CN108315762B - Synthesis method of Ni-Mo-Co hydrogen evolution catalyst with high activity in acidic environment - Google Patents
Synthesis method of Ni-Mo-Co hydrogen evolution catalyst with high activity in acidic environment Download PDFInfo
- Publication number
- CN108315762B CN108315762B CN201810128410.2A CN201810128410A CN108315762B CN 108315762 B CN108315762 B CN 108315762B CN 201810128410 A CN201810128410 A CN 201810128410A CN 108315762 B CN108315762 B CN 108315762B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hydrogen evolution
- electroplating solution
- template
- nickel
- 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.)
- Active
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
-
- 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
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- 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
Abstract
The invention discloses a synthesis method of a Ni-Mo-Co hydrogen evolution catalyst with high activity in an acidic environment, which comprises the following steps: (1) preparing a catalyst electroplating solution; (2) cleaning a substrate; (3) preparing template electrolyte; (4) manufacturing a template; (5) reprocessing the catalyst electroplating solution; (6) the catalyst is deposited. The method has low cost, simple operation and short period, and the prepared hydrogen evolution catalyst can obviously reduce the hydrogen evolution overpotential, and is especially obvious in an acid environment.
Description
Technical Field
The invention belongs to the field of synthesis of hydrogen evolution catalysts, and particularly relates to a synthesis method of a Ni-Mo-Co catalyst with high hydrogen evolution performance in an acidic environment.
Background
Water (H)2O) the process of generating hydrogen and oxygen by direct current electrolysis is called electrolysis of water. The current flows through the water (H)2O), reduction reaction occurs at the cathode to generate hydrogen (H)2) At the anode, the oxidation reaction of water to form oxygen (O)2). Because of less energy consumption and low cost, the hydrogen evolution by electrolyzing water is an important method for preparing hydrogen fuel by replacing steam reforming.
Although the hydrogen evolution reaction is considered to be the simplest electrochemical reaction, there are some limiting factors in the actual hydrogen production process for improvement:
in theory, an external voltage of 1.23V is applied sufficient to cause the water to undergo a decomposition reaction. However, due to each of the reaction systemsThe commercial electrolyzers usually work under the voltage condition of 1.8-2.0V, which is far higher than the theoretical value of 1.23V, and the operation efficiency is low, thereby deriving the concept of overpotential (η), namely overcoming the overpotential of the anode (η)a) And cathode overpotential (η)c) Intrinsic activation barrier, and other overpotentials (η)other) Potentials beyond the theoretical thermodynamic voltage, including solution resistance and contact resistance. Therefore, the voltage (E) necessary for the practical operation of water electrolysisopV) can be represented by the following formula:
EOP= 1.23+ηa+ηc+ηother
from the above formula, it can be seen that in order to promote the water decomposition reaction to occur more energy-saving and more efficient, it is the core problem to adopt appropriate method to reduce the over-potential of the reactionotherHowever, η can only be reduced by using highly active Oxygen Evolution (OER) and Hydrogen Evolution (HER) catalystsaAnd ηcThe numerical value of (c).
The existing hydrogen evolution catalysts are classified into noble metal catalysts and non-noble metal catalysts according to the storage amount of metal elements in the catalysts in nature. Wherein the Pt group noble metal has quite high hydrogen evolution catalytic activity and the performance of the Pt group noble metal is 10mA/cm2Only about 30mV of overpotential is required for the current density of (1). However, the Pt group noble metal catalyst has a small storage capacity and a high price, and cannot meet the actual demand of large-scale hydrogen production, so many researches have been focused in recent years on how to further improve the hydrogen evolution performance of the existing non-noble metal catalyst or develop a novel catalyst with low price and high efficiency.
Non-noble metal catalysts have been studied in recent years and mainly include metal phosphides (nickel phosphide, cobalt phosphide, iron phosphide, molybdenum phosphide, tungsten phosphide, etc.), nitrides (Ni-Mo binary alloy nitrides, tungsten nitride nanorod arrays), carbides (molybdenum carbide, tungsten carbide, etc.), sulfides, selenides, and alloysAnd the more excellent iron phosphide nanowire array is grown on carbon cloth at 10mA/cm2When the over-potential is required to be 58mV, the Tafel slope is 45 mV/dec.
In the research on alloy-based hydrogen evolution catalysts, nickel-based alloys have been receiving attention from researchers due to their good catalytic activity. Researches find that the overpotential of the ternary non-noble metal catalyst prepared by introducing a third non-noble metal element on the basis of the traditional binary non-noble metal catalyst can be effectively reduced in the hydrogen evolution reaction process. At present, the catalytic performances of the most researched catalysts comprise Ni-Mo-Co, Ni-Mo-Zn and the like, which are all excellent, but the catalytic activities of the existing prepared ternary non-noble metal catalyst and a noble metal catalyst are still different; meanwhile, when the current density is increased, the increase amplitude of the hydrogen evolution overpotential is quite obvious. Therefore, it is of great significance to research how to further improve the activity of such catalysts.
The existing method for preparing the alloy hydrogen evolution catalyst mainly comprises a hydrothermal method and an electrodeposition method, and the microstructure of the catalyst can be greatly influenced and the activity of the catalyst can be further influenced due to different preparation methods and processes; on the other hand, because the overpotential ratio is relatively high in an acidic environment due to another half reaction of water electrolysis, in the current industrial application, water electrolysis is generally performed in an alkaline environment in order to reduce the production cost, however, in order to meet the requirements of various industrial production, the research on the 'full-pH' catalyst is more and more important, and because many existing hydrogen evolution catalysts are unstable in an acidic condition, the activity and stability of the catalyst in an acidic environment are important considerations in the research process.
Disclosure of Invention
The invention aims to provide a synthesis method of a Ni-Mo-Co hydrogen evolution catalyst with high activity in an acidic environment, the method has the advantages of low cost, simple operation and short period, and the prepared hydrogen evolution catalyst can obviously reduce hydrogen evolution overpotential, and is especially obvious in the acidic environment.
The invention is realized by the following technical scheme:
a synthetic method of a Ni-Mo-Co hydrogen evolution catalyst with high activity in an acidic environment comprises the following steps:
(1) preparing a catalyst electroplating solution, adding chemical reagents serving as a nickel source, a molybdenum source and a cobalt source into a clean beaker, dissolving the beaker in deionized water, adding sodium pyrophosphate decahydrate and sodium bicarbonate, and stirring the solution by using a magnetic stirrer to prepare the catalyst electroplating solution;
(2) cleaning a substrate, shearing foamed nickel, putting the foamed nickel under concentrated sulfuric acid for ultrasonic treatment to remove dust, and cleaning with a cleaning solution to remove dirt after the ultrasonic treatment is finished to obtain a clean foamed nickel substrate;
(3) preparing a template electroplating solution, dissolving nickel salt in deionized water, adding ammonium chloride and sodium chloride, and stirring for 1-3 hours by using a magnetic stirrer to prepare the template electroplating solution;
(4) preparing a template, taking the clean foam nickel substrate obtained in the step (2), soaking the clean foam nickel substrate in the template electroplating solution prepared in the step (3), depositing by adopting an electrodeposition method by taking nickel ions in the template electroplating solution as deposits, regulating and controlling to form a template with a coral-shaped, spherical accumulation-shaped or pine-shaped appearance, and placing the template in a refrigerator for refrigeration;
(5) reprocessing the catalyst electroplating solution, adding a reducing agent into the catalyst electroplating solution prepared in the step (1), and stirring by using a magnetic stirrer;
(6) and (4) dipping the template prepared in the step (4) into the catalyst electroplating solution treated in the step (5) by using a pulse current method for electrodeposition to obtain the Ni-Mo-Co hydrogen evolution catalyst with compact and flat surface and high activity.
In the catalyst electroplating solution in the step (1), the sodium pyrophosphate decahydrate and the sodium bicarbonate are used for adjusting the pH value and the resistivity of the catalyst electroplating solution, the pH value of the catalyst electroplating solution is about 6.0-9.0, and the resistivity is about 7-20 kilo-ohm cm; similarly, in the template electroplating solution in the step (3), the ammonium chloride and the sodium chloride are used for adjusting the pH value and the resistivity of the template electroplating solution, the pH value of the template electroplating solution is about 4.0-7.0, and the resistivity is about 0.5-5 kilo-ohm cm.
Preferably, in the step (1) of the present invention, the nickel source is nickel chloride hexahydrate with a dissolved concentration of 25-45 mmol/L, the molybdenum source is sodium molybdate dihydrate with a dissolved concentration of 8-35 mmol/L, the cobalt source is cobalt nitrate hexahydrate with a dissolved concentration of 12-42 mmol/L, the dissolved concentration of sodium pyrophosphate decahydrate is 60-100 mmol/L, and the dissolved concentration of sodium bicarbonate is 450-1500 mmol/L.
Preferably, in the step (1) of the present invention, the stirring time by using a magnetic stirrer is 3 to 5 hours, and after the stirring is completed, the catalyst electroplating solution is left to stand in an air atmosphere for 1 to 10 days. The catalyst electroplating solution is supersaturated solution at the beginning of preparation, standing is favorable for enabling the solute of the catalyst electroplating solution to be dispersed more uniformly and enabling undissolved solute in the solution to be precipitated, and experiments prove that the Ni-Mo-Co hydrogen evolution catalyst prepared by using the catalyst electroplating solution which is kept standing has better activity.
Preferably, the ultrasonic treatment in step (2) of the invention has a power of 300-500W and an ultrasonic time of 3-10 minutes, and the cleaning agent is deionized water, absolute ethyl alcohol and acetone, and the substrate is cleaned by adopting an alternate cleaning mode. After the cleaning in the mode, impurities such as oxides, oily substances and the like on the surface of the substrate can be effectively removed, and the influence of the impurities on the effect of electrodeposition is avoided.
Preferably, the nickel salt in the step (3) of the present invention is nickel chloride hexahydrate with a dissolved concentration of 40-250 mmol/L, the dissolved concentration of ammonium chloride is 300-1000 mmol/L, and the dissolved concentration of sodium chloride is 500-2500 mmol/L.
Preferably, the electrodeposition method in the step (4) of the invention adopts a cathode deposition current of 0.5-2.5A, and the refrigeration process is carried out under the conditions of-20-0 ℃ for 1-3 days. And the cold storage is carried out after the electrodeposition, which is beneficial to the growth of crystals on the surface of the substrate.
The template with the coral-shaped, spherical accumulation-shaped or pine-shaped appearance is prepared by depositing nickel on the clean foamed nickel substrate, so that the real specific surface area of the template surface is effectively increased, and more sites are provided for the deposition growth of metal on the template surface in the subsequent electrodeposition process.
Preferably, the reducing agent in the step (5) of the invention is hydrazine hydrate, and the hydrazine hydrate is added dropwise until the concentration is 0.5-3 ml/L, and the stirring time is 5-10 minutes. The hydrazine hydrate has strong reducibility, and is more beneficial to the subsequent electrodeposition.
Preferably, the pulse current method in step (6) of the invention adopts square wave pulse, the duty ratio of the pulse current is 0.2-0.7, the period is 3-7 seconds, and the current density is 50-300 mA/cm2And (3) 500-1500 cycles in total, wherein the temperature in the electrodeposition process is controlled to be 20-50 ℃. The hydrogen evolution catalyst prepared by electrodeposition under the condition has compact and flat surface and shows high activity in hydrogen evolution reaction.
The invention has the following beneficial effects:
1. the synthesis method of the Ni-Mo-Co hydrogen evolution catalyst with high activity in the acidic environment has the advantages of low cost, simple operation and short period, is beneficial to industrialization, reduces production investment after being applied to industrial production, and simplifies production process flow;
2. the invention optimizes the activity and microstructure of the catalyst by combining template manufacture and a pulse current method to form the catalyst between a polycrystalline state and an amorphous state, thereby effectively improving the activity of the catalyst in hydrogen evolution reaction;
3. the Ni-Mo-Co hydrogen evolution catalyst prepared by the method has good catalytic activity in the full pH value range, can effectively reduce the overpotential in the hydrogen evolution reaction, is particularly obvious in an acidic environment, has stable performance in the acidic environment, and can meet the requirements of different researches and industrial production;
4. the hydrogen evolution catalyst has stable performance under the condition of high pressure, and the current density is even higher than that of a noble metal Pt/C catalyst under the condition of high overpotential, namely the performance is more excellent;
5. the gradient of the hydrogen evolution catalyst is small, is only 35 mA/dec, and has a current density of 10mA/cm2、100 mA/cm2、1000 mA/cm2、3000 mA/cm2When the catalyst is used, the required overpotentials are respectively only 24mV, 70 mV, 170 mV and 330mV, which are much lower than that of the prior similar catalyst.
Drawings
FIG. 1 is a schematic view of the apparatus for manufacturing the template in step (4);
FIG. 2 is a schematic view of the apparatus for depositing the catalyst in the step (6);
FIG. 3 is a linear scan graph of the Ni-Mo-Co hydrogen evolution catalyst prepared in example 4 before and after stability testing;
FIG. 4 is a constant voltage graph (with an overpotential set at-65 mV) of a stability test of the Ni-Mo-Co hydrogen evolution catalyst prepared in example 4;
FIG. 5 is a linear scan plot of the Ni-Mo-Co hydrogen evolution catalyst prepared in example 4 at high overpotential;
FIG. 6 is a 1100 times scanning electron microscope of the Ni-Mo-Co hydrogen evolution catalyst prepared in example 4;
FIG. 7 is a 2000-fold electron micrograph of the Ni-Mo-Co hydrogen evolution catalyst prepared in example 4.
The reference numbers are as follows: 1-a wire; 2-platinum wire; 3-platinum sheet electrode clamp; 4-clean foamed nickel substrate; 5-an adjustable power supply; 6-template electroplating solution; 7-beaker; 8-template; 9-catalyst plating solution.
Detailed Description
The invention is illustrated in detail below by means of specific examples:
example 1
(1) Preparing a catalyst electroplating solution, namely adding chemical reagents serving as a nickel source, a molybdenum source and a cobalt source into a clean beaker, and dissolving the beaker in deionized water, wherein the prepared catalyst electroplating solution comprises the following components: 30mmol/L nickel chloride hexahydrate, 8mmol/L sodium molybdate dihydrate, 25mmol/L cobalt nitrate hexahydrate, 100mmol/L sodium pyrophosphate decahydrate and 1300mmol/L sodium bicarbonate; stirring for 4 hours by using a magnetic stirrer, and standing the catalyst electroplating solution in an air atmosphere for 3 days;
(2) cleaning a substrate, cutting 1 × 1cm of foamed nickel, putting the foamed nickel into concentrated sulfuric acid, performing ultrasonic treatment for 7 minutes at the power of 300w, and cleaning and decontaminating the foamed nickel by using deionized water, absolute ethyl alcohol and acetone alternately after the ultrasonic treatment is finished to obtain a clean foamed nickel substrate;
(3) preparing a template electroplating solution, namely preparing the template electroplating solution with the following components by using deionized water: 120mmol/L nickel chloride hexahydrate, 700mmol/L ammonium chloride and 1000mmol/L sodium chloride; stirring for 1 hour by adopting magnetic force;
(4) manufacturing a template as shown in figure 1, taking a platinum wire as a positive electrode, clamping the clean foamed nickel substrate obtained in the step (2) by a platinum sheet electrode clamp as a negative electrode, soaking the platinum wire into the template electroplating solution prepared in the step (3), connecting an adjustable power supply, depositing under the condition of 1.0A cathode deposition current by adopting an electrodeposition method, regulating and controlling to form the template with a coral-shaped, spherical accumulation-shaped or pine-shaped appearance, placing the template in a refrigerator, and refrigerating for 1 day at the temperature of-20 ℃;
(5) retreatment of catalyst electroplating solution hydrazine hydrate is dripped into the catalyst electroplating solution prepared in the step (1) until the concentration of the hydrazine hydrate is 0.50mol/L, and a magnetic stirrer is used for stirring for 8 minutes;
(6) and (3) as shown in figure 2, soaking a platinum wire serving as a positive electrode and a platinum sheet electrode clamp clamping the template prepared in the step (4) serving as a negative electrode in the catalyst electroplating solution treated in the step (5), connecting an adjustable power supply, and adopting a pulse current method to perform pulse current at the current density of 300mA/cm2And carrying out electrodeposition under the conditions that the duty ratio is 0.2, the period is 4 seconds, the cycle number is 1000 and the temperature is 20 ℃ to obtain the Ni-Mo-Co hydrogen evolution catalyst with compact and flat surface and high activity.
Example 2
(1) Preparing a catalyst electroplating solution, namely adding chemical reagents serving as a nickel source, a molybdenum source and a cobalt source into a clean beaker, and dissolving the beaker in deionized water, wherein the prepared catalyst electroplating solution comprises the following components: 25mmol/L nickel chloride hexahydrate, 20mmol/L sodium molybdate dihydrate, 18mmol/L cobalt nitrate hexahydrate, 75mmol/L sodium pyrophosphate decahydrate and 1500mmol/L sodium bicarbonate; stirring for 5 hours by using a magnetic stirrer, and standing the catalyst electroplating solution in an air atmosphere for 5 days;
(2) cleaning a substrate, cutting 1 × 1cm of foamed nickel, putting the foamed nickel into concentrated sulfuric acid, performing ultrasonic treatment for 3 minutes at the power of 450w, and cleaning and decontaminating the foamed nickel by using deionized water, absolute ethyl alcohol and acetone alternately after the ultrasonic treatment is finished to obtain a clean foamed nickel substrate;
(3) preparing a template electroplating solution, namely preparing the template electroplating solution with the following components by using deionized water: 40mmol/L nickel chloride hexahydrate, 400mmol/L ammonium chloride and 1200mmol/L sodium chloride; stirring for 3 hours by adopting magnetic force;
(4) manufacturing a template as shown in figure 1, taking a platinum wire as a positive electrode, clamping the clean foamed nickel substrate obtained in the step (2) by a platinum sheet electrode clamp as a negative electrode, soaking the platinum wire into the template electroplating solution prepared in the step (3), connecting an adjustable power supply, depositing under the condition of 2.5A cathode deposition current by adopting an electrodeposition method, regulating and controlling to form the template with a coral-shaped, spherical accumulation-shaped or pine-shaped appearance, placing the template in a refrigerator, and refrigerating for 3 days at-10 ℃;
(5) retreatment of the catalyst electroplating solution, dropwise adding hydrazine hydrate into the catalyst electroplating solution prepared in the step (1) until the concentration of the hydrazine hydrate is 2.60mol/L, and stirring for 10 minutes by using a magnetic stirrer;
(6) and (3) as shown in figure 2, soaking a platinum wire serving as a positive electrode and a platinum sheet electrode clamp clamping the template prepared in the step (4) serving as a negative electrode in the catalyst electroplating solution treated in the step (5), connecting an adjustable power supply, and adopting a pulse current method to perform pulse current at a current density of 100mA/cm2And carrying out electrodeposition under the conditions that the duty ratio is 0.5, the period is 6 seconds, the cycle number is 1500 and the temperature is 35 ℃ to obtain the Ni-Mo-Co hydrogen evolution catalyst with compact and flat surface and high activity.
Example 3
(1) Preparing a catalyst electroplating solution, namely adding chemical reagents serving as a nickel source, a molybdenum source and a cobalt source into a clean beaker, and dissolving the beaker in deionized water, wherein the prepared catalyst electroplating solution comprises the following components: 35mmol/L nickel chloride hexahydrate, 25mmol/L sodium molybdate dihydrate, 12mmol/L cobalt nitrate hexahydrate, 80mmol/L sodium pyrophosphate decahydrate and 600mmol/L sodium bicarbonate; stirring for 5 hours by using a magnetic stirrer, and standing the catalyst electroplating solution in an air atmosphere for 7 days;
(2) cleaning a substrate, cutting 1 × 1cm of foamed nickel, putting the foamed nickel into concentrated sulfuric acid, performing ultrasonic treatment for 5 minutes at the power of 500w, and cleaning and decontaminating the foamed nickel by using deionized water, absolute ethyl alcohol and acetone alternately after the ultrasonic treatment is finished to obtain a clean foamed nickel substrate;
(3) preparing a template electroplating solution, namely preparing the template electroplating solution with the following components by using deionized water: 200mmol/L nickel chloride hexahydrate, 1000mmol/L ammonium chloride and 500mmol/L sodium chloride; stirring for 2 hours by adopting magnetic force;
(4) manufacturing a template as shown in figure 1, taking a platinum wire as a positive electrode, clamping the clean foamed nickel substrate obtained in the step (2) by a platinum sheet electrode clamp as a negative electrode, soaking the platinum wire into the template electroplating solution prepared in the step (3), connecting an adjustable power supply, depositing under the condition of 0.5A cathode deposition current by adopting an electrodeposition method, regulating and controlling to form the template with a coral-shaped, spherical accumulation-shaped or pine-shaped appearance, placing the template in a refrigerator, and refrigerating for 3 days at the temperature of 0 ℃;
(5) retreatment of catalyst electroplating solution hydrazine hydrate is dripped into the catalyst electroplating solution prepared in the step (1) until the concentration of the hydrazine hydrate is 0.70mol/L, and a magnetic stirrer is used for stirring for 5 minutes;
(6) and (3) as shown in figure 2, soaking a platinum wire serving as a positive electrode and a platinum sheet electrode clamp clamping the template prepared in the step (4) serving as a negative electrode in the catalyst electroplating solution treated in the step (5), connecting an adjustable power supply, and adopting a pulse current method to perform pulse current at a current density of 50mA/cm2And carrying out electrodeposition under the conditions that the duty ratio is 0.3, the period is 5 seconds, the cycle number is 500 and the temperature is 40 ℃ to obtain the Ni-Mo-Co hydrogen evolution catalyst with compact and flat surface and high activity.
Example 4
(1) Preparing a catalyst electroplating solution, namely adding chemical reagents serving as a nickel source, a molybdenum source and a cobalt source into a clean beaker, and dissolving the beaker in deionized water, wherein the prepared catalyst electroplating solution comprises the following components: 43mmol/L nickel chloride hexahydrate, 30mmol/L sodium molybdate dihydrate, 30mmol/L cobalt nitrate hexahydrate, 70mmol/L sodium pyrophosphate decahydrate and 800mmol/L sodium bicarbonate; stirring for 3 hours by using a magnetic stirrer, and standing the catalyst electroplating solution in an air atmosphere for 10 days;
(2) cleaning a substrate, cutting 1 × 1cm of foamed nickel, putting the foamed nickel into concentrated sulfuric acid, performing ultrasonic treatment for 10 minutes at 350w power, and cleaning and decontaminating by using deionized water, absolute ethyl alcohol and acetone alternately after the ultrasonic treatment is finished to obtain a clean foamed nickel substrate;
(3) preparing a template electroplating solution, namely preparing the template electroplating solution with the following components by using deionized water: 180mmol/L nickel chloride hexahydrate, 600mmol/L ammonium chloride and 1500mmol/L sodium chloride; stirring for 3 hours by adopting magnetic force;
(4) manufacturing a template as shown in figure 1, taking a platinum wire as a positive electrode, clamping the clean foamed nickel substrate obtained in the step (2) by a platinum sheet electrode clamp as a negative electrode, soaking the platinum wire into the template electroplating solution prepared in the step (3), connecting an adjustable power supply, depositing under the condition of 2.0A cathode deposition current by adopting an electrodeposition method, regulating and controlling to form the template with a coral-shaped, spherical accumulation-shaped or pine-shaped appearance, placing the template in a refrigerator, and refrigerating for 1 day at-15 ℃;
(5) retreatment of catalyst electroplating solution hydrazine hydrate is dripped into the catalyst electroplating solution prepared in the step (1) until the concentration of the hydrazine hydrate is 3.00mol/L, and a magnetic stirrer is used for stirring for 9 minutes;
(6) and (3) as shown in figure 2, soaking a platinum wire serving as a positive electrode and a platinum sheet electrode clamp clamping the template prepared in the step (4) serving as a negative electrode in the catalyst electroplating solution treated in the step (5), connecting an adjustable power supply, and adopting a pulse current method to perform pulse current at a current density of 150mA/cm2And carrying out electrodeposition under the conditions that the duty ratio is 0.7, the period is 3 seconds, the cycle number is 700 and the temperature is 50 ℃ to obtain the Ni-Mo-Co hydrogen evolution catalyst with compact and flat surface and high activity.
The electrical analysis of the Ni-Mo-Co hydrogen evolution catalyst prepared in this example is performed, and the results are shown in fig. 3 to 5, and fig. 3 and 4 show the excellent performance of the Ni-Mo-Co hydrogen evolution catalyst under low overpotential and the comparison before and after 6000 seconds stability test, and fig. 5 shows that under the same overpotential condition, the Ni-Mo-Co hydrogen evolution catalyst shows a higher current density, i.e. a higher catalytic activity, than the similar catalyst;
the surface of the obtained Ni-Mo-Co hydrogen evolution catalyst was enlarged by an electron microscope, and as a result, as shown in fig. 6 and 7, the Ni-Mo-Co hydrogen evolution catalyst obtained by the method of the present invention had a surface microstructure having a high specific area such as a coral shape, a spherical heap shape, or a pine shape.
Example 5
(1) Preparing a catalyst electroplating solution, namely adding chemical reagents serving as a nickel source, a molybdenum source and a cobalt source into a clean beaker, and dissolving the beaker in deionized water, wherein the prepared catalyst electroplating solution comprises the following components: 40mmol/L nickel chloride hexahydrate, 35mmol/L sodium molybdate dihydrate, 40mmol/L cobalt nitrate hexahydrate, 60mmol/L sodium pyrophosphate decahydrate and 450mmol/L sodium bicarbonate; stirring for 3 hours by using a magnetic stirrer, and standing the catalyst electroplating solution in an air atmosphere for 4 days;
(2) cleaning a substrate, cutting 1 × 1cm of foamed nickel, putting the foamed nickel into concentrated sulfuric acid, performing ultrasonic treatment for 4 minutes at 400w power, and cleaning and decontaminating the foamed nickel by using deionized water, absolute ethyl alcohol and acetone alternately after the ultrasonic treatment is finished to obtain a clean foamed nickel substrate;
(3) preparing a template electroplating solution, namely preparing the template electroplating solution with the following components by using deionized water: 80mmol/L nickel chloride hexahydrate, 500mmol/L ammonium chloride and 1800mmol/L sodium chloride; stirring for 2 hours by adopting magnetic force;
(4) manufacturing a template as shown in figure 1, taking a platinum wire as a positive electrode, clamping the clean foamed nickel substrate obtained in the step (2) by a platinum sheet electrode clamp as a negative electrode, soaking the platinum wire into the template electroplating solution prepared in the step (3), connecting an adjustable power supply, depositing under the condition of 1.5A cathode deposition current by adopting an electrodeposition method, regulating and controlling to form the template with a coral-shaped, spherical accumulation-shaped or pine-shaped appearance, placing the template in a refrigerator, and refrigerating for 2 days at the temperature of-5 ℃;
(5) retreatment of catalyst electroplating solution hydrazine hydrate is dripped into the catalyst electroplating solution prepared in the step (1) until the concentration of the hydrazine hydrate is 1.20mol/L, and a magnetic stirrer is used for stirring for 6 minutes;
(6) and (3) as shown in figure 2, soaking a platinum wire serving as a positive electrode and a platinum sheet electrode clamp clamping the template prepared in the step (4) serving as a negative electrode in the catalyst electroplating solution treated in the step (5), connecting an adjustable power supply, and adopting a pulse current method to perform pulse current at a current density of 250mA/cm2And carrying out electrodeposition under the conditions that the duty ratio is 0.6, the period is 7 seconds, the cycle number is 1300 and the temperature is 25 ℃ to obtain the Ni-Mo-Co hydrogen evolution catalyst with compact and flat surface and high activity.
Example 6
(1) Preparing a catalyst electroplating solution, namely adding chemical reagents serving as a nickel source, a molybdenum source and a cobalt source into a clean beaker, and dissolving the beaker in deionized water, wherein the prepared catalyst electroplating solution comprises the following components: 32mmol/L nickel chloride hexahydrate, 12mmol/L sodium molybdate dihydrate, 42mmol/L cobalt nitrate hexahydrate, 85mmol/L sodium pyrophosphate decahydrate and 900mmol/L sodium bicarbonate; stirring for 5 hours by using a magnetic stirrer, and standing the catalyst electroplating solution in an air atmosphere for 8 days;
(2) cleaning a substrate, cutting 1 × 1cm of foamed nickel, putting the foamed nickel into concentrated sulfuric acid, performing ultrasonic treatment for 8 minutes at 330w power, and cleaning and decontaminating the foamed nickel substrate alternately by using deionized water, absolute ethyl alcohol and acetone after the ultrasonic treatment is finished to obtain a clean foamed nickel substrate;
(3) preparing a template electroplating solution, namely preparing the template electroplating solution with the following components by using deionized water: 250mmol/L nickel chloride hexahydrate, 300mmol/L ammonium chloride and 2500mmol/L sodium chloride; stirring for 1 hour by adopting magnetic force;
(4) manufacturing a template as shown in figure 1, taking a platinum wire as a positive electrode, clamping the clean foamed nickel substrate obtained in the step (2) by a platinum sheet electrode clamp as a negative electrode, soaking the platinum wire into the template electroplating solution prepared in the step (3), connecting an adjustable power supply, depositing under the condition of 1.2A cathode deposition current by adopting an electrodeposition method, regulating and controlling to form the template with a coral-shaped, spherical accumulation-shaped or pine-shaped appearance, placing the template in a refrigerator, and refrigerating for 1 day at-15 ℃;
(5) retreatment of the catalyst electroplating solution, dropwise adding hydrazine hydrate into the catalyst electroplating solution prepared in the step (1) until the concentration of the hydrazine hydrate is 2.00mol/L, and stirring for 5 minutes by using a magnetic stirrer;
(6) and (3) as shown in figure 2, soaking a platinum wire serving as a positive electrode and a platinum sheet electrode clamp clamping the template prepared in the step (4) serving as a negative electrode in the catalyst electroplating solution treated in the step (5), connecting an adjustable power supply, and adopting a pulse current method to perform pulse current at the current density of 200mA/cm2And carrying out electrodeposition under the conditions that the duty ratio is 0.4, the period is 4 seconds, the cycle number is 1100 and the temperature is 45 ℃ to obtain the Ni-Mo-Co hydrogen evolution catalyst with compact and flat surface and high activity.
Example 7
(1) Preparing a catalyst electroplating solution, namely adding chemical reagents serving as a nickel source, a molybdenum source and a cobalt source into a clean beaker, and dissolving the beaker in deionized water, wherein the prepared catalyst electroplating solution comprises the following components: 45mmol/L nickel chloride hexahydrate, 17mmol/L sodium molybdate dihydrate, 35mmol/L cobalt nitrate hexahydrate, 90mmol/L sodium pyrophosphate decahydrate and 1000mmol/L sodium bicarbonate; stirring for 4 hours by using a magnetic stirrer, and standing the catalyst electroplating solution in an air atmosphere for 1 day;
(2) cleaning a substrate, cutting 1 × 1cm of foamed nickel, putting the foamed nickel into concentrated sulfuric acid, performing ultrasonic treatment for 6 minutes at 470w power, and cleaning and decontaminating the foamed nickel substrate alternately by using deionized water, absolute ethyl alcohol and acetone after the ultrasonic treatment is finished to obtain a clean foamed nickel substrate;
(3) preparing a template electroplating solution, namely preparing the template electroplating solution with the following components by using deionized water: 220mmol/L nickel chloride hexahydrate, 800mmol/L ammonium chloride and 2000mmol/L sodium chloride; stirring for 3 hours by adopting magnetic force;
(4) manufacturing a template as shown in figure 1, taking a platinum wire as a positive electrode, clamping the clean foamed nickel substrate obtained in the step (2) by a platinum sheet electrode clamp as a negative electrode, soaking the platinum wire into the template electroplating solution prepared in the step (3), connecting an adjustable power supply, depositing under the condition of 2.2A cathode deposition current by adopting an electrodeposition method, regulating and controlling to form the template with a coral-shaped, spherical accumulation-shaped or pine-shaped appearance, placing the template in a refrigerator, and refrigerating for 2 days at the temperature of-20 ℃;
(5) retreatment of the catalyst electroplating solution, dropwise adding hydrazine hydrate into the catalyst electroplating solution prepared in the step (1) until the concentration of the hydrazine hydrate is 2.30mol/L, and stirring for 10 minutes by using a magnetic stirrer;
(6) and (3) as shown in figure 2, soaking a platinum wire serving as a positive electrode and a platinum sheet electrode clamp clamping the template prepared in the step (4) serving as a negative electrode in the catalyst electroplating solution treated in the step (5), connecting an adjustable power supply, and adopting a pulse current method to perform pulse current at the current density of 170mA/cm2And carrying out electrodeposition under the conditions that the duty ratio is 0.5, the period is 6 seconds, the cycle number is 900 and the temperature is 30 ℃ to obtain the Ni-Mo-Co hydrogen evolution catalyst with compact and flat surface and high activity.
However, the following examples are given for the purpose of illustration and not for the purpose of limitation, and the Ni-Mo-Co hydrogen evolution catalysts obtained in examples 1, 2, 3, 5, 6, 7, when tested, gave results similar to example 4, and therefore any changes within the meaning and scope equivalent to the present invention should be considered to be included in the scope of the present invention.
Claims (7)
1. A method for synthesizing a Ni-Mo-Co hydrogen evolution catalyst with high activity in an acidic environment is characterized by comprising the following steps:
(1) preparing a catalyst electroplating solution, adding chemical reagents serving as a nickel source, a molybdenum source and a cobalt source into a clean beaker, dissolving the beaker in deionized water, adding sodium pyrophosphate decahydrate and sodium bicarbonate, and stirring the solution by using a magnetic stirrer to prepare the catalyst electroplating solution;
(2) cleaning a substrate, shearing foamed nickel, putting the foamed nickel under concentrated sulfuric acid for ultrasonic treatment to remove dust, and cleaning with a cleaning solution to remove dirt after the ultrasonic treatment is finished to obtain a clean foamed nickel substrate;
(3) preparing a template electroplating solution, dissolving nickel salt in deionized water, adding ammonium chloride and sodium chloride, and stirring for 1-3 hours by using a magnetic stirrer to prepare the template electroplating solution;
(4) preparing a template, taking the clean foam nickel substrate obtained in the step (2), soaking the clean foam nickel substrate in the template electroplating solution prepared in the step (3), depositing by adopting an electrodeposition method by taking nickel ions in the template electroplating solution as deposits, regulating and controlling to form a template with a coral-shaped, spherical accumulation-shaped or pine-shaped appearance, and placing the template in a refrigerator for refrigeration;
(5) reprocessing the catalyst electroplating solution, adding a reducing agent into the catalyst electroplating solution prepared in the step (1), and stirring by using a magnetic stirrer;
(6) depositing a catalyst, namely soaking the template prepared in the step (4) in the catalyst electroplating solution treated in the step (5), and performing electrodeposition by adopting a pulse current method to obtain a high-activity Ni-Mo-Co hydrogen evolution catalyst with a compact and flat surface;
the pulse current method in the step (6) adopts square wave pulse, the duty ratio of the pulse current is 0.2-0.7, the period is 3-7 seconds, and the current density is 50-300 mA/cm2And (3) 500-1500 cycles in total, wherein the temperature in the electrodeposition process is controlled to be 20-50 ℃.
2. The method for synthesizing a Ni-Mo-Co hydrogen evolution catalyst with high activity in an acidic environment according to claim 1, wherein the Ni-Mo-Co hydrogen evolution catalyst comprises: the nickel source is nickel chloride hexahydrate with the dissolved concentration equal to 25-45 mmol/L, the molybdenum source is sodium molybdate dihydrate with the dissolved concentration equal to 8-35 mmol/L, the cobalt source is cobalt nitrate hexahydrate with the dissolved concentration equal to 12-42 mmol/L, the dissolved concentration of sodium pyrophosphate decahydrate is 60-100 mmol/L, and the dissolved concentration of sodium bicarbonate is 450-1500 mmol/L.
3. The method for synthesizing a Ni-Mo-Co hydrogen evolution catalyst having high activity in an acidic environment according to claim 1 or 2, wherein: and (2) stirring by using a magnetic stirrer in the step (1) for 3-5 hours, and standing the catalyst electroplating solution in an air atmosphere for 1-10 days after the stirring is finished.
4. The method for synthesizing a Ni-Mo-Co hydrogen evolution catalyst with high activity in an acidic environment according to claim 1, wherein the Ni-Mo-Co hydrogen evolution catalyst comprises: and (3) carrying out ultrasonic treatment in the step (2), wherein the power of the ultrasonic treatment is 300-500W, the ultrasonic treatment time is 3-10 minutes, and the cleaning agent is deionized water, absolute ethyl alcohol and acetone, and cleaning the substrate in an alternate cleaning manner.
5. The method for synthesizing a Ni-Mo-Co hydrogen evolution catalyst with high activity in an acidic environment according to claim 2, wherein the Ni-Mo-Co hydrogen evolution catalyst comprises: the nickel salt in the step (3) is nickel chloride hexahydrate with the dissolved concentration being 40-250 mmol/L, the dissolved concentration of ammonium chloride is 300-1000 mmol/L, and the dissolved concentration of sodium chloride is 500-2500 mmol/L.
6. The method for synthesizing a Ni-Mo-Co hydrogen evolution catalyst with high activity in an acidic environment according to claim 2, wherein the Ni-Mo-Co hydrogen evolution catalyst comprises: the electrodeposition method in the step (4) adopts a cathode deposition current of 0.5-2.5A, and the refrigeration process is carried out under the conditions of-20-0 ℃ for 1-3 days.
7. The method for synthesizing a Ni-Mo-Co hydrogen evolution catalyst with high activity in an acidic environment according to claim 2, wherein the Ni-Mo-Co hydrogen evolution catalyst comprises: and (3) dropwise adding hydrazine hydrate serving as a reducing agent in the step (5) until the concentration is 0.5-3 ml/L, and stirring for 5-10 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810128410.2A CN108315762B (en) | 2018-02-08 | 2018-02-08 | Synthesis method of Ni-Mo-Co hydrogen evolution catalyst with high activity in acidic environment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810128410.2A CN108315762B (en) | 2018-02-08 | 2018-02-08 | Synthesis method of Ni-Mo-Co hydrogen evolution catalyst with high activity in acidic environment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108315762A CN108315762A (en) | 2018-07-24 |
| CN108315762B true CN108315762B (en) | 2020-06-09 |
Family
ID=62902271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810128410.2A Active CN108315762B (en) | 2018-02-08 | 2018-02-08 | Synthesis method of Ni-Mo-Co hydrogen evolution catalyst with high activity in acidic environment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108315762B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108914156B (en) * | 2018-08-30 | 2020-05-05 | 合肥工业大学 | Fe-Co-Mo-P-C amorphous alloy electrocatalyst and preparation method and application thereof |
| CN112108149A (en) * | 2019-06-21 | 2020-12-22 | 南京大学昆山创新研究院 | Preparation method of electrocatalytic material, corresponding material and use method |
| CN110614105B (en) * | 2019-09-25 | 2022-05-31 | 上海应用技术大学 | Mo for hydrogen evolution2C/NiCoSex heterojunction electrocatalytic material and preparation method thereof |
| CN111558387A (en) * | 2020-05-18 | 2020-08-21 | 湖南大学 | Molybdenum carbide/foamed nickel composite material, preparation method thereof and application thereof in electrocatalytic oxygen evolution |
| CN112007645B (en) * | 2020-08-20 | 2023-05-26 | 常州大学 | Preparation method of hollow microsphere structured catalyst |
| CN114293220B (en) * | 2021-12-03 | 2023-07-18 | 华南理工大学 | Co (cobalt) 3-x Fe x Mo 3 N oxygen evolution electrocatalytic material and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4605484A (en) * | 1982-11-30 | 1986-08-12 | Asahi Kasei Kogyo Kabushiki Kaisha | Hydrogen-evolution electrode |
| CN1754011A (en) * | 2003-03-05 | 2006-03-29 | Tdk株式会社 | Rare earth metal magnet and plating bath |
| CN101431885A (en) * | 2008-12-18 | 2009-05-13 | 浙江三元电子科技有限公司 | All-directional conductive foam and producing method thereof |
| CN101509085A (en) * | 2008-02-15 | 2009-08-19 | 湖南大学 | Process for producing foam nickel-molybdenum-cobalt ternary-alloy material |
| CN102134732A (en) * | 2010-12-21 | 2011-07-27 | 北京化工大学 | Method for preparing nickel and nickel alloy one-dimensional superstructure nanometer functional materials by adopting hydrogen separation template method |
| CN102280260A (en) * | 2011-05-18 | 2011-12-14 | 浙江大学 | Three-dimensional porous compound film of super-capacitor and preparation method thereof |
| CN102747389A (en) * | 2012-07-03 | 2012-10-24 | 中国科学院宁波材料技术与工程研究所 | Electroplating solution for preparation of nanocrystalline nickel alloy plating and application thereof |
| CN105040041A (en) * | 2015-05-29 | 2015-11-11 | 广西大学 | Preparation method of Pd/Co3O4/foamed nickel electrode materials |
| CN105714360A (en) * | 2014-12-04 | 2016-06-29 | 中国科学院宁波材料技术与工程研究所 | Alkaline graphene-nickel electroplating liquid, and preparation method and application thereof |
| CN106694005A (en) * | 2016-11-30 | 2017-05-24 | 天津理工大学 | Preparation method of electric catalyst for acidic fully-decomposed water |
| CN107385489A (en) * | 2016-05-15 | 2017-11-24 | 北京化工大学 | A kind of three-dimensional manometer flower-shape Ni-Fe complex hydroxides for carbonate electrolyte analyse oxygen anodes |
-
2018
- 2018-02-08 CN CN201810128410.2A patent/CN108315762B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4605484A (en) * | 1982-11-30 | 1986-08-12 | Asahi Kasei Kogyo Kabushiki Kaisha | Hydrogen-evolution electrode |
| CN1754011A (en) * | 2003-03-05 | 2006-03-29 | Tdk株式会社 | Rare earth metal magnet and plating bath |
| CN101509085A (en) * | 2008-02-15 | 2009-08-19 | 湖南大学 | Process for producing foam nickel-molybdenum-cobalt ternary-alloy material |
| CN101431885A (en) * | 2008-12-18 | 2009-05-13 | 浙江三元电子科技有限公司 | All-directional conductive foam and producing method thereof |
| CN102134732A (en) * | 2010-12-21 | 2011-07-27 | 北京化工大学 | Method for preparing nickel and nickel alloy one-dimensional superstructure nanometer functional materials by adopting hydrogen separation template method |
| CN102280260A (en) * | 2011-05-18 | 2011-12-14 | 浙江大学 | Three-dimensional porous compound film of super-capacitor and preparation method thereof |
| CN102747389A (en) * | 2012-07-03 | 2012-10-24 | 中国科学院宁波材料技术与工程研究所 | Electroplating solution for preparation of nanocrystalline nickel alloy plating and application thereof |
| CN105714360A (en) * | 2014-12-04 | 2016-06-29 | 中国科学院宁波材料技术与工程研究所 | Alkaline graphene-nickel electroplating liquid, and preparation method and application thereof |
| CN105040041A (en) * | 2015-05-29 | 2015-11-11 | 广西大学 | Preparation method of Pd/Co3O4/foamed nickel electrode materials |
| CN107385489A (en) * | 2016-05-15 | 2017-11-24 | 北京化工大学 | A kind of three-dimensional manometer flower-shape Ni-Fe complex hydroxides for carbonate electrolyte analyse oxygen anodes |
| CN106694005A (en) * | 2016-11-30 | 2017-05-24 | 天津理工大学 | Preparation method of electric catalyst for acidic fully-decomposed water |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108315762A (en) | 2018-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108315762B (en) | Synthesis method of Ni-Mo-Co hydrogen evolution catalyst with high activity in acidic environment | |
| CN106917105B (en) | A kind of preparation method of water decomposition self-supporting transient metal sulfide foam electrode | |
| CN108360030B (en) | Method for preparing self-supporting nano cobalt-based bimetal phosphide catalytic hydrogen evolution electrode material by electrodeposition in eutectic ionic liquid | |
| CN110205636B (en) | Preparation method of self-supporting three-dimensional porous structure bifunctional catalytic electrode | |
| CN110344078A (en) | A kind of nickel foam@cobalt molybdenum phosphide/ferronickel double-hydroxide electrode and the preparation method and application thereof | |
| CN105107535A (en) | Self-supporting transition metal-phosphorus alloy catalyst, and preparation method and application thereof | |
| CN110424023B (en) | Nickel/vanadium oxide hydrogen evolution electrode and preparation method and application thereof | |
| CN108083242A (en) | The purposes of ternary phosphatization ferronickel nanometer sheet, its preparation method and electrolysis water | |
| CN107469835B (en) | High-efficiency water splitting bifunctional electrocatalyst and preparation method and application thereof | |
| CN113136597B (en) | Copper-tin composite material and preparation method and application thereof | |
| CN105148920A (en) | Self-supporting transition metal-metal alloy catalyst as well as preparation method and application of self-supporting transition metal-metal alloy catalyst | |
| CN113908870B (en) | Controllable preparation of double-function non-noble metal nitride catalyst and high-current electrolytic urea hydrogen production application | |
| CN108823591B (en) | Nickel-iron-selenium compound and preparation method and application thereof | |
| CN114686917A (en) | Electro-catalytic catalyst for synthesizing ammonia by reducing nitrate, preparation method and application thereof | |
| CN114408886B (en) | Preparation of noble metal doped porous iron-nickel phosphide | |
| CN113235125B (en) | Nickel-based NiCo 2 O 4 Electrocatalyst and its use in electrocatalytic oxidation of glycerol | |
| CN111604061A (en) | Caterpillar nickel-cobalt sulfide nano array and its synthesis and application | |
| CN114875442A (en) | Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof | |
| CN101717950B (en) | Method for preparing anode-catalyzed electrode for electrolyzing slurry coal | |
| CN111589459A (en) | Bifunctional catalyst for efficiently electrolyzing water, and preparation method and application thereof | |
| CN114045509B (en) | Seawater electrolysis device with sodium ion conduction and application thereof | |
| CN113463131B (en) | Copper monatomic catalyst and preparation method and application thereof | |
| CN114892206A (en) | Multi-metal nitride heterojunction nanorod array composite electrocatalyst and preparation method and application thereof | |
| CN112981448A (en) | Preparation and application of carbon sphere @ nickel sulfide compound hydrogen evolution catalyst | |
| CN114318410B (en) | Cobalt-based electrolyzed water catalyst, preparation method thereof and application thereof in electrolyzed water |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |