CN109485103A - A kind of cobalt doped ferrous disulfide Porous hollow flower-like nanometer raw powder's production technology of defect and electro-catalysis application - Google Patents

A kind of cobalt doped ferrous disulfide Porous hollow flower-like nanometer raw powder's production technology of defect and electro-catalysis application Download PDF

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CN109485103A
CN109485103A CN201811512094.5A CN201811512094A CN109485103A CN 109485103 A CN109485103 A CN 109485103A CN 201811512094 A CN201811512094 A CN 201811512094A CN 109485103 A CN109485103 A CN 109485103A
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cobalt
ferrous disulfide
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孙旭
郭成英
高令峰
马晓晶
匡轩
魏琴
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University of Jinan
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Abstract

The present invention provides a kind of defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer raw powder's production technology of tool and electro-catalysis applications.Firstly, preparing iron, cobalt reaction solution, heating synthesizes amorphous Co ferrite Nano powder；Then solvent-thermal method carries out vulcanization reaction and cobalt doped ferrous disulfide flower-like nanometer powder is made；Finally, making annealing treatment under inert gas protection, defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder is obtained.Defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder application produces oxygen reaction (OER) to electro-catalysis and has excellent catalytic properties, and overpotential is down to 0.270 V(relative standard hydrogen electrode), Tafel slope is down to 40 mV/dec.

Description

A kind of preparation side of the cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder of defect Method and electro-catalysis application
Technical field
The present invention relates to the preparation of inorganic nanometer powder and application fields, and in particular to one kind is based on solvent-thermal method preparation tool The method of defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder and application in electrocatalytic decomposition water.
Background technique
The pollutant that the scarcity of the fossil fuels such as petroleum, coal and its exergonic process are discharged is sustainable development The significant problem faced, it is contemplated that the increasingly increase that people require quality of life is explored and cleans, is efficient, reproducible novel The energy (wind energy, tide energy, Hydrogen Energy, solar energy etc.) has become the focus of world today's research.It is worth noting that, hydrogen energy source because Its continuous-stable, cleaning is renewable, energy density is high etc., and superiority feature successfully attracts attention.Therefore, clean, Efficiently, safe electrocatalytic decomposition aquatic products hydrogen method has obtained in-depth study and has achieved important breakthrough.However, electric so far Catalytic decomposition aquatic products hydrogen is still faced with the problems such as overpotential is high, dynamics is slow, seriously hinders the industrialized production of Hydrogen Energy, because How this reduces overpotential, accelerates reaction rate to reduce energy consumption and realize that hydrogen economy is concerned.It is well known that noble metal (for example, platinum, ruthenium) is the best electrocatalytic decomposition water catalyst of current effect, however noble metal rare limited, valence on earth Lattice valuableness makes the industrial applications still faces enormous challenge of electrocatalytic decomposition water.So seeking cheap and easy to get, rich content, new Clever efficient electrolysis water catalyst is extremely urgent.
Recent report discovery, transition metal is due to rich content, cheap, electronic structure easy-regulating, chemistry abundant The advantages that valence state, shows excellent performance in fields such as battery, electro-catalysis, supercapacitors, especially leads in electro-catalysis water decomposition Domain, which is had excellent performance, to be attracted attention.However, transition metal generally has, band gap width is big, electronics transfer resistance is big, living Property site it is few the disadvantages of so that it is still faced significant challenge on becoming ideal elctro-catalyst road.As people are to transition metal The development of understanding further goed deep into and benefit from various control measures instantly, transition metal will become most ergastic electricity and urge Change one of candidate.In addition, vulcanization is as a kind of optimising and adjustment material electronics structure and active site to improve material catalysis The means of property, which have been obtained, to be widely applied.
Modification regulation is carried out to nano material with various effective chemical means, the intrinsic catalytic performance of material may be implemented Optimization.In many chemical means, doping and manufacturing defect may be implemented as a kind of simple, effective performance control measures Optimization to performances such as material coordination environment, active site, electronic structures.For example, we it has been reported that pass through vanadium metal former The optimising and adjustment of molybdenum disulfide electronic structure is realized in son doping, reduces molybdenum disulfide forbidden bandwidth, its catalytic performance of final optimization pass. Cation doping usually can be with the electronic structure of controlled material to promote catalytic activity, and after cation introduces, Ke Yigai The local coordination environment for becoming intrinsic material, there is important application value to the slight change of surrounding space structure, while doped with Conducive to the more defect sites of creation.In addition, annealing keeps material crystal form more perfect, and manufacturing defect on the surface of the material, make to receive Rice piece surface has portion fractures and gap, forms Porous hollow nanostructure, effectively reduces volume during cell reaction Catalytic brought by expanding declines problem, significantly improves the stability of material, and has increased considerably and electrolyte Contact area to promoting catalytic activity.In recent years, by cation doping and manufacturing defect realize to the activity of catalyst into Row Effective Regulation becomes the important method of catalyst optimization.In consideration of it, the present invention provides a kind of defective cobalt dopeds two of tool The catalysis material of iron sulfide significantly promotes catalysis by optimising and adjustment electronic structure, creation defect sites, raising turnover frequency Activity.
Summary of the invention
1. a kind of simple preparation method of the cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder of defect, step is such as Under: (1) cobalt, the iron pre-reaction solution of special ratios are prepared, heating reaction obtains the amorphous ferro-cobalt oxygen of taupe after a certain period of time Body nano-powder；(2) sulphur source compound and amorphous Co ferrite Nano powder carry out solvent thermal reaction, and reaction is after a certain period of time Obtain cobalt doped ferrous disulfide flower-like nanometer powder；(3) cobalt doped ferrous disulfide flower-like nanometer powder is placed in tube furnace It is made annealing treatment under inert atmosphere, obtains defect cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder.
2. a kind of simple preparation method of the cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder of defect, step (1) In, cobalt source is cabaltous nitrate hexahydrate, cobalt chloride hexahydrate, acetylacetone cobalt, potassium cobalticyanide, four water cobalt acetates, cobalt sesquioxide One or more of combination, concentration be 0.01 ~ 0.06 mol/L；It is optimal be cabaltous nitrate hexahydrate, cobalt chloride hexahydrate, Optimal concentration is 0.02 ~ 0.04 mol/L.
3. a kind of simple preparation method of the cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder of defect, step (1) In, source of iron is one or more of Fe(NO3)39H2O, Iron(III) chloride hexahydrate, the potassium ferricyanide, ferric citrate, ferric sulfate Combination, concentration be 0.03 ~ 0.2 mol/L；Optimal is Fe(NO3)39H2O, Iron(III) chloride hexahydrate；Concentration is optimal to be 0.06 ~ 0.12 mol/L。
4. a kind of simple preparation method of the cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder of defect, step (1) In, the molar ratio of cobalt source and source of iron is 1 ~ 2: 3 ~ 6；Optimal is 1 ~ 2: 2 ~ 4.
5. a kind of simple preparation method of the cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder of defect, the step Suddenly in (1), heating reaction temperature is 180oC ~ 220 oC, reaction time are 10 ~ 30 h；Optimal Temperature is 190oC ~ 200 oC, peak optimization reaction time are 16 ~ 20 h.
6. a kind of simple preparation method of the cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder of defect, the step Suddenly in (2), sulphur source is the combination of one or more of thioacetamide, thiocarbamide, vulcanized sodium, lawesson reagent, and sulphur source solution is dense Degree is 0.05 ~ 0.3 mol/L；Optimal sulphur source is thioacetamide, lawesson reagent, and optimal sulphur source concentration is 0.1 ~ 0.2 mol/L。
7. a kind of simple preparation method of the cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder of defect, the step Suddenly in (2), the concentration of amorphous Co ferrite Nano powder is 0.6 ~ 1.8 mg/mL, amorphous Co ferrite Nano powder Optimal concentration be 1 ~ 1.25 mg/mL.
8. a kind of simple preparation method of the cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder of defect, the step Suddenly in (2), reaction temperature 150oC ~ 190 oC, reaction time are 8 ~ 17 h；Peak optimization reaction temperature is 180oC ~ 190 oC, peak optimization reaction time are 10 ~ 15 h.
9. a kind of simple preparation method of the cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder of defect, the step Suddenly it in (3), is placed in tube furnace and is passed through inert gas N2Or Ar, annealing temperature 400 oC ~ 600 oC, annealing time be 5 ~ 8 h；Optimal annealing temperature is 450 oC ~ 500 oC, optimal annealing time is 6 ~ 7 h.
10. the simple preparation and electro-catalysis of a kind of cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder of defect are answered With using three-electrode system, the progress electrocatalytic decomposition aquatic products oxygen performance test on occasion China 660E electrochemical workstation, to be coated with Glass-carbon electrode with cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder is working electrode, with platinum electrode be to electrode, Using Ag/AgCl electrode as reference electrode；Using 1 mol/L potassium hydroxide solution as electrolyte；It is electrolysis with H-type glass electrolytic cell Reaction unit.
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
Step 1: taking 50 mL hydrothermal reaction kettle of use for laboratory, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner. It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, Fe(NO3)39H2O (0.8080 is sequentially added under stirring G, 2.0 mmol), cabaltous nitrate hexahydrate (0.2910 g, 1.0 mmol), the sealing of hydro-thermal autoclave is placed on 190 °C of baking 18 h of case inside holding.After natural cooling, respectively with obtaining amorphous ferro-cobalt oxygen after deionized water, ethyl alcohol centrifuge washing vacuum drying Body nano-powder.
Step 2: taking 50 mL hydrothermal reaction kettle of use for laboratory, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylene (PTFE) Liner.It takes 40 mL that dehydrated alcohol is gone to be added in 50 mL polytetrafluoroethylliner liners, sequentially adds thioacetamide under stirring (0.3757 g, 5.0 mmol), amorphous Co ferrite Nano powder (50 mg), persistently stirs 3 h, then by hydro-thermal high pressure Kettle sealing is placed on 180 °C of 12 h of baking oven inside holding.After natural cooling, dehydrated alcohol centrifuge washing vacuum drying is used respectively After obtain black cobalt doped ferrous disulfide flower-like nanometer powder.
Step 3: cobalt doped ferrous disulfide flower-like nanometer powder is placed in tube furnace in N2With 1 under gas shieldedoC/min Heating rate, 500oC keeps the temperature 6 h, then natural cooling, obtain having defective black cobalt doped ferrous disulfide it is porous in Empty flower-like nanometer powder.
Step 4: having defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder electrolysis water application
1. weighing 5 mg has defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder, be added to 1mL ethyl alcohol with The in the mixed solvent (volume ratio of ethyl alcohol and water is 3: 7) of water, while 50 μ L Nafion solutions are added, ultrasound 10 minutes, Obtain black 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 cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder as working electrode, with Platinum electrode is to electrode, and Ag/AgCl electrode is reference electrode.Using 1 mol/L potassium hydroxide solution as electrolyte, with H-type glass Electrolytic cell is reaction unit.
3. to be coated with the glass-carbon electrode for having defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder as work Electrode 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. Sampling interval is 0.001 V, and 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 cobalt doped ferrous 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 cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder as work Electrode 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, and low frequency is 0.1 Hz.Amplitude is 0.005 V, and quiescent time is 2 s.Through data processing and calculating Afterwards, have defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder application to OER excellent effect, be catalyzed water decomposition The overpotential for producing oxygen is 0.270 V(relative standard hydrogen electrode), Tafel slope is 40 mV/dec.
Embodiment 2
Step 1: taking 50 mL hydrothermal reaction kettle of use for laboratory, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner. It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, cobalt chloride hexahydrate (0.3569 is sequentially added under stirring G, 1.5 mmol), cobalt chloride hexahydrate (0.4054 g, 1.5 mmol), the sealing of hydro-thermal autoclave is placed on 200 °C of baking 20 h of case inside holding.After natural cooling, respectively with obtaining amorphous ferro-cobalt oxygen after deionized water, ethyl alcohol centrifuge washing vacuum drying Body nano-powder.
Step 2: taking 50 mL hydrothermal reaction kettle of use for laboratory, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylene (PTFE) Liner.It takes 40 mL that dehydrated alcohol is gone to be added in 50 mL polytetrafluoroethylliner liners, sequentially adds lawesson reagent under stirring (1.6179 g, 4.0 mmol), amorphous Co ferrite Nano powder (40 mg), persistently stirs 3 h, then by hydro-thermal high pressure Kettle sealing is placed on 190 °C of 10 h of baking oven inside holding.After natural cooling, dehydrated alcohol centrifuge washing vacuum drying is used respectively After obtain black cobalt doped ferrous disulfide flower-like nanometer powder.
Step 3: cobalt doped ferrous disulfide flower-like nanometer powder is placed in tube furnace under Ar gas shielded with 1oC/min Heating rate, 450oC keeps the temperature 7 h, then natural cooling, obtain having defective black cobalt doped ferrous disulfide it is porous in Empty flower-like nanometer powder.
Step 4: having defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder electrolysis water application
1. weighing 5 mg has defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder, be added to 1mL ethyl alcohol with The in the mixed solvent (volume ratio of ethyl alcohol and water is 3: 7) of water, while 50 μ L Nafion solutions are added, ultrasound 10 minutes, Obtain black 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 cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder as working electrode, with Platinum electrode is to electrode, and Ag/AgCl electrode is reference electrode.Using 1 mol/L potassium hydroxide solution as electrolyte, with H-type glass Electrolytic cell is reaction unit.
3. to be coated with the glass-carbon electrode for having defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder as work Electrode 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. Sampling interval is 0.001 V, and 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 cobalt doped ferrous 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 cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder as work Electrode 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, and low frequency is 0.1 Hz.Amplitude is 0.005 V, and quiescent time is 2 s.Through data processing and calculating Afterwards, have defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder application to OER excellent effect, be catalyzed water decomposition The overpotential for producing oxygen is 0.272 V(relative standard hydrogen electrode), Tafel slope is 40 mV/dec.
Embodiment 3
Step 1: taking 50 mL hydrothermal reaction kettle of use for laboratory, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner. Take 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, sequentially added under stirring acetylacetone cobalt (0.3206 g, 0.9 mmol), ferric citrate (1.1789 g, 4.5 mmol), by hydro-thermal autoclave sealing be placed in 180 °C of baking oven Keep the temperature 10 h.After natural cooling, received respectively with obtaining amorphous Conjugate ferrite after deionized water, ethyl alcohol centrifuge washing vacuum drying Rice flour body.
Step 2: taking 50 mL hydrothermal reaction kettle of use for laboratory, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylene (PTFE) Liner.It takes 40 mL that dehydrated alcohol is gone to be added in 50 mL polytetrafluoroethylliner liners, thiocarbamide (0.1522 is sequentially added under stirring G, 2.0 mmol), amorphous Co ferrite Nano powder (30 mg), persistently stir 3 h, then will hydro-thermal autoclave sealing after It is placed in 150 °C of 17 h of baking oven inside holding.It is black with being obtained after dehydrated alcohol centrifuge washing vacuum drying respectively after natural cooling Color cobalt doped ferrous disulfide flower-like nanometer powder.
Step 3: cobalt doped ferrous disulfide flower-like nanometer powder is placed in tube furnace in N2With 1 under gas shieldedoC/min Heating rate, 400oC keeps the temperature 8 h, then natural cooling, obtain having defective black cobalt doped ferrous disulfide it is porous in Empty flower-like nanometer powder.
Step 4: having defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder electrolysis water application
1. weighing 5 mg has defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder, be added to 1mL ethyl alcohol with The in the mixed solvent (volume ratio of ethyl alcohol and water is 3: 7) of water, while 50 μ L Nafion solutions are added, ultrasound 10 minutes, Obtain black 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 cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder as working electrode, with Platinum electrode is to electrode, and Ag/AgCl electrode is reference electrode.Using 1 mol/L potassium hydroxide solution as electrolyte, with H-type glass Electrolytic cell is reaction unit.
3. to be coated with the glass-carbon electrode for having defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder as work Electrode 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. Sampling interval is 0.001 V, and 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 cobalt doped ferrous 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 cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder as work Electrode 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, and low frequency is 0.1 Hz.Amplitude is 0.005 V, and quiescent time is 2 s.Through data processing and calculating Afterwards, have defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder application to OER excellent effect, be catalyzed water decomposition The overpotential for producing oxygen is 0.276 V(relative standard hydrogen electrode), Tafel slope is 42 mV/dec.
Embodiment 4
Step 1: taking 50 mL hydrothermal reaction kettle of use for laboratory, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner. It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, four acetate hydrate cobalts (0.5978 is sequentially added under stirring G, 2.4 mmol), cobalt sesquioxide (0.1991 g, 1.2 mmol), the sealing of hydro-thermal autoclave is placed on 220 °C of baking oven 30 h of inside holding.After natural cooling, respectively with obtaining amorphous Conjugate ferrite after deionized water, ethyl alcohol centrifuge washing vacuum drying Nano-powder.
Step 2: taking 50 mL hydrothermal reaction kettle of use for laboratory, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylene (PTFE) Liner.It takes 40 mL that dehydrated alcohol is gone to be added in 50 mL polytetrafluoroethylliner liners, vulcanized sodium (0.3122 is sequentially added under stirring G, 4.0 mmol), amorphous Co ferrite Nano powder (70 mg), persistently stir 3 h, then will hydro-thermal autoclave sealing after It is placed in 160 °C of 8 h of baking oven inside holding.After natural cooling, respectively with obtaining black after dehydrated alcohol centrifuge washing vacuum drying Cobalt doped ferrous disulfide flower-like nanometer powder.
Step 3: cobalt doped ferrous disulfide flower-like nanometer powder is placed in tube furnace under Ar gas shielded with 1oC/min Heating rate, 600oC keeps the temperature 5 h, then natural cooling, obtain having defective black cobalt doped ferrous disulfide it is porous in Empty flower-like nanometer powder.
Step 4: having defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder electrolysis water application
1. weighing 5 mg has defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder, be added to 1mL ethyl alcohol with The in the mixed solvent (volume ratio of ethyl alcohol and water is 3: 7) of water, while 50 μ L Nafion solutions are added, ultrasound 10 minutes, Obtain black 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 cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder as working electrode, with Platinum electrode is to electrode, and Ag/AgCl electrode is reference electrode.Using 1 mol/L potassium hydroxide solution as electrolyte, with H-type glass Electrolytic cell is reaction unit.
3. to be coated with the glass-carbon electrode for having defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder as work Electrode 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. Sampling interval is 0.001 V, and 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 cobalt doped ferrous 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 cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder as work Electrode 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, and low frequency is 0.1 Hz.Amplitude is 0.005 V, and quiescent time is 2 s.Through data processing and calculating Afterwards, have defective cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder application to OER excellent effect, be catalyzed water decomposition The overpotential for producing oxygen is 0.273 V(relative standard hydrogen electrode), Tafel slope is 41 mV/dec.

Claims (6)

1. a kind of cobalt doped ferrous disulfide Porous hollow flower-like nanometer raw powder's production technology of defect, which is characterized in that preparation Steps are as follows: (1) preparing a certain proportion of cobalt, iron pre-reaction liquid, heating reaction obtains amorphous Conjugate ferrite after a certain period of time Nano-powder；(2) sulphur source compound and amorphous Co ferrite Nano powder carry out solvent thermal reaction, obtain cobalt after a certain period of time Adulterate ferrous disulfide flower-like nanometer powder；(3) cobalt doped ferrous disulfide flower-like nanometer powder is placed in tube furnace, certain temperature Under, annealing obtains the cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder with defect under an inert atmosphere.
2. a kind of preparation side of the cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder of defect according to claim 1 Method, which is characterized in that in the step (1), cobalt source is cabaltous nitrate hexahydrate, cobalt chloride hexahydrate, acetylacetone cobalt, cobalt cyaniding The combination of one or more of potassium, four acetate hydrate cobalts, cobalt sesquioxide, in pre-reaction liquid the concentration of cobalt be 0.01 ~ 0.06 mol/L；Source of iron is Fe(NO3)39H2O, Iron(III) chloride hexahydrate, the potassium ferricyanide, ferric citrate, one in ferric sulfate Kind or several combinations, the concentration of iron is 0.03 ~ 0.2 mol/L in pre-reaction liquid；The molar ratio of cobalt and iron is 1 ~ 2: 3 ~ 6。
3. a kind of preparation side of the cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder of defect according to claim 1 Method, which is characterized in that in the step (1), pre-reaction liquid is in 180oC ~ 220 o10 ~ 30 h of heating reaction under C.
4. a kind of preparation side of the cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder of defect according to claim 1 Method, which is characterized in that in the step (2), sulphur source is one of thioacetamide, thiocarbamide, vulcanized sodium, lawesson reagent or several Kind combination, in solvent thermal reaction, sulphur source concentration is 0.05 ~ 0.3 mol/L, the concentration of amorphous Co ferrite Nano powder For 0.6 ~ 1.8 mg/mL.
5. a kind of preparation side of the cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder of defect according to claim 1 Method, which is characterized in that in the step (2), reaction temperature 150oC ~ 190 oC, reaction time are 8 ~ 17 h.
6. a kind of preparation side of the cobalt doped ferrous disulfide Porous hollow flower-like nanometer powder of defect according to claim 1 Method, which is characterized in that in the step (3), be placed in tube furnace and be passed through inert gas N2Or Ar, annealing temperature 400 oC ~ 600 oC, annealing time are 5 ~ 8 h, heating rate 1oC/min。
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CN111359634A (en) * 2020-03-18 2020-07-03 同济大学 Iron-doped cobalt disulfide nanoparticles and preparation method thereof
CN112960700A (en) * 2021-01-29 2021-06-15 天目湖先进储能技术研究院有限公司 Preparation method and application of iron-sulfur compound composite material doped with carbon or transition metal
CN114657596A (en) * 2022-03-09 2022-06-24 济南大学 Electro-catalytic nitrate radical reduction catalyst Fe-CoS2Preparation method of/CC

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CN108892175A (en) * 2018-08-31 2018-11-27 济南大学 A kind of preparation method and electro-catalysis application having defective vanadium doping molybdenum disulfide nano flower

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Publication number Priority date Publication date Assignee Title
CN111359634A (en) * 2020-03-18 2020-07-03 同济大学 Iron-doped cobalt disulfide nanoparticles and preparation method thereof
CN112960700A (en) * 2021-01-29 2021-06-15 天目湖先进储能技术研究院有限公司 Preparation method and application of iron-sulfur compound composite material doped with carbon or transition metal
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