CN108411324A - The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind and preparation and application - Google Patents
The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind and preparation and application Download PDFInfo
- Publication number
- CN108411324A CN108411324A CN201810269322.4A CN201810269322A CN108411324A CN 108411324 A CN108411324 A CN 108411324A CN 201810269322 A CN201810269322 A CN 201810269322A CN 108411324 A CN108411324 A CN 108411324A
- Authority
- CN
- China
- Prior art keywords
- cobalt sulfide
- nitrogen
- sulfur
- graphene
- supported cobalt
- 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
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
- 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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to electrochemical material fields, disclose the sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind and preparation and application.In a solvent by the dissolving of metal cobalt source, nickel source and thiocarbamide, ultrasonic agitation mixing, is then added dropwise ammonium hydroxide, it is stirred, graphene oxide is then added, hydro-thermal process is carried out after ultrasonic agitation mixing, centrifuge washing again, freeze-drying, obtains graphene-supported cobalt sulfide nickel composite material；Then calcination processing is carried out in a nitrogen atmosphere, and further redox graphene obtains sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material.The synthetic method of the present invention is simple, of low cost, energy consumption is relatively low, environmental-friendly, and products therefrom has good electric conductivity and electrochemical catalysis performance, is suitble to the practical application of the cathode and anode catalysis material of water-splitting.
Description
Technical field
The invention belongs to electrochemical material fields, and in particular to a kind of sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalysis
Material and preparation and application.
Background technology
The development of current social causes our economy easily by fossil fuel price wave the height dependence of fossil fuel
Dynamic influence；In addition, the excessive use of fossil fuel exacerbates environmental pollution and greenhouse effects.Therefore, develop it is a kind of cleaning, can
Regeneration, environmental-friendly, free of contamination alternative energy source is extremely urgent.Using oil, coal, natural gas as the primary energy of representative most
Replaced at last by clean reproducible energies such as solar energy, wind energy, ocean energy and biomass energies.Various fungible energy sources are compared,
Hydrogen Energy can be produced as a kind of round-the-clock resource by electrolysis water.And tellurian water resource is extremely abundant, be take no
To the greatest extent, nexhaustible, there are unrivaled huge advantage and wide application prospect with water hydrogen manufacturing.
Water electrolysis is made of two half-reactions, is that (OER) reaction is precipitated in Hydrogen evolving reaction (HER) and oxygen respectively.It is the widest
General electrolysis water cathode catalyst for preparing hydrogen is platinum group (Pt) precious metal simple substance, this is because the elements such as noble metal platinum are in catalysis water power
Higher electron transport ability and smaller overpotential and comparison suitable Hydrogen chemisorption free energy are shown when solution.Except Pt
Other than the precious metal element of series, transition metal atoms are suitable for hydrogen since the d tracks of its outermost electron layer are also easy to produce hole
The adsorption process of atom.Simultaneously because perfluoro sulfonic acid membrane (solid electrolytic widely used in solid polymer electrolytic slot at present
Matter) highly acid (sulfuric acid solution for being equivalent to 10% mass fraction) can be shown in water, Pt races etc. are in Strong acidic electrolyte
The metal and its alloy for having higher stability and catalytic activity are widely adopted, but we it should be noted that noble metal production
Amount is rare and expensive, this directly results in the hydrogen cost increase produced.And as the half-reaction of electrocatalytic decomposition water, hair
The raw analysis oxygen catalytic process in anode is related to the transfer of 4 electronics, the reaction of poor oxygen evolution kinetic and higher analysis oxygen mistake
Hydrolytic hydrogen production efficiency caused by current potential reduces, and noble metal oxygen-separating catalyst (RuO2And IrO2) use limit its big rule
Mould application.Therefore, the research and development of liberation of hydrogen oxygen-separating catalyst novel, efficient, cheap and easy to get are to realize the pass of scale hydrolytic hydrogen production
Key.In recent years, the property of First Transition metal and its oxide as liberation of hydrogen oxygen-separating catalyst cheap and easy to get has been extensively studied in people
Can, such as Ni bases, Co bases, Fe bases, Mn base liberation of hydrogen oxygen-separating catalysts.But its poorly conductive, active surface area are limited and are catalyzed
The problems such as stability is poor limits it and substitutes noble metal (RuO2、IrO2With Pt etc.) catalyst is to realize commercial applications.Passing through
Learn the modified and structurally-modified liberation of hydrogen analysis oxygen performance that can further increase catalyst of transition metal oxide：Wherein chemical modification
It is that binary or ternary metallic compound is synthesized by element doping, structurally-modified changed by changing the nanostructure of catalyst
The physical properties such as its electric conductivity, hydrophily, rough surface, to increase the active site of catalyst.
Until up to now, there are no sulfur and nitrogen co-doped graphene-supported spherical cobalt sulfide nickel material is applied to catalytic water
The relevant report with oxygen evolution reaction is precipitated in hydrogen in electrolysis.
Invention content
In place of the above shortcoming and defect of the existing technology, the primary purpose of the present invention is that providing a kind of sulphur nitrogen
The graphene-supported cobalt sulfide nickel of codope (rGO@SN-CoNi2S4) catalysis material preparation method.The present invention utilizes a step hydro-thermal
Method by metal salt and thiocarbamide with graphene oxide is compound prepares sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel composite material, tool
Have the advantages that preparation method is simple, cost is relatively low, environmental-friendly, the development of scale water electrolysis catalyst agent material can be promoted.
It is negative that another object of the present invention is to provide a kind of sulfur and nitrogen co-doped graphenes being prepared by the above method
Carry cobalt sulfide nickel catalytic material.
It is still another object of the present invention to provide above-mentioned sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic materials in water
Electrolysis hydrogen is precipitated and the application in catalysis reaction is precipitated in oxygen.The rGO@SN-CoNi of the present invention2S4Can improve material electric conductivity and
Structural stability, to improve the chemical property of water electrolysis double-function catalyzing agent material.
The object of the invention is achieved through the following technical solutions：
A kind of sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel (rGO@SN-CoNi2S4) catalysis material preparation method, packet
Include following steps：
(1) in a solvent by the dissolving of metal cobalt source, nickel source and thiocarbamide, ultrasonic agitation mixing, is then added dropwise ammonium hydroxide, and stirring is mixed
It closes, obtains homogeneous solution；
(2) it adds graphene oxide into the homogeneous solution in step (1), is carried out at hydro-thermal after ultrasonic agitation mixing
Reason, then centrifuge washing, freeze-drying, obtain graphene-supported cobalt sulfide nickel composite material；
(3) graphene-supported cobalt sulfide nickel composite material obtained by step (2) is subjected to calcination processing in a nitrogen atmosphere, into
One step redox graphene obtains sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material.
Preferably, cobalt source and nickel source described in step (1) are respectively cobalt acetate and nickel acetate.
Preferably, solvent described in step (1) is at least one of the tert-butyl alcohol, water and absolute ethyl alcohol.
Preferably, the time that mixing is stirred by ultrasonic described in step (1) is 2~4h, the dropwise addition ammonium hydroxide is stirred
Time be 1~2h.
Preferably, the time that mixing is stirred by ultrasonic described in step (2) is 1~2h.
Preferably, the temperature of hydro-thermal process described in step (2) is 150~200 DEG C, the time is 10~15h.
Preferably, washing described in step (2) refers to being washed respectively 3~5 times with water and absolute ethyl alcohol.
Preferably, freeze-drying described in step (2) is dry 24~48h in freeze drying box.
Preferably, being carried on the vulcanization of graphene in graphene-supported cobalt sulfide nickel composite material described in step (2)
Cobalt nickel is sphere, and grain size is 200~300nm.
Preferably, the cobalt sulfide nickel (CoNi of the addition of graphene oxide described in step (2) and load2S4) matter
Amount is than being 1:(1~10).
Preferably, calcination processing described in step (3) refers to 3~5h of calcining at 300~500 DEG C.
A kind of sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel (rGO@SN-CoNi2S4) catalysis material, pass through the above method
It is prepared.The sulfur and nitrogen co-doped graphene-supported cobalt sulfide Raney nickel material by sphere cobalt sulfide nickel particle uniform load in
It is constituted on graphene layer；The sphere cobalt sulfide nickel particle grain size is 200~300nm.
Above-mentioned sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material is precipitated in water electrolysis hydrogen and catalysis is precipitated instead in oxygen
Application in answering.
The present invention preparation method and obtained product has the following advantages that and advantageous effect：
(1) since graphene has good electric conductivity, the conductivity of material can be increased so that sulphur nitrogen of the present invention is co-doped with
Miscellaneous graphene-supported cobalt sulfide nickel catalytic material has lower deposition potential during being catalyzed hydrogen and being precipitated with oxygen evolution reaction,
Larger current density；Meanwhile the load coating function of graphene makes material have preferable stability.
(2) doping of sulphur nitrogen, the grapheme material of sulphur N doping also can in the grapheme material loaded
Improve the electric conductivity and electrochemical catalysis performance of material.
(3) present invention using one step hydro thermal method by metal salt and thiocarbamide and graphene oxide it is compound prepare it is sulfur and nitrogen co-doped
Graphene-supported cobalt sulfide nickel composite material, synthetic method is simple, of low cost, energy consumption is relatively low, environmental-friendly, can promote to advise
The development of modelling water electrolysis catalyst agent material.
Description of the drawings
Fig. 1 is the XRD diagram of the sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of gained in the embodiment of the present invention 1.
Fig. 2 is the thermogravimetric point of the sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of gained in the embodiment of the present invention 1
Analysis figure.
Fig. 3 is the SEM figures of the sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of gained in the embodiment of the present invention 1.
Fig. 4 is the TEM figures of the sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of gained in the embodiment of the present invention 1.
Fig. 5 is the sulfur and nitrogen co-doped graphene-supported cobalt sulfide Raney nickel material of gained in the embodiment of the present invention 1 as hydrogen
Linear sweep voltammetry curve (LSV) performance map of evolution reaction catalyst material.
Fig. 6 is that the sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of gained is analysed as hydrogen in the embodiment of the present invention 1
Go out the CV stable circulation performance figures of catalytic reaction agent material.
Fig. 7 is that the sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of gained is analysed as oxygen in the embodiment of the present invention 1
Go out linear sweep voltammetry curve (LSV) performance map of catalytic reaction agent material.
Fig. 8 is that the sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of gained is analysed as oxygen in the embodiment of the present invention 1
Go out the CV stable circulation performance figures of catalytic reaction agent material.
Specific implementation mode
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) thiocarbamide for weighing the cobalt acetate of 1mmol, the nickel acetate of 2mmol and 9mmol is dissolved into the water and 30mL of 20mL
In t-butanol solution, after stirring 2h at room temperature, uniformly mixed solution is obtained；The ammonium hydroxide of 2mL is slowly added dropwise and stirs 2h, obtains
Homogeneous solution.
(2) the graphene oxide colloidal sol of 40mg is added in the homogeneous solution into step (1), ultrasound is uniform and stirs 1h；
Solution obtained above is transferred in the reaction kettle of 100mL, hydro-thermal reaction 12h is carried out at 180 DEG C；By hydro-thermal reaction product
It is centrifuged, after washing 3 times respectively with water and absolute ethyl alcohol, carries out freezing processing and the drying in vacuum freezing drying oven
For 24 hours, graphene-supported cobalt sulfide nickel composite material is obtained.
(3) obtained graphene-supported cobalt sulfide nickel composite material is put into porcelain boat and is placed in tube furnace, in nitrogen gas
Under atmosphere protection, 400 DEG C of reaction 3h are finally cooled to room temperature, obtain sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material.
The XRD diagram of sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material obtained by the present embodiment is as shown in Figure 1.X is penetrated
Line powder diffraction (XRD) analysis shows gained product be pure cobalt sulfide nickel and carbon, do not find metal dephasign, illustrate purity compared with
It is high.The thermogravimetric analysis figure of the sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of gained is as shown in Figure 2.From thermogravimetric analysis figure
In it can be seen that, the weight change of material is divided into three phases, is the phase change stage of water, graphene and cobalt sulfide nickel respectively,
Mass percent by can be calculated water, graphene and cobalt sulfide nickel is 15.37%, 40.55% and 44.08% respectively.Institute
SEM figures and the TEM difference for obtaining sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material are as shown in Figure 3 and Figure 4.From scanning electricity
Sub- microscope (SEM) and transmission electron microscope (TEM) it can be seen from the figure that cobalt sulfide nickel particle are uniformly embedded in graphene, grain size
For 200~300nm.
Sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel (rGO@SN-CoNi obtained by the present embodiment2S4) catalysis material is in water power
Xie Qing is precipitated and the application test in catalysis reaction is precipitated in oxygen：
The Nafion (5wt.%) for pipetting 100 μ L is dissolved in second alcohol and water (volume ratio=1 of 1mL:4) second is prepared in mixed liquor
Alcohol-water-Nafion solution is spare.Weigh 4.0mg rGO@SN-CoNi2S4It is scattered in matched alcohol-water-Nafion solution, surpasses
It is spare that sound 1h prepares suspension.Then the dispersant liquid drop for pipetting 20 μ L is coated onto on glass-carbon electrode, and naturally dry has obtained rGO@SN-
CoNi2S4The electrode of-Nafion modifications.The rGO@SN-CoNi of above-mentioned preparation2S4Work electricity is precipitated as hydrogen in-Nafion electrodes
Pole, saturated calomel electrode are used as reference electrode, charcoal bar electrode to electrode.This three electrodes one end is connected to electrochemical workstation
(Shanghai Chen Hua 660E), the other end immerse in 1M KOH (pH=13.94 ± 0.04) electrolyte.Using linear sweep voltammetry curve
Catalytic performance, sweep speed 2mV/s, scanning voltage range -0.8V~-2V is precipitated in method test material hydrogen.Gained sulphur nitrogen is co-doped with
Linear sweep voltammetry curve (LSV) of the miscellaneous graphene-supported cobalt sulfide Raney nickel material as Hydrogen evolving reaction catalyst material
Performance map is as shown in Figure 5.In the electrolyte of 1M KOH, rGO@SN-CoNi2S4Deposition potential (relative to mark after impedance correction
Quasi- potential) it is about 35mV；As current density j=10mA/cm2When, there is voltage 138.3mV good electrochemical hydrogen to be precipitated
Catalytic performance.CV of the sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of gained as Hydrogen evolving reaction catalyst material
Stable circulation performance figure is as shown in Figure 6.It can be seen that test material performance after 3000 circle of CV (cyclic voltammetry) scannings, deposition potential
Do not decay with current density, there is preferable stability.It is precipitated in catalytic performance test in water electrolysis oxygen, in use
State the rGO@SN-CoNi of preparation2S4Working electrode is precipitated as oxygen in-Nafion electrodes, saturated calomel electrode as reference electrode,
Gauze platinum electrode is used as to electrode.This three electrodes one end connects rotating disk electrode (r.d.e), and the other end immerses in 1M KOH electrolyte.Using
Catalytic performance, rotating speed 1600rpm, sweep speed 5mV/s, scanning electricity is precipitated in linear sweep voltammetry curve method test material oxygen
Press range 0V~1V.The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of gained is as oxygen evolution reaction catalyst material
Linear sweep voltammetry curve (LSV) performance map it is as shown in Figure 7.In the electrolyte of 1M KOH, rGO@SN-CoNi2S4Precipitation
Current potential is about 1.52V (relative to standard electrode potential after impedance correction)；As current density j=10mA/cm2When, voltage 1.56V,
Catalytic performance is precipitated with good electrochemistry oxygen.The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of gained is as oxygen
The CV stable circulation performance figures of evolution reaction catalyst material are as shown in Figure 8.It can be seen that after 1000 circle of CV (cyclic voltammetry) scannings
Test material performance, deposition potential are not decayed with current density, have preferable stability.
Embodiment 2
(1) thiocarbamide for weighing the cobalt acetate of 1mmol, the nickel acetate of 2mmol and 9mmol is dissolved into the water and 30mL of 20mL
In t-butanol solution, after stirring 3h at room temperature, uniformly mixed solution is obtained；The ammonium hydroxide of 2mL is slowly added dropwise and stirs 1h, obtains
Homogeneous solution.
(2) the graphene oxide colloidal sol of 30.4mg is added in the homogeneous solution into step (1), ultrasound is uniform and stirs
1h；Solution obtained above is transferred in the reaction kettle of 100mL, hydro-thermal reaction 10h is carried out at 150 DEG C；By hydro-thermal reaction
Product is centrifuged, and after washing 3 times respectively with water and absolute ethyl alcohol, carries out freezing processing and in vacuum freezing drying oven
Dry 48h, obtains graphene-supported cobalt sulfide nickel composite material.
(3) obtained graphene-supported cobalt sulfide nickel composite material is put into porcelain boat and is placed in tube furnace, in nitrogen gas
Under atmosphere protection, 300 DEG C of reaction 5h are finally cooled to room temperature, obtain sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material.
Sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel (rGO@SN-CoNi obtained by the present embodiment2S4) catalysis material is in water power
Xie Qing is precipitated and the application test in catalysis reaction is precipitated in oxygen：
The Nafion (5wt.%) for pipetting 100 μ L is dissolved in second alcohol and water (volume ratio=1 of 1mL:4) second is prepared in mixed liquor
Alcohol-water-Nafion solution is spare.Weigh 4.0mg rGO@SN-CoNi2S4It is scattered in matched alcohol-water-Nafion solution, surpasses
It is spare that sound 1h prepares suspension.Then the dispersant liquid drop for pipetting 20 μ L is coated onto on glass-carbon electrode, and naturally dry has obtained rGO@SN-
CoNi2S4The electrode of-Nafion modifications.The rGO@SN-CoNi of above-mentioned preparation2S4Work electricity is precipitated as hydrogen in-Nafion electrodes
Pole, saturated calomel electrode are used as reference electrode, charcoal bar electrode to electrode.This three electrodes one end is connected to electrochemical workstation
(Shanghai Chen Hua 660E), the other end immerse in 1M KOH (pH=13.94 ± 0.04) electrolyte.Using linear sweep voltammetry curve
Catalytic performance, sweep speed 2mV/s, scanning voltage range -0.8V~-2V is precipitated in method test material hydrogen.In the electricity of 1M KOH
It solves in liquid, rGO@SN-CoNi2S4Deposition potential (relative to standard electrode potential after impedance correction) be about 30mV；As current density j
=10mA/cm2When, there is voltage 130.1mV good electrochemical hydrogen catalytic performance is precipitated.CV (cyclic voltammetry) is scanned
Test material performance after 3000 circles, deposition potential are not decayed with current density, have preferable stability.In water
It is electrolysed oxygen to be precipitated in catalytic performance test, using the rGO@SN-CoNi of above-mentioned preparation2S4Work is precipitated as oxygen in-Nafion electrodes
Electrode, saturated calomel electrode are used as reference electrode, gauze platinum electrode to electrode.This three electrodes one end connects rotating circular disk electricity
Pole, the other end immerse in 1M KOH electrolyte.Catalytic performance, rotating speed are precipitated using linear sweep voltammetry curve method test material oxygen
For 1600rpm, sweep speed 5mV/s, scanning voltage range 0V~1V.In the electrolyte of 1M KOH, rGO@SN-CoNi2S4
Deposition potential (relative to standard electrode potential after impedance correction) be about 1.49V；As current density j=10mA/cm2When, voltage is
There is 1.54V good electrochemistry oxygen catalytic performance is precipitated.Test material performance after 1000 circle of CV (cyclic voltammetry) scannings,
Its deposition potential is not decayed with current density, has preferable stability.
Embodiment 3
(1) thiocarbamide for weighing the cobalt acetate of 1mmol, the nickel acetate of 2mmol and 9mmol is dissolved into the water and 30mL of 20mL
In t-butanol solution, after stirring 4h at room temperature, uniformly mixed solution is obtained；The ammonium hydroxide of 2mL is slowly added dropwise and stirs 1h, obtains
Homogeneous solution.
(2) the graphene oxide colloidal sol of 304mg is added in the homogeneous solution into step (1), ultrasound is uniform and stirs 2h；
Solution obtained above is transferred in the reaction kettle of 100mL, hydro-thermal reaction 15h is carried out at 200 DEG C；By hydro-thermal reaction product
It is centrifuged, after washing 3 times respectively with water and absolute ethyl alcohol, carries out freezing processing and the drying in vacuum freezing drying oven
36h obtains graphene-supported cobalt sulfide nickel composite material.
(3) obtained graphene-supported cobalt sulfide nickel composite material is put into porcelain boat and is placed in tube furnace, in nitrogen gas
Under atmosphere protection, 500 DEG C of reaction 4h are finally cooled to room temperature, obtain sulfur and nitrogen co-doped graphene-supported cobalt sulfide ni-mh be precipitated and
Catalyst material is precipitated in oxygen.
Sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel (rGO@SN-CoNi obtained by the present embodiment2S4) catalysis material is in water power
Xie Qing is precipitated and the application test in catalysis reaction is precipitated in oxygen：
The Nafion (5wt.%) for pipetting 100 μ L is dissolved in second alcohol and water (volume ratio=1 of 1mL:4) second is prepared in mixed liquor
Alcohol-water-Nafion solution is spare.Weigh 4.0mg rGO@SN-CoNi2S4It is scattered in matched alcohol-water-Nafion solution, surpasses
It is spare that sound 1h prepares suspension.Then the dispersant liquid drop for pipetting 20 μ L is coated onto on glass-carbon electrode, and naturally dry has obtained rGO@SN-
CoNi2S4The electrode of-Nafion modifications.The rGO@SN-CoNi of above-mentioned preparation2S4Work electricity is precipitated as hydrogen in-Nafion electrodes
Pole, saturated calomel electrode are used as reference electrode, charcoal bar electrode to electrode.This three electrodes one end is connected to electrochemical workstation
(Shanghai Chen Hua 660E), the other end immerse in 1M KOH (pH=13.94 ± 0.04) electrolyte.Using linear sweep voltammetry curve
Catalytic performance, sweep speed 2mV/s, scanning voltage range -0.8V~-2V is precipitated in method test material hydrogen.In the electricity of 1M KOH
It solves in liquid, rGO@SN-CoNi2S4Deposition potential (relative to standard electrode potential after impedance correction) be about 33mV；As current density j
=10mA/cm2When, there is voltage 135.2mV good electrochemical hydrogen catalytic performance is precipitated.CV (cyclic voltammetry) is scanned
Test material performance after 3000 circles, deposition potential are not decayed with current density, have preferable stability.In water
It is electrolysed oxygen to be precipitated in catalytic performance test, using the rGO@SN-CoNi of above-mentioned preparation2S4Work is precipitated as oxygen in-Nafion electrodes
Electrode, saturated calomel electrode are used as reference electrode, gauze platinum electrode to electrode.This three electrodes one end connects rotating circular disk electricity
Pole, the other end immerse in 1M KOH electrolyte.Catalytic performance, rotating speed are precipitated using linear sweep voltammetry curve method test material oxygen
For 1600rpm, sweep speed 5mV/s, scanning voltage range 0V~1V.In the electrolyte of 1M KOH, rGO@SN-CoNi2S4
Deposition potential (relative to standard electrode potential after impedance correction) be about 1.495V；As current density j=10mA/cm2When, voltage is
There is 1.543V good electrochemistry oxygen catalytic performance is precipitated.Test material performance after 1000 circle of CV (cyclic voltammetry) scannings,
Its deposition potential is not decayed with current density, has preferable stability.
Comparative example 1
(1) thiocarbamide for weighing the cobalt acetate of 3mmol, the nickel acetate of 0mmol and 9mmol is dissolved into the water and 30mL of 20mL
In t-butanol solution, after stirring 2h at room temperature, uniformly mixed solution is obtained；The ammonium hydroxide of 2mL is slowly added dropwise and stirs 2h, obtains
Homogeneous solution.
(2) the graphene oxide colloidal sol of 40mg is added in the homogeneous solution into step (1), ultrasound is uniform and stirs 1h；
Solution obtained above is transferred in the reaction kettle of 100mL, hydro-thermal reaction 12h is carried out at 180 DEG C；By hydro-thermal reaction product
It is centrifuged, after washing 3 times respectively with water and absolute ethyl alcohol, carries out freezing processing and the drying in lyophilizer
For 24 hours, graphene-supported cobalt disulfide composite material is obtained.
(3) obtained graphene-supported cobalt disulfide composite material is put into porcelain boat and is placed in tube furnace, in nitrogen gas
Under atmosphere protection, 400 DEG C of reaction 3h are finally cooled to room temperature, obtain sulfur and nitrogen co-doped graphene-supported cobalt disulfide (rGO@SN-
CoS2) catalysis material.
The sulfur and nitrogen co-doped graphene-supported cobalt disulfide and saturated calomel electrode and carbon rod group prepared using this comparative example
It dresses up hydrogen and three-electrode system is precipitated.In the electrolyte of 1M KOH, rGO@SN-CoS2Hydrogen be precipitated take-off potential (impedance correction
Afterwards relative to standard electrode potential) it is about 202mV；As current density j=10mA/cm2When, voltage 316.6mV, therefore it has electricity
Chemical hydrogen is precipitated catalytic performance and is significantly worse than sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel rGO@SN- made from embodiment 1
CoNi2S4.Test material performance after 3000 circle of CV (cyclic voltammetry) scannings, deposition potential exist with current density attenuation rate
Within 10%, therefore its stability also can not show a candle to sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel rGO@SN-CoNi2S4。
Sulfur and nitrogen co-doped graphene-supported cobalt disulfide is assembled into saturated calomel electrode and platinum guaze in the test that oxygen is precipitated
Three-electrode system is precipitated in oxygen.In the electrolyte of 1M KOH, rGO@SN-CoS2Oxygen take-off potential (phase after impedance correction is precipitated
For standard electrode potential) it is about 1.532mV；As current density j=10mA/cm2When, voltage 1.576V, therefore its electricity for having
Chemical oxygen is precipitated catalytic performance and is also significantly worse than sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel rGO@SN- made from embodiment 1
CoNi2S4。
Comparative example 2
(1) thiocarbamide for weighing the cobalt acetate of 0mmol, the nickel acetate of 3mmol and 9mmol is dissolved into the water and 30mL of 20mL
In t-butanol solution, after stirring 2h at room temperature, uniformly mixed solution is obtained；The ammonium hydroxide of 2mL is slowly added dropwise and stirs 2h, obtains
Homogeneous solution.
(2) the graphene oxide colloidal sol of 40mg is added in the homogeneous solution into step (1), ultrasound is uniform and stirs 1h；
Solution obtained above is transferred in the reaction kettle of 100mL, hydro-thermal reaction 12h is carried out at 180 DEG C；By hydro-thermal reaction product
It is centrifuged, after washing 3 times respectively with water and absolute ethyl alcohol, carries out freezing processing and the drying in lyophilizer
For 24 hours, graphene-supported curing nickel composite material is obtained.
(3) obtained graphene-supported curing nickel composite material is put into porcelain boat and is placed in tube furnace, in nitrogen gas
Under atmosphere protection, 400 DEG C of reaction 3h are finally cooled to room temperature, obtain sulfur and nitrogen co-doped graphene-supported curing nickel catalytic material.
The sulfur and nitrogen co-doped graphene-supported curing nickel and saturated calomel electrode and carbon rod group prepared using this comparative example
Dress up three-electrode system.In the electrolyte of 1M KOH, rGO@SN-NiS2Hydrogen that take-off potential is precipitated is (opposite after impedance correction
In standard electrode potential) it is about 255.3mV；As current density j=10mA/cm2When, voltage 367.4mV, therefore its electrification for having
It learns hydrogen precipitation catalytic performance and is significantly worse than sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel rGO@SN- made from embodiment 1
CoNi2S4.Test material performance after 3000 circle of CV (cyclic voltammetry) scannings, deposition potential exist with current density attenuation rate
Within 10%, therefore its stability also can not show a candle to sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel rGO@SN-CoNi2S4。
Sulfur and nitrogen co-doped graphene-supported curing nickel is assembled into saturated calomel electrode and platinum guaze in the test that oxygen is precipitated
Three-electrode system is precipitated in oxygen.In the electrolyte of 1M KOH, rGO@SN-NiS2Oxygen take-off potential (phase after impedance correction is precipitated
For standard electrode potential) it is about 1.541mV；As current density j=10mA/cm2When, voltage 1.584V, therefore its electricity for having
Chemical oxygen is precipitated catalytic performance and is also significantly worse than sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel rGO@SN- made from embodiment 1
CoNi2S4。
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material, it is characterised in that including following step
Suddenly：
(1) in a solvent by the dissolving of metal cobalt source, nickel source and thiocarbamide, ultrasonic agitation mixing, is then added dropwise ammonium hydroxide, is stirred,
Obtain homogeneous solution；
(2) it adds graphene oxide into the homogeneous solution in step (1), hydro-thermal process is carried out after ultrasonic agitation mixing, then
Centrifuge washing, freeze-drying, obtains graphene-supported cobalt sulfide nickel composite material；
(3) graphene-supported cobalt sulfide nickel composite material obtained by step (2) is subjected to calcination processing in a nitrogen atmosphere, further
Redox graphene obtains sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material.
2. a kind of preparation method of sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material according to claim 1,
It is characterized in that：Cobalt source and nickel source are respectively cobalt acetate and nickel acetate described in step (1).
3. a kind of preparation method of sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material according to claim 1,
It is characterized in that：Solvent described in step (1) is at least one of the tert-butyl alcohol, water and absolute ethyl alcohol.
4. a kind of preparation method of sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material according to claim 1,
It is characterized in that：The time that mixing is stirred by ultrasonic described in step (1) is 2~4h, the time that ammonium hydroxide is added dropwise and is stirred
For 1~2h；The time that mixing is stirred by ultrasonic described in step (2) is 1~2h.
5. a kind of preparation method of sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material according to claim 1,
It is characterized in that：The temperature of hydro-thermal process described in step (2) is 150~200 DEG C, and the time is 10~15h.
6. a kind of preparation method of sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material according to claim 1,
It is characterized in that：The cobalt sulfide nickel that graphene is carried in graphene-supported cobalt sulfide nickel composite material described in step (2) is
Sphere, grain size are 200~300nm.
7. a kind of preparation method of sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material according to claim 1,
It is characterized in that：The mass ratio of the cobalt sulfide nickel of the addition and load of graphene oxide described in step (2) is 1:(1~
10)。
8. a kind of preparation method of sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material according to claim 1,
It is characterized in that：Calcination processing described in step (3) refers to 3~5h of calcining at 300~500 DEG C.
9. a kind of sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material, it is characterised in that：Pass through claim 1~8 times
Method described in one is prepared；The sulfur and nitrogen co-doped graphene-supported cobalt sulfide Raney nickel material is by sphere cobalt sulfide
Nickel particle uniform load on graphene layer in constituting；The sphere cobalt sulfide nickel particle grain size is 200~300nm.
10. the sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind described in claim 9 is precipitated in water electrolysis hydrogen
The application in catalysis reaction is precipitated with oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810269322.4A CN108411324A (en) | 2018-03-29 | 2018-03-29 | The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind and preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810269322.4A CN108411324A (en) | 2018-03-29 | 2018-03-29 | The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind and preparation and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108411324A true CN108411324A (en) | 2018-08-17 |
Family
ID=63133800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810269322.4A Pending CN108411324A (en) | 2018-03-29 | 2018-03-29 | The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind and preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108411324A (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109378483A (en) * | 2018-10-09 | 2019-02-22 | 大连理工大学 | A kind of novel magnesium air cell catalyst layer material, preparation process and application |
| CN109518219A (en) * | 2018-12-24 | 2019-03-26 | 江苏大学 | A kind of preparation method and applications of graphene-based nickel cobalt bimetallic oxygen-separating catalyst |
| CN109659544A (en) * | 2018-12-24 | 2019-04-19 | 肇庆市华师大光电产业研究院 | A kind of lithium/anode material of lithium-ion battery preparation method of graphene coated bimetallic sulfide |
| CN109672075A (en) * | 2019-02-18 | 2019-04-23 | 哈尔滨工程大学 | A kind of preparation method of multi-wavelength optical fiber laser and its curing nickel mode-locking device |
| CN109675605A (en) * | 2019-01-09 | 2019-04-26 | 上海应用技术大学 | A kind of Ni/Co-NCs liberation of hydrogen material, preparation method and applications |
| CN109759120A (en) * | 2019-03-07 | 2019-05-17 | 燕山大学 | A kind of nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece and its preparation method and application |
| CN109759066A (en) * | 2019-01-29 | 2019-05-17 | 济南大学 | A kind of preparation method for the cobalt nickel bimetal oxide oxygen-separating catalyst that boron doping is graphene-supported |
| CN109806887A (en) * | 2019-02-22 | 2019-05-28 | 沈阳师范大学 | A kind of electrolysis aquatic products hydrogen catalyst and preparation method thereof |
| CN109939716A (en) * | 2019-04-10 | 2019-06-28 | 黑龙江大学 | A kind of nitrogen vacancy carbon-supported catalysts and preparation method thereof for hydrogen manufacturing |
| CN109950512A (en) * | 2019-04-19 | 2019-06-28 | 陕西科技大学 | A kind of nitrogen sulphur codope three-dimensional grapheme and transient metal sulfide composite material and its universality preparation method and application |
| CN110280271A (en) * | 2019-06-06 | 2019-09-27 | 中南林业科技大学 | The preparation method of OER composite electrocatalyst |
| CN110336047A (en) * | 2019-07-16 | 2019-10-15 | 运城学院 | Nickel cobalt sulfide/graphene composite material zinc and air cell bifunctional catalyst preparation method |
| CN111111725A (en) * | 2018-12-10 | 2020-05-08 | 天津大学 | Graphite-like carbon nitride supported nickel-cobalt-sulfur particle composite material, preparation method and application thereof |
| CN111268671A (en) * | 2020-01-20 | 2020-06-12 | 广东工业大学 | Graphene-loaded tin-doped cobalt disulfide composite material and preparation method and application thereof |
| CN111383848A (en) * | 2018-12-27 | 2020-07-07 | 郑州轻工业学院 | graphene-CoNi for super capacitor2S4Nanocomposite and method for preparing same |
| CN111573745A (en) * | 2020-05-06 | 2020-08-25 | 电子科技大学 | Preparation method of nickel-cobalt sulfide and graphene composite material rich in elemental sulfur |
| CN112226780A (en) * | 2020-10-17 | 2021-01-15 | 石河子大学 | NiCo for total water splitting2S4Preparation method of/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst |
| CN113174601A (en) * | 2021-04-27 | 2021-07-27 | 陕西科技大学 | Nickel sulfide electrocatalyst based on in-situ growth on nitrogen and sulfur co-doped reduced graphene oxide, and preparation method and application thereof |
| CN113403629A (en) * | 2021-06-07 | 2021-09-17 | 嘉寓氢能源科技(辽宁)有限公司 | Catalyst for water electrolysis hydrogen production system and preparation method thereof |
| CN114515552A (en) * | 2022-03-11 | 2022-05-20 | 山东大学 | NiCo alloy @ nitrogen-doped graphene hierarchical pore aerogel, preparation method thereof and application thereof in zinc-air battery |
| CN115106112A (en) * | 2022-05-19 | 2022-09-27 | 华南理工大学 | Preparation method of 3D cobalt sulfide cocatalyst and application of cocatalyst in Fenton reaction |
| CN115261915A (en) * | 2022-08-29 | 2022-11-01 | 长春大学 | Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105244482A (en) * | 2015-09-12 | 2016-01-13 | 复旦大学 | Nickel cobalt sulfide/graphene/carbon nanotube composite material and preparation method and application thereof |
| CN105296970A (en) * | 2015-09-25 | 2016-02-03 | 上海交通大学 | Method for preparing nitrogen-doped graphene and nickel sulfide quantum dot nanometer composite material |
| CN105293590A (en) * | 2015-10-16 | 2016-02-03 | 复旦大学 | Vulcanized cobalt-nickel/graphene/carbon nano fiber composite material and preparation method thereof |
| CN106082188A (en) * | 2016-06-12 | 2016-11-09 | 陈超 | A kind of preparation method of transition metal nitrogen and sulphur codope three-dimensional grapheme material |
| CN106328947A (en) * | 2016-10-12 | 2017-01-11 | 北京化工大学 | Graphene aerogel loaded two-phase transition metal sulfide as well as preparation method and application thereof |
| CN107393725A (en) * | 2017-06-20 | 2017-11-24 | 中国科学院福建物质结构研究所 | A kind of carbon material supported NiCo of porous, electrically conductive2O4Composite and its preparation method and application |
-
2018
- 2018-03-29 CN CN201810269322.4A patent/CN108411324A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105244482A (en) * | 2015-09-12 | 2016-01-13 | 复旦大学 | Nickel cobalt sulfide/graphene/carbon nanotube composite material and preparation method and application thereof |
| CN105296970A (en) * | 2015-09-25 | 2016-02-03 | 上海交通大学 | Method for preparing nitrogen-doped graphene and nickel sulfide quantum dot nanometer composite material |
| CN105293590A (en) * | 2015-10-16 | 2016-02-03 | 复旦大学 | Vulcanized cobalt-nickel/graphene/carbon nano fiber composite material and preparation method thereof |
| CN106082188A (en) * | 2016-06-12 | 2016-11-09 | 陈超 | A kind of preparation method of transition metal nitrogen and sulphur codope three-dimensional grapheme material |
| CN106328947A (en) * | 2016-10-12 | 2017-01-11 | 北京化工大学 | Graphene aerogel loaded two-phase transition metal sulfide as well as preparation method and application thereof |
| CN107393725A (en) * | 2017-06-20 | 2017-11-24 | 中国科学院福建物质结构研究所 | A kind of carbon material supported NiCo of porous, electrically conductive2O4Composite and its preparation method and application |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109378483A (en) * | 2018-10-09 | 2019-02-22 | 大连理工大学 | A kind of novel magnesium air cell catalyst layer material, preparation process and application |
| CN111111725A (en) * | 2018-12-10 | 2020-05-08 | 天津大学 | Graphite-like carbon nitride supported nickel-cobalt-sulfur particle composite material, preparation method and application thereof |
| CN109518219A (en) * | 2018-12-24 | 2019-03-26 | 江苏大学 | A kind of preparation method and applications of graphene-based nickel cobalt bimetallic oxygen-separating catalyst |
| CN109659544A (en) * | 2018-12-24 | 2019-04-19 | 肇庆市华师大光电产业研究院 | A kind of lithium/anode material of lithium-ion battery preparation method of graphene coated bimetallic sulfide |
| CN109659544B (en) * | 2018-12-24 | 2021-03-16 | 肇庆市华师大光电产业研究院 | Preparation method of graphene-coated bimetallic sulfide lithium/sodium ion battery negative electrode material |
| CN111383848A (en) * | 2018-12-27 | 2020-07-07 | 郑州轻工业学院 | graphene-CoNi for super capacitor2S4Nanocomposite and method for preparing same |
| CN109675605A (en) * | 2019-01-09 | 2019-04-26 | 上海应用技术大学 | A kind of Ni/Co-NCs liberation of hydrogen material, preparation method and applications |
| CN109759066A (en) * | 2019-01-29 | 2019-05-17 | 济南大学 | A kind of preparation method for the cobalt nickel bimetal oxide oxygen-separating catalyst that boron doping is graphene-supported |
| CN109759066B (en) * | 2019-01-29 | 2022-06-28 | 济南大学 | Preparation method of boron-doped graphene-loaded cobalt-nickel bimetallic oxide oxygen evolution catalyst |
| CN109672075A (en) * | 2019-02-18 | 2019-04-23 | 哈尔滨工程大学 | A kind of preparation method of multi-wavelength optical fiber laser and its curing nickel mode-locking device |
| CN109806887A (en) * | 2019-02-22 | 2019-05-28 | 沈阳师范大学 | A kind of electrolysis aquatic products hydrogen catalyst and preparation method thereof |
| CN109806887B (en) * | 2019-02-22 | 2021-09-24 | 沈阳师范大学 | Catalyst for producing hydrogen by electrolyzing water and preparation method thereof |
| CN109759120A (en) * | 2019-03-07 | 2019-05-17 | 燕山大学 | A kind of nitrogen, nickel co-doped cobaltous selenide ultrathin nanometer piece and its preparation method and application |
| CN109939716A (en) * | 2019-04-10 | 2019-06-28 | 黑龙江大学 | A kind of nitrogen vacancy carbon-supported catalysts and preparation method thereof for hydrogen manufacturing |
| CN109939716B (en) * | 2019-04-10 | 2022-04-29 | 黑龙江大学 | Nitrogen vacancy carbon-based catalyst for hydrogen production and preparation method thereof |
| CN109950512A (en) * | 2019-04-19 | 2019-06-28 | 陕西科技大学 | A kind of nitrogen sulphur codope three-dimensional grapheme and transient metal sulfide composite material and its universality preparation method and application |
| CN110280271A (en) * | 2019-06-06 | 2019-09-27 | 中南林业科技大学 | The preparation method of OER composite electrocatalyst |
| CN110280271B (en) * | 2019-06-06 | 2022-09-09 | 中南林业科技大学 | Preparation method of OER composite electrocatalyst |
| CN110336047B (en) * | 2019-07-16 | 2022-06-14 | 运城学院 | Preparation method of nickel cobalt sulfide/graphene composite material zinc-air battery bifunctional catalyst |
| CN110336047A (en) * | 2019-07-16 | 2019-10-15 | 运城学院 | Nickel cobalt sulfide/graphene composite material zinc and air cell bifunctional catalyst preparation method |
| CN111268671A (en) * | 2020-01-20 | 2020-06-12 | 广东工业大学 | Graphene-loaded tin-doped cobalt disulfide composite material and preparation method and application thereof |
| CN111573745A (en) * | 2020-05-06 | 2020-08-25 | 电子科技大学 | Preparation method of nickel-cobalt sulfide and graphene composite material rich in elemental sulfur |
| CN111573745B (en) * | 2020-05-06 | 2021-06-01 | 电子科技大学 | Preparation method of nickel-cobalt sulfide and graphene composite material rich in elemental sulfur |
| CN112226780A (en) * | 2020-10-17 | 2021-01-15 | 石河子大学 | NiCo for total water splitting2S4Preparation method of/nitrogen and sulfur co-doped reduced graphene oxide bifunctional electrocatalyst |
| CN112226780B (en) * | 2020-10-17 | 2023-09-29 | 石河子大学 | NiCo for full water dissolution 2 S 4 Preparation method of nitrogen/sulfur co-doped reduced graphene oxide bifunctional electrocatalyst |
| CN113174601A (en) * | 2021-04-27 | 2021-07-27 | 陕西科技大学 | Nickel sulfide electrocatalyst based on in-situ growth on nitrogen and sulfur co-doped reduced graphene oxide, and preparation method and application thereof |
| CN113403629A (en) * | 2021-06-07 | 2021-09-17 | 嘉寓氢能源科技(辽宁)有限公司 | Catalyst for water electrolysis hydrogen production system and preparation method thereof |
| CN114515552A (en) * | 2022-03-11 | 2022-05-20 | 山东大学 | NiCo alloy @ nitrogen-doped graphene hierarchical pore aerogel, preparation method thereof and application thereof in zinc-air battery |
| CN114515552B (en) * | 2022-03-11 | 2023-03-07 | 山东大学 | NiCo alloy @ nitrogen-doped graphene hierarchical pore aerogel, preparation method thereof and application thereof in zinc-air battery |
| CN115106112A (en) * | 2022-05-19 | 2022-09-27 | 华南理工大学 | Preparation method of 3D cobalt sulfide cocatalyst and application of cocatalyst in Fenton reaction |
| CN115106112B (en) * | 2022-05-19 | 2023-10-03 | 华南理工大学 | Preparation method of 3D cobalt sulfide cocatalyst and application of cocatalyst in catalyzing Fenton reaction |
| CN115261915A (en) * | 2022-08-29 | 2022-11-01 | 长春大学 | Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof |
| CN115261915B (en) * | 2022-08-29 | 2023-07-07 | 长春大学 | Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108411324A (en) | The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind and preparation and application | |
| CN109234755B (en) | Layered double-metal hydroxide composite structure electrocatalyst and preparation method thereof | |
| CN108736031B (en) | Self-supporting PtCo alloy nanoparticle catalyst and preparation method and application thereof | |
| CN107904614B (en) | A kind of Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode and the preparation method and application thereof | |
| CN104857976B (en) | A kind of three-dimensional molybdenum disulfide nano flower graphene composite material and its application | |
| CN108796551B (en) | Sea urchin-shaped cobalt sulfide catalyst loaded on foamed nickel, preparation method thereof and application of catalyst as electrolyzed water oxygen evolution catalyst | |
| CN109019602A (en) | Be carbonized molybdenum material, molybdenum carbide vulcanization molybdenum composite material and preparation method and application | |
| CN109908938A (en) | A kind of preparation method of Novel electrolytic water Oxygen anodic evolution catalyst Co@NC/CNT | |
| CN110373685B (en) | NiS2-MoS2PVEIB/PPy/GO material and HER electrocatalytic modified electrode based on same | |
| CN113388847B (en) | Prussian blue analogue derived metal sulfide/nitrogen-doped carbon electrocatalyst and preparation method and application thereof | |
| CN113026045B (en) | Foam nickel loaded Ni (OH) 2 Preparation method of/FeOOH nano-flower material | |
| CN108892175A (en) | A kind of preparation method and electro-catalysis application having defective vanadium doping molybdenum disulfide nano flower | |
| Chang et al. | Fabrication of bimetallic Co/Zn leaf blade structure template derived Co3O4-ZIF/Zn and its ORR catalytic performance for MFC | |
| Wang et al. | Dissolution reconstruction of electron-transfer enhanced hierarchical NiSx-MoO2 nanosponges as a promising industrialized hydrogen evolution catalyst beyond Pt/C | |
| CN108358181A (en) | A kind of the evolving hydrogen reaction elctro-catalyst and preparation method and application of phosphide | |
| CN113104862A (en) | Method for rapidly preparing Prussian blue or analogues thereof in batches and application of method | |
| Lv et al. | Energy-efficient hydrogen production via electrochemical methanol oxidation using a bifunctional nickel nanoparticle-embedded carbon prism-like microrod electrode | |
| CN105449230A (en) | LaCoO3/N-rGO compound and preparation method and application method therefor | |
| CN110504456A (en) | It is a kind of based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode and its preparation method and application | |
| CN110699701B (en) | Foam nickel loaded with metal nickel and vanadium trioxide compound and preparation method and application thereof | |
| Li et al. | Bimetal-MOF and bacterial cellulose-derived three-dimensional N-doped carbon sheets loaded Co/CoFe nanoparticles wrapped graphite carbon supported on porous carbon nanofibers: An efficient multifunctional electrocatalyst for Zn-air batteries and overall water splitting | |
| CN111995760A (en) | Cobalt-metal organic framework nanosheet and preparation method and application thereof | |
| CN109860645B (en) | Preparation method and application of biogel nitrogen fixation doped porous carbon | |
| Wang et al. | Synchronous Electrocatalytic Design of Architectural and Electronic Structure Based on Bifunctional LDH‐Co3O4/NF toward Water Splitting | |
| CN109763139A (en) | α-Co(OH)2/ PPy/GO nanometer sheet and OER electro-catalysis modified electrode based on it |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180817 |
|
| RJ01 | Rejection of invention patent application after publication |