Electrochemical testing: the electrocatalysis OER oxygen evolution performance test adopts a Shanghai Chenghua electrochemical workstation and a three-electrode test system, a carbon cloth loaded nickel-cobalt-sulfur nano catalyst is cut into 1cm multiplied by 1cm to be used as a working electrode, and a reversible hydrogen reference electrode and a graphite rod electrode are respectively used as a reference electrode and a counter electrode. At O2The electrochemical OER performance was tested in saturated 1.0M KOH solution to give an LSV curve at a sweep rate of 1 mV/s.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be fully described below with reference to the accompanying drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
The present invention will be described in detail with reference to specific examples.
Example 1
(1) Pretreatment of the carbon cloth: a large-size carbon cloth is cut into a proper size (3cm multiplied by 4cm) by an art designer knife and a ruler, the cut carbon cloth is put into a 50mL glass beaker and is cleaned for 30min by an ultrasonic instrument in acetone, distilled water and absolute ethyl alcohol in sequence, and the purpose of the step is to remove impurities on the surface of the carbon cloth. The carbon cloth after the ultrasonic cleaning treatment is placed in a nitric acid solution with the mass percentage concentration of 40%, the nitric acid solution is prepared by 68% concentrated nitric acid, the carbon cloth is subjected to oxidation treatment for 30min under the ultrasonic condition, and the nitric acid solution is replaced every 15min, so that the purposes of improving the wettability of the carbon cloth, reducing the contact angle, improving the surface energy of a substrate and better growing a catalyst are achieved.
(2) Preparing a nickel-cobalt hydroxide precursor: 1.4551g of cobalt nitrate hexahydrate (5mmol) was weighed into a 50mL glass beaker, 0.3003g of urea (5mmol) was weighed into the beaker, and finally 0.1454g of nickel nitrate hexahydrate (0.5mmol) was weighed into the 50mL beaker, wherein the molar ratio of nickel element to cobalt element was 1: 10. measuring 35mL of deionized water by using a measuring cylinder, adding the deionized water into a 50mL beaker, respectively adding magnetons, placing the beaker on a magnetic stirrer, and magnetically stirring the beaker at room temperature for 30min to dissolve the deionized water into a uniform solution; and (3) finally, transferring the stirred mixed solution into a 50mL stainless steel high-pressure hydrothermal reaction kettle, obliquely placing the carbon cloth processed in advance in the step (1) in the reaction kettle, soaking the carbon cloth in the reaction kettle, screwing a kettle cover, and placing the stainless steel high-pressure hydrothermal reaction kettle into an oven to react for 12 hours at 120 ℃.
(3) After the reaction is finished, after the high-pressure reaction kettle is cooled to room temperature, taking out the carbon cloth loaded with the product, respectively washing the carbon cloth with deionized water and ethanol for 3 times, and drying the carbon cloth in an oven for 6 hours at 60 ℃; obtaining the nickel-cobalt molar ratio of 1:10 nickel cobalt hydroxide precursor.
(4) 1.9135g of sodium sulfide nonahydrate (8mmol) is weighed into a 50mL glass beaker, 40mL of deionized water is weighed into the beaker by using a measuring cylinder, the mixture is mixed and dissolved at room temperature, after magnetons are added, the beaker is placed on a magnetic stirrer, and the mixture is magnetically stirred at room temperature for 30min to form a uniform clear solution.
(5) After stirring, transferring the clear solution obtained in the step (4) to a 60mL stainless steel high-pressure reaction kettle, and enabling the molar ratio of nickel and cobalt loaded in the step (2) to be 1:10, obliquely placing the carbon cloth of the nickel-cobalt hydroxide precursor in a reaction kettle, and finally placing the reaction kettle in an oven to react for 4 hours at 120 ℃.
(6) After the reaction is finished, after the reaction kettle is cooled to room temperature, taking out the carbon cloth, putting the carbon cloth into a beaker, respectively washing the carbon cloth for 3 times by deionized water and ethanol, and drying the carbon cloth in an oven for 6 hours at the temperature of 60 ℃. So as to obtain the nickel-cobalt molar ratio of 1:10 NiCo2S4Catalyst (noted NiCo)2S4-1：10)。
(7) Electrochemical OER performance testing: the test adopts a standard three-electrode test system, a reversible hydrogen reference electrode (RHE) is used as a reference electrode, a graphite rod is used as a counter electrode, and the prepared nickel-cobalt-sulfur catalyst is used as a working electrode. Cutting the catalyst-loaded carbon cloth prepared in the step (6) into sizes of 1cm multiplied by 1cm, taking two 25mL glass beakers, respectively adding 1.0M KOH solution and deionized water, putting the cut carbon cloth into the deionized water, soaking for 3-5 min, then clamping the carbon cloth by a carbon rod electrode clamp, and soaking for 3-5 min in the 1.0M KOH solution. At O2Electrochemical OER performance was tested in a 1.0M KOH solution as saturated electrolyte, and all data were obtained without iR compensation testing.
NiCo prepared in example 12S4-1:10 SEM of the drawing shown in FIG. 1, NiCo2S4The-1: 10 sulfide had a nanosheet structure, and the nanosheet surface was not smooth with some wrinkling. The OER performance of the catalyst is shown in FIG. 5 at a current density of 10mA/cm2At an overpotential of 300mV, but lower than that of the NiCo prepared in example 22S4Overpotential (215mV) of 1: 4.
Example 2
(1) Pretreatment of the carbon cloth: a large-size carbon cloth is cut into a proper size (3cm multiplied by 4cm) by an art designer knife and a ruler, the cut carbon cloth is put into a 50mL glass beaker and is cleaned for 30min by an ultrasonic instrument in acetone, distilled water and absolute ethyl alcohol in sequence, and the purpose of the step is to remove impurities on the surface of the carbon cloth. The carbon cloth after the ultrasonic cleaning treatment is placed in a nitric acid solution with the mass percentage concentration of 40%, the nitric acid solution is prepared by 68% concentrated nitric acid, the carbon cloth is subjected to oxidation treatment for 30min under the ultrasonic condition, and the nitric acid solution is replaced every 15min, so that the purposes of improving the wettability of the carbon cloth, reducing the contact angle, improving the surface energy of a substrate and better growing a catalyst are achieved.
(2) Preparing a nickel-cobalt hydroxide precursor: 1.4551g of cobalt nitrate hexahydrate (5mmol) was weighed into a 50mL glass beaker, 0.3003g of urea (5mmol) was weighed into the beaker, and 0.3634g of nickel nitrate hexahydrate (1.25mmol) was weighed into the 50mL beaker, wherein the molar ratio of nickel element to cobalt element was 1: 4. measuring 35mL of deionized water by using a measuring cylinder, adding the deionized water into a 50mL beaker, respectively adding magnetons, placing the beaker on a magnetic stirrer, and magnetically stirring the beaker at room temperature for 30min to dissolve the deionized water into a uniform solution; and (3) finally, transferring the stirred mixed solution into a 50mL stainless steel high-pressure hydrothermal reaction kettle, obliquely placing the carbon cloth processed in advance in the step (1) in the reaction kettle, soaking the carbon cloth in the reaction kettle, screwing a kettle cover, and placing the stainless steel high-pressure hydrothermal reaction kettle into an oven to react for 12 hours at 120 ℃.
(3) After the reaction is finished, after the high-pressure reaction kettle is cooled to room temperature, taking out the carbon cloth loaded with the product, respectively washing the carbon cloth with deionized water and ethanol for 3 times, and drying the carbon cloth in an oven for 6 hours at 60 ℃; obtaining the nickel-cobalt molar ratio of 1:4 nickel cobalt hydroxide precursor.
(4) 1.9135g of sodium sulfide nonahydrate (8mmol) is weighed into a 50mL glass beaker, 40mL of deionized water is weighed into the beaker by using a measuring cylinder, the mixture is mixed and dissolved at room temperature, after magnetons are added, the beaker is placed on a magnetic stirrer, and the mixture is magnetically stirred at room temperature for 30min to form a uniform clear solution.
(5) After stirring, transferring the clear solution obtained in the step (4) to a 60mL stainless steel high-pressure reaction kettle, and enabling the molar ratio of nickel and cobalt loaded in the step (2) to be 1:4, obliquely placing the carbon cloth of the nickel-cobalt hydroxide precursor in the reaction kettle, and finally placing the reaction kettle in an oven to react for 4 hours at 120 ℃.
(6) After the reaction is finished, after the reaction kettle is cooled to room temperature, taking out the carbon cloth, putting the carbon cloth into a beaker, respectively washing the carbon cloth for 3 times by deionized water and ethanol, and drying the carbon cloth in an oven for 6 hours at the temperature of 60 ℃. So as to obtain the nickel-cobalt molar ratio of 1:4 NiCo2S4Catalyst (noted NiCo)2S4-1：4)。
(7) Electrochemical OER performance testing: the test adopts a standard three-electrode test system, a reversible hydrogen reference electrode (RHE) is used as a reference electrode, a graphite rod is used as a counter electrode, and the prepared nickel-cobalt-sulfur catalyst is used as a working electrode. Cutting the catalyst-loaded carbon cloth prepared in the step (6) into sizes of 1cm multiplied by 1cm, taking two 25mL glass beakers, respectively adding 1.0M KOH solution and deionized water, putting the cut carbon cloth into the deionized water, soaking for 3-5 min, then clamping the carbon cloth by a carbon rod electrode clamp, and soaking for 3-5 min in the 1.0M KOH solution. At O2Electrochemical OER performance was tested in a 1.0M KOH solution as saturated electrolyte, and all data were obtained without iR compensation testing.
NiCo prepared in example 22S4-1:4, the XRD pattern of the nickel cobalt sulfide is shown in figure 2, the XRD diffraction peak of the nickel cobalt sulfide corresponds to PDF card being PDF #24-0334 and being NiCo with a spinel structure2S4. As shown in FIG. 3, NiCo2S4-1:4 has a shape similar to a starfish-shaped nanorod structure, uniformly grows on carbon cloth, is beneficial to the precipitation of gas products, and the OER performance test result of the catalyst is shown in figure 5, and the OER performance test result of the catalyst is that the current density is 10mA/cm2The overpotential of (A) is 215mV, far exceeding that of commercial RuO2OER catalytic performance (10 mA/cm)2At an overpotential of 321mV) and NiCo in other proportions2S4。
Example 3
(1) Pretreatment of the carbon cloth: a large-size carbon cloth is cut into a proper size (3cm multiplied by 4cm) by an art designer knife and a ruler, the cut carbon cloth is put into a 50mL glass beaker and is cleaned for 30min by an ultrasonic instrument in acetone, distilled water and absolute ethyl alcohol in sequence, and the purpose of the step is to remove impurities on the surface of the carbon cloth. The carbon cloth after the ultrasonic cleaning treatment is placed in a nitric acid solution with the mass percentage concentration of 40%, the nitric acid solution is prepared by 68% concentrated nitric acid, the carbon cloth is subjected to oxidation treatment for 30min under the ultrasonic condition, and the nitric acid solution is replaced every 15min, so that the purposes of improving the wettability of the carbon cloth, reducing the contact angle, improving the surface energy of a substrate and better growing a catalyst are achieved.
(2) Preparing a nickel-cobalt hydroxide precursor: 1.4551g of cobalt nitrate hexahydrate (5mmol) was weighed into a 50mL glass beaker, 0.3003g of urea (5mmol) was weighed into the beaker, and 0.7270g of nickel nitrate hexahydrate (2.5mmol) was weighed into the 50mL beaker, wherein the molar ratio of nickel element to cobalt element was 1: 2. measuring 35mL of deionized water by using a measuring cylinder, adding the deionized water into a 50mL beaker, respectively adding magnetons, placing the beaker on a magnetic stirrer, and magnetically stirring the beaker at room temperature for 30min to dissolve the deionized water into a uniform solution; and (3) finally, transferring the stirred mixed solution into a 50mL stainless steel high-pressure hydrothermal reaction kettle, obliquely placing the carbon cloth processed in advance in the step (1) in the reaction kettle, soaking the carbon cloth in the reaction kettle, screwing a kettle cover, and placing the stainless steel high-pressure hydrothermal reaction kettle into an oven to react for 12 hours at 120 ℃.
(3) After the reaction is finished, after the high-pressure reaction kettle is cooled to room temperature, taking out the carbon cloth loaded with the product, respectively washing the carbon cloth with deionized water and ethanol for 3 times, and drying the carbon cloth in an oven for 6 hours at 60 ℃; obtaining the nickel-cobalt molar ratio of 1:2 nickel cobalt hydroxide precursor.
(4) 1.9135g of sodium sulfide nonahydrate (8mmol) is weighed into a 50mL glass beaker, 40mL of deionized water is weighed into the beaker by using a measuring cylinder, the mixture is mixed and dissolved at room temperature, after magnetons are added, the beaker is placed on a magnetic stirrer, and the mixture is magnetically stirred at room temperature for 30min to form a uniform clear solution.
(5) After stirring, transferring the clear solution obtained in the step (4) to a 60mL stainless steel high-pressure reaction kettle, and enabling the molar ratio of nickel and cobalt loaded in the step (2) to be 1:2, obliquely placing the carbon cloth of the nickel-cobalt hydroxide precursor in the reaction kettle, and finally placing the reaction kettle in an oven to react for 4 hours at 120 ℃.
(6) After the reaction is finished, after the reaction kettle is cooled to room temperature, taking out the carbon cloth, putting the carbon cloth into a beaker, respectively washing the carbon cloth for 3 times by deionized water and ethanol, and drying the carbon cloth in an oven for 6 hours at the temperature of 60 ℃. So as to obtain the nickel-cobalt molar ratio of 1: NiCo of 22S4Catalyst (noted NiCo)2S4-1：2)。
(7) Electrochemical OER performance testing: standard three-electrode test body for testingThe system takes a reversible hydrogen reference electrode (RHE) as a reference electrode, a graphite rod as a counter electrode and a prepared nickel-cobalt-sulfur catalyst as a working electrode. Cutting the catalyst-loaded carbon cloth prepared in the step (6) into sizes of 1cm multiplied by 1cm, taking two 25mL glass beakers, respectively adding 1.0M KOH solution and deionized water, putting the cut carbon cloth into the deionized water, soaking for 3-5 min, then clamping the carbon cloth by a carbon rod electrode clamp, and soaking for 3-5 min in the 1.0M KOH solution. At O2Electrochemical OER performance was tested in a 1.0M KOH solution as saturated electrolyte, and all data were obtained without iR compensation testing.
NiCo prepared in example 32S4-1:2 SEM image as shown in FIG. 4, NiCo2S4The-1: 2 sulfide has the structure of nanowires, and there is some adhesion between the nanowires. The OER performance of the catalyst is shown in FIG. 5 at a current density of 10mA/cm2At an overpotential of 283mV, but lower than the NiCo prepared in example 22S4Overpotential (215mV) of 1: 4.
It should be understood that while the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein, and any combination of the various embodiments may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
Claims (9)
1. The preparation method of the nickel-cobalt-sulfur material is characterized by comprising the following specific steps of:
(1) carrying out ultrasonic cleaning and oxidation treatment on the carbon cloth to obtain a pretreated carbon cloth;
(2) respectively weighing cobalt nitrate hexahydrate, urea and nickel nitrate hexahydrate into a beaker, weighing deionized water by using a measuring cylinder, adding deionized water into the deionized water, magnetically stirring and dissolving the mixture uniformly at room temperature, transferring the mixed solution into a stainless steel high-pressure hydrothermal reaction kettle, soaking the carbon cloth treated in the step (1) into the reaction kettle, screwing a kettle cover, putting the stainless steel high-pressure hydrothermal reaction kettle into an oven, and reacting for 12 hours at 120 ℃ to obtain the carbon cloth loaded with a nickel-cobalt hydroxide precursor;
(3) after the reaction is finished, cooling the reaction kettle to room temperature, taking out the carbon cloth loaded with the product, washing and drying;
(4) weighing sodium sulfide nonahydrate, dissolving in deionized water, and magnetically stirring at room temperature to form a uniform clear solution;
(5) transferring the clear solution obtained in the step (4) into a stainless steel high-pressure reaction kettle, soaking the carbon cloth loaded with the nickel-cobalt hydroxide precursor prepared in the step (2) in the reaction kettle, and putting the reaction kettle into an oven to react for 4 hours at 120 ℃;
(6) after the reaction is finished, after the reaction kettle is cooled to room temperature, taking out the carbon cloth, washing and drying to obtain the nickel-cobalt-sulfur material.
2. The method for preparing a nickel-cobalt-sulfur material as claimed in claim 1, wherein in the step (1), the method for performing ultrasonic cleaning and oxidation treatment on the carbon cloth comprises the following steps: cutting the carbon cloth into blocks, carrying out ultrasonic cleaning in acetone, distilled water and absolute ethyl alcohol in sequence, placing the carbon cloth subjected to the ultrasonic cleaning treatment in a nitric acid solution, and carrying out oxidation treatment under the ultrasonic condition.
3. The method of claim 2, wherein the bulk size is 3cm x 4cm, and the ultrasonic cleaning time is 30 min; the mass percentage concentration of the nitric acid solution is 40%, and the oxidation treatment time is 30 min.
4. The method for preparing a nickel cobalt sulfur material as claimed in claim 1, wherein in step (2), the ratio of cobalt nitrate hexahydrate, urea, nickel nitrate hexahydrate and deionized water is 5 mmol: 5 mmol: 0.5-2.5 mmol: 35 mL; the magnetic stirring time is 30 min.
5. The method of claim 4, wherein the ratio of cobalt nitrate hexahydrate, urea, nickel nitrate hexahydrate and deionized water is 5 mmol: 5 mmol: 1.25 mmol: 35 mL.
6. The method for preparing Ni-Co-S material of claim 1 wherein in step (3), the washing step is carried out 3-5 times by using deionized water and absolute ethyl alcohol, and the drying step is carried out in an oven at 60 ℃ for 6 h.
7. The method of claim 1, wherein in step (4), the ratio of the sodium sulfide nonahydrate to the cobalt nitrate hexahydrate and the deionized water in step (2) is 8 mmol: 5 mmol: 40mL, magnetic stirring time is 30 min.
8. The method of claim 1, wherein in the step (6), the washing step is carried out 3-5 times by using deionized water and absolute ethyl alcohol respectively, and the drying step is carried out in an oven at 60 ℃ for 6 hours by air drying.
9. Use of the nickel cobalt sulfide material prepared by the preparation method of claims 1-8 as an electrocatalytic OER catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111090927.5A CN113832492A (en) | 2021-09-17 | 2021-09-17 | Nickel-cobalt-sulfur material, preparation method and application in electrocatalytic OER |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111090927.5A CN113832492A (en) | 2021-09-17 | 2021-09-17 | Nickel-cobalt-sulfur material, preparation method and application in electrocatalytic OER |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113832492A true CN113832492A (en) | 2021-12-24 |
Family
ID=78959729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111090927.5A Pending CN113832492A (en) | 2021-09-17 | 2021-09-17 | Nickel-cobalt-sulfur material, preparation method and application in electrocatalytic OER |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113832492A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114411132A (en) * | 2022-01-25 | 2022-04-29 | 安徽理工大学 | Preparation method of cobalt-nickel alloy particle hydrophilic carbon cloth composite material with corn cob-like heterostructure |
| CN114717586A (en) * | 2022-04-06 | 2022-07-08 | 苏州大学 | Nickel-cobalt-sulfur/nickel net composite hydrogen and oxygen evolution electrode and preparation method thereof |
| CN115094476A (en) * | 2022-07-11 | 2022-09-23 | 南京师范大学 | Co 9 S 8 /Co 3 S 4 /Cu 2 S hybrid nano material and preparation method and application thereof |
-
2021
- 2021-09-17 CN CN202111090927.5A patent/CN113832492A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114411132A (en) * | 2022-01-25 | 2022-04-29 | 安徽理工大学 | Preparation method of cobalt-nickel alloy particle hydrophilic carbon cloth composite material with corn cob-like heterostructure |
| CN114717586A (en) * | 2022-04-06 | 2022-07-08 | 苏州大学 | Nickel-cobalt-sulfur/nickel net composite hydrogen and oxygen evolution electrode and preparation method thereof |
| CN114717586B (en) * | 2022-04-06 | 2023-03-10 | 苏州大学 | Nickel-cobalt-sulfur/nickel net composite hydrogen and oxygen evolution electrode and preparation method thereof |
| CN115094476A (en) * | 2022-07-11 | 2022-09-23 | 南京师范大学 | Co 9 S 8 /Co 3 S 4 /Cu 2 S hybrid nano material and preparation method and application thereof |
| CN115094476B (en) * | 2022-07-11 | 2023-09-22 | 南京师范大学 | Co (cobalt) 9 S 8 /Co 3 S 4 /Cu 2 S-hybridized nano material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107376958B (en) | NiFeP difunctional transition metal phosphide catalyst and preparation and application thereof | |
| CN108554413B (en) | Three-dimensional multi-stage structure high-dispersion nickel-based electro-catalytic material and preparation method thereof | |
| CN110055557B (en) | Three-dimensional nickel-doped iron-based oxygen evolution catalyst and preparation method and application thereof | |
| CN111282582A (en) | Preparation method of foam nickel-based catalyst for hydrogen production by water electrolysis | |
| CN112023946A (en) | Preparation method of self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst | |
| CN109954503B (en) | Nickel selenide and ternary nickel-iron selenide composite electrocatalyst, preparation method and application | |
| CN113832492A (en) | Nickel-cobalt-sulfur material, preparation method and application in electrocatalytic OER | |
| CN110512228B (en) | Preparation method of nickel phosphide/nickel foam electrochemical functional hydrogen evolution material | |
| CN109628951B (en) | Nickel sulfide hydrogen evolution electrocatalyst and preparation method and application thereof | |
| CN108479808B (en) | 3D self-assembled flower ball-shaped vanadium modified Ni3S2Method of synthesis of | |
| CN113832478B (en) | Preparation method of high-current oxygen evolution reaction electrocatalyst with three-dimensional heterostructure | |
| CN109433228B (en) | Angular Ni with hierarchical structure3S2/VS4Electrode material and preparation method thereof | |
| CN110711590B (en) | One-dimensional cobalt-sulfur compound/cuprous sulfide compound nano-array @ foamy copper material and preparation method and application thereof | |
| CN110965076A (en) | Preparation method of electrolytic water electrode with double-function three-dimensional layered core-shell structure | |
| CN114289043B (en) | Preparation method and application of self-supporting porous nano-plate cobalt-nickel phosphide catalyst | |
| CN111939947B (en) | Preparation method of nanosheet array electrocatalyst | |
| CN110624540A (en) | Novel ruthenium-based self-supporting electro-catalytic material, preparation method thereof and application thereof in electro-catalytic nitrogen reduction for producing ammonia | |
| CN114892206B (en) | Multi-metal nitride heterojunction nanorod array composite electrocatalyst and preparation method and application thereof | |
| CN111036307B (en) | Preparation method of composite efficient oxygen evolution catalyst | |
| CN110013855B (en) | High-efficiency cobalt nickel oxide/nickel hydroxide compound electrocatalyst and preparation method and application thereof | |
| CN111118564B (en) | Nickel-nickel oxide ultrathin nanosheet material and electrodeposition preparation method and application thereof | |
| CN110354870B (en) | Preparation method and application of high-performance silver-doped cobalt sulfide oxygen evolution catalyst | |
| CN110586196B (en) | Preparation method of FeOOH @ Ni-BDC water electrolysis catalyst | |
| CN117107289A (en) | Kennel-shaped nickel cobaltate@iron oxyhydroxide hierarchical nano-array catalyst material | |
| CN115611324B (en) | Nickel-cobalt bimetallic base submicron flower cluster and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |