CN108892175A - A kind of preparation method and electro-catalysis application having defective vanadium doping molybdenum disulfide nano flower - Google Patents
A kind of preparation method and electro-catalysis application having defective vanadium doping molybdenum disulfide nano flower Download PDFInfo
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- CN108892175A CN108892175A CN201811007161.8A CN201811007161A CN108892175A CN 108892175 A CN108892175 A CN 108892175A CN 201811007161 A CN201811007161 A CN 201811007161A CN 108892175 A CN108892175 A CN 108892175A
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- molybdenum disulfide
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- 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
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- 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 present invention provides a kind of preparation methods and electro-catalysis application for having defective vanadium doping molybdenum disulfide nano flower.Firstly, preparing molybdenum, sulphur pre-reaction liquid, heating reaction solution synthesizes defect molybdenum disulfide nano powder；Then, defect molybdenum disulfide nano powder synthesizes the spherical nano-powder of vanadium doping molybdenum disulfide with vanadium source compound hydro-thermal reaction；It makes annealing treatment under inert gas protection, obtains vanadium doping molybdenum disulfide nano flower-like nanometer powder.Have defective vanadium doping molybdenum disulfide and is applied to electro-catalysis production hydrogen reaction（HER）Middle catalytic performance is excellent, and overpotential is down to -0.160V（Relative standard's hydrogen electrode）, Tafel slope is down to 46 mV/dec.
Description
Technical field
The present invention relates to the preparation of inorganic nanometer powder and application fields, and in particular to one kind is had based on hydro-thermal method preparation
The method that the vanadium doping molybdenum disulfide nano of defect is spent and the application in electrocatalytic decomposition water.
Background technique
Pollution gas, the particle discharged in the finiteness and its consumption process of fossil fuel is world today's sustainable development
The significant problem that developable surface faces, with the enhancing of people's environmental protection consciousness, exploitation is cleaned, is efficient, reproducible new energy has become
For the focus studied at present.Due to the green energy resources such as solar energy, ocean energy, wind energy using exist intermittence, unstability,
The disadvantages of domain property, green energy resource can not be utilized generally on a large scale, and hydrogen as energy source is renewable, steady because having high-energy density, cleaning
The advantages that fixed continuous, causes the extensive concern of people.Electrocatalytic decomposition aquatic products hydrogen is as a kind of cleaning, efficient, safety, operation
The simple hydrogen methods that produce are shown one's talent in all voluminous hydrogen approach.However electrocatalytic decomposition aquatic products hydrogen be also faced with overpotential it is high,
The slow problem urgent need to resolve of dynamics.It is well known that noble metal（For example, platinum）The electrocatalytic decomposition best as current effect
Aquatic products hydrogen catalyst, however because it is expensive, the limited industrial applications for making electrocatalytic decomposition aquatic products hydrogen of content face it is huge
Challenge.So it is extremely urgent to seek cheap and easy to get, rich content, novelty, efficient production hydrogen catalyst.
Due to unique dimensional effect, nano-powder material has been assigned novel physicochemical properties, and leads in catalysis
Domain shows good application.Transient metal sulfide has important application in fields such as catalysis, batteries, for clean new energy
The development and utilization in source provides novel, efficient catalysis material.Existing document report transient metal sulfide because rich content,
It is cheap and easy to get to hold promise as efficient catalyst water decomposition production hydrogen.However, because its intrinsic low electric conductivity makes catalysis live
The promotion of property faces huge challenge.Vanadium, cobalt metal material are because of its excellent effect in terms of catalytic electrolysis water, various cobalt-baseds, vanadium
The design of base-catalyst becomes the important directions of catalyticing research with synthesis.As people understand transient metal sulfide property
Further deeply, and benefit from many nano ZnO control measures of current development, transient metal sulfide material
Using that will be widened significantly, significant Social benefit and economic benefit is generated.
Modification regulation is carried out to nano material using effective chemical means, changing for material intrinsic performance often may be implemented
It is kind, for optimizing its function with practical operation value and research significance.In many means, Heteroatom doping is as a kind of letter
Single, effective performance control measures, may be implemented the optimization to performances such as material conductivity, active site, stability.For example,
It has been reported that the regulation by cobalt atom doping realization to molybdenum dioxide nanosphere electronic structure, promotes leading for molybdenum dioxide nanosphere
Electrically, the optimization of catalytic performance is finally realized；It is doped in ferronickel bimolecular stratiform compound structure by cobalt atom,
Optimising and adjustment can also be can be carried out to the electrocatalysis of ferronickel bimolecular lamellar compound.Cation doping usually promotes material
Electric conductivity is to promote catalytic activity, and after cation introduces, thus it is possible to vary the local coordination environment of assertive evidence material, to surrounding
The slight change of space structure has important application value, while adulterating hetero atom and being easier to create more defect sites.Closely
Year, realize that carrying out Effective Regulation to the activity of catalyst becomes the important method of catalyst optimization by cation doping.In mistake
It crosses in metal sulfide to regulate and control to realize that the optimization of catalytic performance is still problem to be solved by cation doping.Probe into sun from
The change of bring electronic property after son doping, and the optimization of its catalytic performance is studied, novel electro-catalysis is realized for design
Agent is of great significance.In consideration of it, the present invention provides a kind of materials of vanadium doping molybdenum disulfide by improving electric conductivity, increasing
Active site promotes catalytic activity.
Summary of the invention
1. a kind of preparation method for having defective vanadium doping molybdenum disulfide nano flower, includes the following steps：（1）It prepares
Molybdenum, the sulphur pre-reaction liquid of special ratios, heating reaction certain time synthesize defect molybdenum disulfide nano powder；（2）Vanadium source chemical combination
Object and defect molybdenum disulfide nano powder hydro-thermal reaction obtain the spherical nano-powder intermediate of vanadium doping molybdenum disulfide；（3）By vanadium
Doping molybdenum disulfide nano powder intermediate is placed in tube furnace to be made annealing treatment under inert gas protection, finally obtains vanadium doping
Molybdenum disulfide nano flower-like nanometer powder.
2. a kind of simple preparation method for having defective vanadium doping molybdenum disulfide nano flower, the step（1）In, molybdenum
Source is that molybdenum source is ammonium molybdate, molybdenum trioxide, four thio ammonium molybdate, acetyl acetone, molybdenum pentachloride, one of sodium molybdate or several
The combination of kind, optimal is ammonium molybdate, sodium molybdate；The concentration of molybdenum saline solution is 0.1 ~ 0.15 mol/L, it is optimal be 0.1 ~
0.13 mol/L。
3. a kind of simple preparation method for having defective vanadium doping molybdenum disulfide nano flower, the step（1）In, sulphur
Source be one or more of potassium rhodanide, thioacetamide, cysteine, thiocarbamide, it is optimal to be：Thioacetamide, thiocarbamide；Sulphur
Source concentration is 0.35 ~ 1.3 mol/L, and optimal is 0.8 ~ 1.0 mol/L.
4. a kind of simple preparation method for having defective vanadium doping molybdenum disulfide nano flower, the step（1）In, molybdenum
The molar ratio of source and sulphur source is 1 ~ 2:5 ~ 10, optimal is 1: 8.
5. a kind of simple preparation method for having defective vanadium doping molybdenum disulfide nano flower, the step（1）In, instead
Answering temperature is 180oC ~ 210 oC reacts 20 ~ 30 h, and optimal is 190 ~ 200oC reacts 24 ~ 26 h.
6. a kind of simple preparation method for having defective vanadium doping molybdenum disulfide nano flower, the step（2）In, vanadium
Source is inclined alum acid ammonium, sodium orthovanadate, vanadic anhydride, vanadium trioxide, vanadyl acetylacetonate, vanadyl oxalate, sodium metavanadate, sulphur
The combination of one or more of sour vanadium, vanadium trichloride, potassium vanadate, vanadium phosphate, it is optimal to be：Sodium metavanadate, sodium orthovanadate；Vanadium source
Concentration of aqueous solution is 0.02 ~ 0.08 mol/L, and optimal is 0.03 ~ 0.05 mol/L.
7. a kind of simple preparation method for having defective vanadium doping molybdenum disulfide nano flower, the step（2）In, it lacks
The concentration for falling into molybdenum disulfide is 0.3 ~ 0.5 mol/L, and optimal is 0.35 ~ 0.4 mol/L.
8. a kind of simple preparation for having defective vanadium doping molybdenum disulfide nano flower, is characterized in that, the step（2）
In, reaction temperature 120oC ~ 150 oC reacts 10 ~ 15 h, and optimal is 130oC ~ 145 oC, reaction 12 ~ 15
h。
9. a kind of simple preparation for having defective vanadium doping molybdenum disulfide nano flower, is characterized in that, the step（3）
In, inert gas N2, Ar, annealing temperature be 250 ~ 350oC, annealing time are 2 ~ 5 h, and optimal is 290 ~ 320oC
Anneal 3 ~ 4 h.
10. a kind of simple preparation for having defective vanadium doping molybdenum disulfide nano flower and electro-catalysis application, feature exist
In using three-electrode system, the progress electrocatalytic decomposition aquatic products oxygen performance test on occasion China 660E electrochemical workstation, to be coated with
The glass-carbon electrode of molybdenum disulfide with vanadium doping is working electrode, is to electrode, using Ag/AgCl electrode as reference with platinum electrode
Electrode；Using 1 mol/L potassium hydroxide solution as electrolyte；Using H-type glass electrolytic cell as electrolysis reaction device.
Specific embodiment mode
In order to further appreciate that the present invention, the preferred embodiment of the invention is described below with reference to embodiment, but should
Understand, these descriptions are only further explanation the features and advantages of the present invention, rather than limiting to the claimed invention.
Embodiment 1
The first step：50 mL hydrothermal reaction kettle of use for laboratory is taken, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner.
It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, sequentially adds molybdenum trioxide under stirring（0.5760 g,
4.0 mmol）, potassium rhodanide（1.9436 g, 20 mmol）, the sealing of hydro-thermal autoclave is placed on to 180 °C of baking oven inside holding
30 h.After natural cooling, respectively with obtaining having defective black curing after deionized water, ethyl alcohol centrifuge washing vacuum drying
Molybdenum nano-powder.
Second step：50 mL hydrothermal reaction kettle of use for laboratory is taken, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylene (PTFE)
Liner.It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, sequentially adds vanadium trichloride under stirring（0.1573
G, 1.0 mmol）, defect molybdenum disulfide（1.9208 g, 12 mmol）, continue to stir 1 h, it then will be after the sealing of hydro-thermal autoclave
It is placed in 150 °C of 10 h of baking oven inside holding.After natural cooling, obtained after using deionized water, ethyl alcohol centrifuge washing vacuum drying respectively
To the defective vanadium doping molybdenum disulfide nano powder of tool.
Third step：Vanadium doping molybdenum disulfide nano powder is placed in tube furnace under protection of argon gas with 2oThe liter of C/min
Warm rate, 350oC keeps the temperature 5 hours, then natural cooling, obtains having defective black vanadium doping molybdenum disulfide nano flower-shaped
Nano-powder.
4th step：Has defective vanadium doping molybdenum disulfide nano flower-like nanometer powder electrolysis water application
1. weighing 5 mg has defective vanadium doping molybdenum disulfide nano flower-like nanometer powder, it is added to 1mL ethyl alcohol and water
In the mixed solvent（The volume ratio of ethyl alcohol and water is 3: 7）, while 50 μ L Nafion solutions are added, ultrasound 10 minutes obtains
Black clarifies dispersion liquid.The 5 above-mentioned dispersion liquids of μ L are taken, drop coating is 3 mm in glassy carbon electrode surface, glass-carbon electrode diameter, is dried in the air naturally
It is dry.
2. using three-electrode system, electrocatalytic decomposition water H2-producing capacity is carried out on occasion China 660E electrochemical workstation and is surveyed
Examination.To be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano flower-like nanometer powder as working electrode, with platinum electricity
Extremely to electrode, Ag/AgCl electrode is reference electrode.Using 0.5 mol/L sulfuric acid solution as electrolyte, with H-type glass electrolytic cell
For reaction unit.
3. to be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano flower-like nanometer powder as work electricity
Pole carries out cyclic voltammetry in three-electrode system, activates sample.Cyclic voltammetry voltage range is 0 ~ 0.8 V,
0.8 V of maximum potential, 0 V of potential minimum, beginning current potential are 0 V, and termination current potential is 0.8 V.Sweep speed is 0.05 V/s.It adopts
0.001 V is divided between sample, time of repose is 2 s, and scanning number of segment is 500.
4. after cyclic voltammetry, to be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano material
For working electrode, linear voltage sweep test is carried out in three-electrode system, voltage range is 0 ~ 0.8 V.Initial potential is 0
V, termination current potential are 0.8 V.Sweep speed is 5 mV/s.Sampling interval is 0.001 V.Time of repose is 2 s.
5. to be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano flower-like nanometer powder as work electricity
Pole carries out ac impedance measurement to catalyst, to carry out kinetic Process Analysis.Parameter setting is as follows, initial potential 0.6
V, high frequency are 100000 Hz, low frequency 0.1Hz.Amplitude is 0.005 V, and quiescent time is 2 s.After data processing and calculating,
Have defective vanadium doping molybdenum disulfide nano flower-like nanometer powder in the beneficial effect for being applied to OER, is catalyzed water electrolysis and produces
The overpotential of oxygen is -0.164 V（Relative standard's hydrogen electrode）, Tafel slope is 48 mV/dec.
Embodiment 2
The first step：50 mL hydrothermal reaction kettle of use for laboratory is taken, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner.
It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, sequentially adds ammonium molybdate under stirring（0.7840 g, 4.0
mmol）, thioacetamide（2.4042 g, 32 mmol）, the sealing of hydro-thermal autoclave is placed on to 190 °C of baking oven inside holding 26
h.After natural cooling, respectively with obtaining having defective black molybdenum disulfide after deionized water, ethyl alcohol centrifuge washing vacuum drying
Nano-powder.
Second step：50 mL hydrothermal reaction kettle of use for laboratory is taken, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylene (PTFE)
Liner.It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, inclined alum acid ammonium is sequentially added under stirring（0.1404
G, 1.2 mmol）, defect molybdenum disulfide（2.4011 g, 15 mmol）, continue to stir 1 h, it then will be after the sealing of hydro-thermal autoclave
It is placed in 130 °C of 15 h of baking oven inside holding.After natural cooling, obtained after using deionized water, ethyl alcohol centrifuge washing vacuum drying respectively
To the defective vanadium doping molybdenum disulfide nano powder of tool.
Third step：Vanadium doping molybdenum disulfide nano powder is placed in tube furnace in N2With 2 under protectionoThe heating of C/min
Rate, 300oC keeps the temperature 3 hours, then natural cooling, obtains having that defective black vanadium doping molybdenum disulfide nano is flower-shaped to be received
Rice flour body.
4th step：Has defective vanadium doping molybdenum disulfide nano flower-like nanometer powder electrolysis water application
1. weighing 5 mg has defective vanadium doping molybdenum disulfide nano flower-like nanometer powder, it is added to 1mL ethyl alcohol and water
In the mixed solvent（The volume ratio of ethyl alcohol and water is 3: 7）, while 50 μ L Nafion solutions are added, ultrasound 10 minutes obtains
Black clarifies dispersion liquid.The 5 above-mentioned dispersion liquids of μ L are taken, drop coating is 3 mm in glassy carbon electrode surface, glass-carbon electrode diameter, is dried in the air naturally
It is dry.
2. using three-electrode system, electrocatalytic decomposition water H2-producing capacity is carried out on occasion China 660E electrochemical workstation and is surveyed
Examination.To be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano flower-like nanometer powder as working electrode, with platinum electricity
Extremely to electrode, Ag/AgCl electrode is reference electrode.Using 0.5 mol/L sulfuric acid solution as electrolyte, with H-type glass electrolytic cell
For reaction unit.
3. to be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano flower-like nanometer powder as work electricity
Pole carries out cyclic voltammetry in three-electrode system, activates sample.Cyclic voltammetry voltage range is 0 ~ 0.8 V,
0.8 V of maximum potential, 0 V of potential minimum, beginning current potential are 0 V, and termination current potential is 0.8 V.Sweep speed is 0.05 V/s.It adopts
0.001 V is divided between sample, time of repose is 2 s, and scanning number of segment is 500.
4. after cyclic voltammetry, to be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano material
For working electrode, linear voltage sweep test is carried out in three-electrode system, voltage range is 0 ~ 0.8 V.Initial potential is 0
V, termination current potential are 0.8 V.Sweep speed is 5 mV/s.Sampling interval is 0.001 V.Time of repose is 2 s.
5. to be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano flower-like nanometer powder as work electricity
Pole carries out ac impedance measurement to catalyst, to carry out kinetic Process Analysis.Parameter setting is as follows, initial potential 0.6
V, high frequency are 100000 Hz, low frequency 0.1Hz.Amplitude is 0.005 V, and quiescent time is 2 s.After data processing and calculating,
Have defective vanadium doping molybdenum disulfide nano flower-like nanometer powder in the beneficial effect for being applied to OER, is catalyzed water electrolysis and produces
The overpotential of oxygen is -0.160 V（Relative standard's hydrogen electrode）, Tafel slope is 46 mV/dec.
Embodiment 3
The first step：50 mL hydrothermal reaction kettle of use for laboratory is taken, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner.
It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, sequentially adds sodium molybdate under stirring（1.2098 g, 5.0
mmol）, thiocarbamide（3.8060 g, 50 mmol）, the sealing of hydro-thermal autoclave is placed on to 200 °C of 24 h of baking oven inside holding.From
After so cooling, respectively with obtaining having defective black molybdenum disulfide nano after deionized water, ethyl alcohol centrifuge washing vacuum drying
Powder.
Second step：50 mL hydrothermal reaction kettle of use for laboratory is taken, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylene (PTFE)
Liner.It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, sequentially adds vanadic anhydride under stirring
（0.3640 g, 2.0 mmol）, defect molybdenum disulfide（2.8813 g, 18 mmol）, continue to stir 1 h, then by hydro-thermal high pressure
Kettle sealing is placed on 145 °C of 13 h of baking oven inside holding.After natural cooling, deionized water, ethyl alcohol centrifuge washing vacuum are used respectively
Obtain having defective vanadium doping molybdenum disulfide nano powder after drying.
Third step：Vanadium doping molybdenum disulfide nano powder is placed in tube furnace under Ar protection with 2oThe heating of C/min
Rate, 350oC keeps the temperature 3 hours, then natural cooling, obtains having that defective black vanadium doping molybdenum disulfide nano is flower-shaped to be received
Rice flour body.
4th step：Has defective vanadium doping molybdenum disulfide nano flower-like nanometer powder electrolysis water application
1. weighing 5 mg has defective vanadium doping molybdenum disulfide nano flower-like nanometer powder, it is added to 1mL ethyl alcohol and water
In the mixed solvent（The volume ratio of ethyl alcohol and water is 3: 7）, while 50 μ L Nafion solutions are added, ultrasound 10 minutes obtains
Black clarifies dispersion liquid.The 5 above-mentioned dispersion liquids of μ L are taken, drop coating is 3 mm in glassy carbon electrode surface, glass-carbon electrode diameter, is dried in the air naturally
It is dry.
2. using three-electrode system, electrocatalytic decomposition water H2-producing capacity is carried out on occasion China 660E electrochemical workstation and is surveyed
Examination.To be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano flower-like nanometer powder as working electrode, with platinum electricity
Extremely to electrode, Ag/AgCl electrode is reference electrode.Using 0.5 mol/L sulfuric acid solution as electrolyte, with H-type glass electrolytic cell
For reaction unit.
3. to be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano flower-like nanometer powder as work electricity
Pole carries out cyclic voltammetry in three-electrode system, activates sample.Cyclic voltammetry voltage range is 0 ~ 0.8 V,
0.8 V of maximum potential, 0 V of potential minimum, beginning current potential are 0 V, and termination current potential is 0.8 V.Sweep speed is 0.05 V/s.It adopts
0.001 V is divided between sample, time of repose is 2 s, and scanning number of segment is 500.
4. after cyclic voltammetry, to be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano material
For working electrode, linear voltage sweep test is carried out in three-electrode system, voltage range is 0 ~ 0.8 V.Initial potential is 0
V, termination current potential are 0.8 V.Sweep speed is 5 mV/s.Sampling interval is 0.001 V.Time of repose is 2 s.
5. to be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano flower-like nanometer powder as work electricity
Pole carries out ac impedance measurement to catalyst, to carry out kinetic Process Analysis.Parameter setting is as follows, initial potential 0.6
V, high frequency are 100000 Hz, low frequency 0.1Hz.Amplitude is 0.005 V, and quiescent time is 2 s.After data processing and calculating,
Have defective vanadium doping molybdenum disulfide nano flower-like nanometer powder in the beneficial effect for being applied to OER, is catalyzed water electrolysis and produces
The overpotential of oxygen is -0.163 V（Relative standard's hydrogen electrode）, Tafel slope is 46 mV/dec.
Embodiment 4
The first step：50 mL hydrothermal reaction kettle of use for laboratory is taken, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner.
It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, sequentially adds ammonium molybdate under stirring（0.8821 g, 4.5
mmol）, thiocarbamide（2.7403 g, 36 mmol）, the sealing of hydro-thermal autoclave is placed on to 195 °C of 25 h of baking oven inside holding.From
After so cooling, respectively with obtaining having defective black molybdenum disulfide nano after deionized water, ethyl alcohol centrifuge washing vacuum drying
Powder.
Second step：50 mL hydrothermal reaction kettle of use for laboratory is taken, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylene (PTFE)
Liner.It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, sequentially adds sodium orthovanadate under stirring（0.2759
G, 1.5 mmol）, defect molybdenum disulfide（2.2410 g, 14 mmol）, continue to stir 1 h, it then will be after the sealing of hydro-thermal autoclave
It is placed in 150 °C of 10 h of baking oven inside holding.After natural cooling, obtained after using deionized water, ethyl alcohol centrifuge washing vacuum drying respectively
To the defective vanadium doping molybdenum disulfide nano powder of tool.
Third step：Vanadium doping molybdenum disulfide nano powder is placed in tube furnace under Ar protection with 2oThe heating of C/min
Rate, 320oC keeps the temperature 3 hours, then natural cooling, obtains having that defective black vanadium doping molybdenum disulfide nano is flower-shaped to be received
Rice flour body.
4th step：Has defective vanadium doping molybdenum disulfide nano flower-like nanometer powder electrolysis water application
1. weighing 5 mg has defective vanadium doping molybdenum disulfide nano flower-like nanometer powder, it is added to 1mL ethyl alcohol and water
In the mixed solvent（The volume ratio of ethyl alcohol and water is 3: 7）, while 50 μ L Nafion solutions are added, ultrasound 10 minutes obtains
Black clarifies dispersion liquid.The 5 above-mentioned dispersion liquids of μ L are taken, drop coating is 3 mm in glassy carbon electrode surface, glass-carbon electrode diameter, is dried in the air naturally
It is dry.
2. using three-electrode system, electrocatalytic decomposition water H2-producing capacity is carried out on occasion China 660E electrochemical workstation and is surveyed
Examination.To be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano flower-like nanometer powder as working electrode, with platinum electricity
Extremely to electrode, Ag/AgCl electrode is reference electrode.Using 0.5 mol/L sulfuric acid solution as electrolyte, with H-type glass electrolytic cell
For reaction unit.
3. to be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano flower-like nanometer powder as work electricity
Pole carries out cyclic voltammetry in three-electrode system, activates sample.Cyclic voltammetry voltage range is 0 ~ 0.8 V,
0.8 V of maximum potential, 0 V of potential minimum, beginning current potential are 0 V, and termination current potential is 0.8 V.Sweep speed is 0.05 V/s.It adopts
0.001 V is divided between sample, time of repose is 2 s, and scanning number of segment is 500.
4. after cyclic voltammetry, to be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano material
For working electrode, linear voltage sweep test is carried out in three-electrode system, voltage range is 0 ~ 0.8 V.Initial potential is 0
V, termination current potential are 0.8 V.Sweep speed is 5 mV/s.Sampling interval is 0.001 V.Time of repose is 2 s.
5. to be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano flower-like nanometer powder as work electricity
Pole carries out ac impedance measurement to catalyst, to carry out kinetic Process Analysis.Parameter setting is as follows, initial potential 0.6
V, high frequency are 100000 Hz, low frequency 0.1Hz.Amplitude is 0.005 V, and quiescent time is 2 s.After data processing and calculating,
Have defective vanadium doping molybdenum disulfide nano flower-like nanometer powder in the beneficial effect for being applied to OER, is catalyzed water electrolysis and produces
The overpotential of oxygen is -0.161 V（Relative standard's hydrogen electrode）, Tafel slope is 47 mV/dec.
Embodiment 5
The first step：50 mL hydrothermal reaction kettle of use for laboratory is taken, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner.
It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, four or six generation ammonium molybdates is sequentially added under stirring（1.5617
G, 6.0 mmol）, cysteine（3.6347 g, 30 mmol）, the sealing of hydro-thermal autoclave is placed in 180 °C of baking oven and is protected
20 h of temperature.After natural cooling, respectively with obtaining having defective two sulphur of black after deionized water, ethyl alcohol centrifuge washing vacuum drying
Change molybdenum nano-powder.
Second step：50 mL hydrothermal reaction kettle of use for laboratory is taken, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylene (PTFE)
Liner.It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, inclined alum acid ammonium is sequentially added under stirring（0.3743
G, 3.2 mmol）, defect molybdenum disulfide（1.921 g, 12 mmol）, continue to stir 1 h, it then will be after the sealing of hydro-thermal autoclave
It is placed in 120 °C of 15 h of baking oven inside holding.After natural cooling, obtained after using deionized water, ethyl alcohol centrifuge washing vacuum drying respectively
To the defective vanadium doping molybdenum disulfide nano powder of tool.
Third step：Vanadium doping molybdenum disulfide nano powder is placed in tube furnace in N2With 2 under protectionoThe heating of C/min
Rate, 250oC keeps the temperature 2 hours, then natural cooling, obtains having that defective black vanadium doping molybdenum disulfide nano is flower-shaped to be received
Rice flour body.
4th step：Has defective vanadium doping molybdenum disulfide nano flower-like nanometer powder electrolysis water application
1. weighing 5 mg has defective vanadium doping molybdenum disulfide nano flower-like nanometer powder, it is added to 1mL ethyl alcohol and water
In the mixed solvent（The volume ratio of ethyl alcohol and water is 3: 7）, while 50 μ L Nafion solutions are added, ultrasound 10 minutes obtains
Black clarifies dispersion liquid.The 5 above-mentioned dispersion liquids of μ L are taken, drop coating is 3 mm in glassy carbon electrode surface, glass-carbon electrode diameter, is dried in the air naturally
It is dry.
2. using three-electrode system, electrocatalytic decomposition water H2-producing capacity is carried out on occasion China 660E electrochemical workstation and is surveyed
Examination.To be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano flower-like nanometer powder as working electrode, with platinum electricity
Extremely to electrode, Ag/AgCl electrode is reference electrode.Using 0.5 mol/L sulfuric acid solution as electrolyte, with H-type glass electrolytic cell
For reaction unit.
3. to be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano flower-like nanometer powder as work electricity
Pole carries out cyclic voltammetry in three-electrode system, activates sample.Cyclic voltammetry voltage range is 0 ~ 0.8 V,
0.8 V of maximum potential, 0 V of potential minimum, beginning current potential are 0 V, and termination current potential is 0.8 V.Sweep speed is 0.05 V/s.It adopts
0.001 V is divided between sample, time of repose is 2 s, and scanning number of segment is 500.
4. after cyclic voltammetry, to be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano material
For working electrode, linear voltage sweep test is carried out in three-electrode system, voltage range is 0 ~ 0.8 V.Initial potential is 0
V, termination current potential are 0.8 V.Sweep speed is 5 mV/s.Sampling interval is 0.001 V.Time of repose is 2 s.
5. to be coated with the glass-carbon electrode for having defective vanadium doping molybdenum disulfide nano flower-like nanometer powder as work electricity
Pole carries out ac impedance measurement to catalyst, to carry out kinetic Process Analysis.Parameter setting is as follows, initial potential 0.6
V, high frequency are 100000 Hz, low frequency 0.1Hz.Amplitude is 0.005 V, and quiescent time is 2 s.After data processing and calculating,
Have defective vanadium doping molybdenum disulfide nano flower-like nanometer powder in the beneficial effect for being applied to OER, is catalyzed water electrolysis and produces
The overpotential of oxygen is -0.168 V（Relative standard's hydrogen electrode）, Tafel slope is 49 mV/dec.
Claims (6)
1. a kind of preparation method for having defective vanadium doping molybdenum disulfide nano flower, which is characterized in that preparation step is as follows：
（1）Molybdenum, the sulphur pre-reaction liquid of special ratios are prepared, heating reaction obtains defect molybdenum disulfide nano powder after a certain period of time；（2）
Vanadium source compound and defect molybdenum disulfide nano powder carry out hydro-thermal reaction, obtain the spherical nano-powder of vanadium doping molybdenum disulfide；
（3）The spherical nano-powder of vanadium doping molybdenum disulfide is placed in tube furnace and is made annealing treatment under an inert atmosphere, vanadium doping two is obtained
Molybdenum sulfide nano flower-like nano-powder.
2. a kind of preparation method for having defective vanadium doping molybdenum disulfide nano flower according to claim 1, feature
It is, the step（1）In, molybdenum source is ammonium molybdate, molybdenum trioxide, molybdenum pentachloride, four thio ammonium molybdate, acetyl acetone, molybdenum
The combination of one or more of sour sodium, the concentration of molybdenum saline solution are 0.1 ~ 0.15 mol/L；Sulphur source is potassium rhodanide, sulphur
For one or more of acetamide, cysteine, thiocarbamide, sulphur source concentration is 0.35 ~ 1.3 mol/L；Molybdenum source and sulphur source
Molar ratio is 1 ~ 2: 5 ~10.
3. a kind of preparation method for having defective vanadium doping molybdenum disulfide nano flower according to claim 1, feature
It is, the step（1）In, heating reaction temperature is 180oC ~ 210 oC, reaction time are 20 ~ 30 h.
4. a kind of preparation method for having defective vanadium doping molybdenum disulfide nano flower according to claim 1, feature
It is, the step（2）In, vanadium source is inclined alum acid ammonium, sodium orthovanadate, vanadic anhydride, vanadium trioxide, acetylacetone,2,4-pentanedione oxygen
The combination of one or more of vanadium, vanadyl oxalate, sodium metavanadate, vanadic sulfate, vanadium trichloride, potassium vanadate, vanadium phosphate, vanadium
Concentration of aqueous solution is 0.02 ~ 0.08 mol/L, and the concentration of defect molybdenum disulfide nano powder is 0.3 ~ 0.5 mol/L.
5. a kind of preparation method for having defective vanadium doping molybdenum disulfide nano flower according to claim 1, feature
It is, the step（2）In, hydrothermal temperature 120oC ~ 150 oC, reaction time are 10 ~ 15 h.
6. a kind of preparation method for having defective vanadium doping molybdenum disulfide nano flower according to claim 1, feature exist
In the step（3）In, it is placed in tube furnace and is passed through inert gas N2Or Ar, annealing temperature are 250 ~ 350oC, when annealing
Between be 2 ~ 5 h.
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Application publication date: 20181127 |