CN109516506A - A kind of N doping CoFe2O4The preparation and electro-catalysis application of nano-powder - Google Patents

A kind of N doping CoFe2O4The preparation and electro-catalysis application of nano-powder Download PDF

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CN109516506A
CN109516506A CN201910078235.5A CN201910078235A CN109516506A CN 109516506 A CN109516506 A CN 109516506A CN 201910078235 A CN201910078235 A CN 201910078235A CN 109516506 A CN109516506 A CN 109516506A
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nano
powder
cofe
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cobalt
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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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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
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Abstract

The present invention provides a kind of N doping CoFe2O4The preparation method and its electro-catalysis application of nano-powder.Firstly, the obtained ferro-cobalt pre-reaction liquid of a certain proportion of cobalt, source of iron is added in reaction solution, heating ferro-cobalt pre-reaction liquid certain time obtains CoFe2O4Nano-powder；Then, CoFe2O4Nano-powder finally obtains N doping CoFe by calcining incorporation nitrogen under ammonia atmosphere2O4Nano-powder.N doping CoFe2O4Produced in electro-catalysis and show excellent catalytic activity in oxygen reaction (OER), overpotential is 0.282 V(relative standard hydrogen electrode), for Tafel slope down to 40 mV/dec, charge transfer resistance is reduced to 30 Ω.

Description

A kind of N doping CoFe2O4The preparation and electro-catalysis application of nano-powder
Technical field
The present invention relates to the preparation of inorganic nanometer powder and application fields, and in particular to one kind prepares nitrogen based on solvent-thermal method Adulterate CoFe2O4The method of nano-powder and its application in electro-catalysis water decomposition field.
Background technique
With the progress in epoch, people gradually increase the dependence of the energy, however fossil fuel finiteness and put The adjoint problem of environmental pollution of energy process causes the great attention of people, therefore explores exploitation cleaning, reproducible New Energy Source becomes the emphasis of world today's research.Hydrogen Energy, success the advantages that because of its high-energy density, cleanliness without any pollution, recyclable regenerative Ground has attracted the concern of people.In numerous production hydrogen approach, electrocatalytic decomposition aquatic products hydrogen is as a kind of safe, controllable, efficient side Method becomes the focus of world today's research.However, half-reaction of the oxygen evolution reaction as electrocatalytic decomposition water, four complicated electricity Sub- course makes the promotion of electrolysis water hydrogen-producing speed receive very big obstruction.Therefore, it explores and develops efficient catalyst promotion analysis oxygen Reaction rate becomes the important ring for realizing electrocatalytic decomposition aquatic products hydrogen industrialized production.A large amount of report displays, mention so far Rising the most effective catalyst of oxygen evolution reaction is precious metal iridium, ruthenium and its compound, but itself expensive price and rare Content limits it and further develops.Therefore, design synthesis is cheap, be easy to get, efficient oxygen-separating catalyst becomes new energy development The essential step utilized.
Nano material has been assigned many special physics, chemical property due to its small size.With nanotechnology Development, make a general survey of each research field nano material and all show to be widely applied, it is especially significant in catalytic field.It crosses The advantages that crossing metal, easily being adjusted due to its cheap, nontoxic, easy preparation, electronic structure is attracting people applied to electro-catalysis field Sight.But the disadvantages of itself intrinsic low electric conductivity, high adsorption energy, limits it and further develops, therefore needs effective Control measures optimize the properties such as its electric conductivity, adsorption energy, active site.Existing lot of documents report, by vulcanization, phosphatization, The means such as doping, oriented growth, crystal face regulation can optimize electric conductivity, adsorption energy, activity with the electronic structure of Effective Regulation material Electric charge transfer speed is improved to promote the catalytic activity of material in site.Wherein, doping is used as a kind of common control measures, can By reducing energy barrier, increasing the approach realizations such as active site, reduction band gap width to the optimising and adjustment of material catalytic performance.Cause This, ion doping is extensively studied as a kind of effective control measures.In the recent period, profound and powerful writing seminar in Nanyang Technolohy University building grinds Study carefully discovery, carboanion adulterates nickel, cobalt composition metal phosphide can be by promoting surface area, increasing the properties such as electric conductivity substantially Degree promotes the catalytic activity of the phosphide.
As a kind of transition metal oxide, CoFe2O4It is being urged because spinel structure assigns its excellent stability Show one's talent in change field.But the properties such as its high overpotential, rare active site, low electric conductivity hinder it as elctro-catalyst Large-scale application.With the further research to transition metal oxide property, and benefit from currentElement doping regulation hand The development of section, spinel-type CoFe2O4As the important member of transition metal oxide, its application value will be promoted significantly simultaneously Generate significant social benefit.In consideration of it, the present invention provides one kind to CoFe under conditions of keeping crystal structure2O4Knot Structure carries out the doping of anion nitrogen to significantly promote its catalytic activity, N doping CoFe2O4The exploitation of catalyst is closed At and electro-catalysis apply and for the development and exploration of cheap, efficient novel electro-catalytic agent provide direction.
Summary of the invention
Present invention solves the problem in that providing a kind of N doping CoFe2O4The preparation method and its electro-catalysis of nano-powder Performance applications.In order to solve the above problem the technical solution of the present invention is as follows:
1. a kind of N doping CoFe2O4The preparation method of nano-powder, preparation step are as follows: (1) in special reaction solution The obtained ferro-cobalt pre-reaction liquid of a certain proportion of cobalt, source of iron reagent is added, stirs 2 h, heats pre-reaction liquid certain time, it is naturally cold But, it is collected after washing is dry and obtains CoFe2O4Nano-powder；(2) by CoFe2O4Nano-powder is placed in tube furnace, in ammonia atmosphere Under enclosing, N doping CoFe is obtained with specific temperature calcining certain time2O4Nano-powder.
2. a kind of N doping CoFe2O4The preparation method of nano-powder, in the step (1), reaction solution be ethylene glycol, Glycerine, isopropanol are mixed with the ratio that volume ratio is 1 ~ 2: 1 ~ 2: 2 ~ 9, optimal are as follows: ethylene glycol, the third three Alcohol, isopropanol are mixed with the ratio that volume ratio is 1: 1: 8.
3. a kind of N doping CoFe2O4The preparation method of nano-powder, in the step (1), source of iron is six ferric sulfate hydrates Ammonium, Fe(NO3)39H2O, Iron(III) chloride hexahydrate, ferric sulfate, FeOOH, di-iron trioxide, ferroso-ferric oxide, ferric acetate One or more of, the concentration of source of iron solution is 0.01 ~ 0.10 mol/L.It is optimal are as follows: six ferric sulfate hydrate ammoniums, six hydrations Ferric trichloride, concentration are 0.05 ~ 0.08 mol/L.
4. a kind of N doping CoFe2O4The preparation method of nano-powder, in the step (1), cobalt source is six nitric hydrates One of cobalt, cobaltous sulfate, cobalt acetate, acetylacetone cobalt, cobalt chloride hexahydrate, cobalt sesquioxide, cobaltosic oxide, cobalt powder or Several, the concentration of cobalt source is 0.01 ~ 0.04 mol/L.It is optimal are as follows: cobalt chloride hexahydrate, cobaltous sulfate, concentration be 0.01 ~ 0.03 mol/L。
5. a kind of N doping CoFe2O4The preparation method of nano-powder, in the step (1), mole of cobalt source and source of iron It is optimal are as follows: 1: 2 than being 1 ~ 2: 2 ~ 4.
6. a kind of N doping CoFe2O4The preparation method of nano-powder, in the step (1), by gained ferro-cobalt pre-reaction Liquid is 130oC ~ 160 oHeating reaction 18 ~ 30 hours, optimal are as follows: 150 under CoC ~ 160 oCLower heating reaction 20 ~ 24 h。
7. a kind of N doping CoFe2O4The preparation method of nano-powder, in the step (2), gas required for calcining For ammonia, gas flow rate is 20 ~ 50 mL/min, optimal are as follows: 30 ~ 40 mL/min.
8. a kind of N doping CoFe2O4The preparation method of nano-powder, in the step (2), calcination temperature 300oC ~ 450 oBetween C, calcination time is 1 ~ 6 h, heating rate 0.5oC/min, it is optimal are as follows: 400oC calcines 2 ~ 5 h.
9. a kind of N doping CoFe2O4The simple preparation and electro-catalysis application of nano-powder, which is characterized in that using three electricity Electrode systems are tested, and carry out the oxygen performance test of electrocatalytic decomposition aquatic products, on electrochemical workstation to be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, is to electrode, using Ag/AgCl electrode as reference electrode with platinum electrode； Using 1 mol/L potassium hydroxide solution as electrolyte；Using H-type glass electrolytic cell as electrolysis reaction device.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiment of the invention is described below with reference to embodiment, these Description is 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 kettles, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner.Take 8 mL second Glycol, 8 mL glycerine, 24 mL isopropanols are added in 50 mL polytetrafluoroethylliner liners, and nine hydration nitre are sequentially added under stirring Sour iron (1.4544 g, 3.6 mmol), cabaltous nitrate hexahydrate (0.3492 g, 1.2 mmol), the magneton for being put into suitable size stirs 2 h are mixed, are then transferred in polytetrafluoroethylliner liner.It places it in 130 °C of baking oven and protects after sealing hydrothermal reaction kettle 30 h of temperature.After natural cooling, black CoFe is obtained for several times, after vacuum drying with dehydrated alcohol centrifuge washing2O4Nano-powder.
Step 2: taking 50 mg CoFe2O4Nano-powder is placed in tube furnace, 300 under ammonia atmosphereoC calcines 6 h heating Rate is 0.5oC/min, ammonia flow are 50 mL/min.Obtain the CoFe of N doping2O4Nano-powder.
Step 3: N doping CoFe2O4Nano-powder electrolysis water application
1. weighing the CoFe of 5 mg N dopings2O4Nano-powder, be added to 1mL ethyl alcohol and water in the mixed solvent (ethyl alcohol with The volume ratio of water is 3: 7), while 50 μ L Nafion solutions is added, 1 h of ultrasound obtains black even dispersion liquid.Take 4 μ L Above-mentioned dispersion liquid, drop coating is in glassy carbon electrode surface, and wherein glass-carbon electrode diameter is 3 mm, naturally dry.
2. using three-electrode system, electrocatalytic decomposition aquatic products oxygen performance is carried out on occasion China 660E electrochemical workstation and is surveyed Examination.To be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, is to electrode, Ag/AgCl electricity with platinum electrode Extremely reference electrode.Using 1 mol/L potassium hydroxide solution as electrolyte, using H-type glass electrolytic cell as reaction unit.
3. to be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, is carried out in three-electrode system Cyclic voltammetry activates sample.Cyclic voltammetry voltage range is 0 ~ 0.8 V(with respect to Ag/AgCl electrode), highest 0.8 V of current 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.Between sampling It is divided into 0.001 V, time of repose is 2 s, and scanning number of segment is 500.
4. after cyclic voltammetry, to be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, Linear voltage sweep test is carried out in three-electrode system, voltage range is 0 ~ 0.8 V(with respect to Ag/AgCl electrode).Initial electricity Position is 0 V, and termination current potential is 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 CoFe of N doping2O4The glass-carbon electrode of nano-powder is working electrode, is exchanged catalyst Testing impedance, to carry out kinetic Process Analysis.Parameter setting is as follows, and initial potential is 0.6 V(with respect to Ag/AgCl electrode), High frequency is 100000 Hz, low frequency 0.1Hz.Amplitude is 0.005 V, and quiescent time is 2 s.After data processing and calculating, nitrogen The CoFe of doping2O4It is being applied to OER excellent effect, the overpotential that catalysis water electrolysis produces oxygen is 0.284 V(relative standard's hydrogen Electrode), Tafel slope is 45 mV/dec, and charge transfer resistance is 33 Ω.
Embodiment 2
Step 1: taking 50 mL hydrothermal reaction kettles, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner.Take 4 mL second Glycol, 4 mL glycerine, 32 mL isopropanols are added in 50 mL polytetrafluoroethylliner liners, and six hydration sulphur are sequentially added under stirring Sour iron ammonium (0.8976 g, 2.4 mmol), cobaltous sulfate (0.3374 g, 1.2 mmol) are put into the magneton stirring 2 of suitable size H is then transferred in polytetrafluoroethylliner liner.150 °C of baking oven inside holding 24 is placed it in after sealing hydrothermal reaction kettle h.After natural cooling, black CoFe is obtained for several times, after vacuum drying with dehydrated alcohol centrifuge washing2O4Nano-powder.
Step 2: taking 50 mg CoFe2O4Nano-powder is placed in tube furnace, 400 under ammonia atmosphereoC calcines 3 h heating Rate is 0.5oC/min, ammonia flow are 30 mL/min.Obtain the CoFe of N doping2O4Nano-powder.
Step 3: N doping CoFe2O4Nano-powder electrolysis water application
1. weighing the CoFe of 5 mg N dopings2O4Nano-powder, be added to 1mL ethyl alcohol and water in the mixed solvent (ethyl alcohol with The volume ratio of water is 3: 7), while 50 μ L Nafion solutions is added, 1 h of ultrasound obtains black even dispersion liquid.Take 4 μ L Above-mentioned dispersion liquid, drop coating is in glassy carbon electrode surface, and wherein glass-carbon electrode diameter is 3 mm, naturally dry.
2. using three-electrode system, electrocatalytic decomposition aquatic products oxygen performance is carried out on occasion China 660E electrochemical workstation and is surveyed Examination.To be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, is to electrode, Ag/AgCl electricity with platinum electrode Extremely reference electrode.Using 1 mol/L potassium hydroxide solution as electrolyte, using H-type glass electrolytic cell as reaction unit.
3. to be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, is carried out in three-electrode system Cyclic voltammetry activates sample.Cyclic voltammetry voltage range is 0 ~ 0.8 V(with respect to Ag/AgCl electrode), highest 0.8 V of current 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.Between sampling It is divided into 0.001 V, time of repose is 2 s, and scanning number of segment is 500.
4. after cyclic voltammetry, to be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, Linear voltage sweep test is carried out in three-electrode system, voltage range is 0 ~ 0.8 V(with respect to Ag/AgCl electrode).Initial electricity Position is 0 V, and termination current potential is 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 CoFe of N doping2O4The glass-carbon electrode of nano-powder is working electrode, is exchanged catalyst Testing impedance, to carry out kinetic Process Analysis.Parameter setting is as follows, and initial potential is 0.6 V(with respect to Ag/AgCl electrode), High frequency is 100000 Hz, low frequency 0.1Hz.Amplitude is 0.005 V, and quiescent time is 2 s.After data processing and calculating, nitrogen The CoFe of doping2O4It is being applied to OER excellent effect, the overpotential that catalysis water electrolysis produces oxygen is 0.282 V(relative standard's hydrogen Electrode), Tafel slope is 40 mV/dec, and charge transfer resistance is 31 Ω.
Embodiment 3
Step 1: taking 50 mL hydrothermal reaction kettles, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner.Take 4 mL second Glycol, 4 mL glycerine, 32 mL isopropanols are added in 50 mL polytetrafluoroethylliner liners, and six hydrations three are sequentially added under stirring Iron chloride (0.4325 g, 1.6 mmol), cobalt chloride hexahydrate (0.1903 g, 0.8 mmol), are put into the magneton of suitable size 2 h are stirred, are then transferred in polytetrafluoroethylliner liner.It is placed it in after sealing hydrothermal reaction kettle in 160 °C of baking oven Keep the temperature 20 h.After natural cooling, black CoFe is obtained for several times, after vacuum drying with dehydrated alcohol centrifuge washing2O4Nano-powder.
Step 2: taking 50 mg CoFe2O4Nano-powder is placed in tube furnace, 400 under ammonia atmosphereoC calcines 2 h heating Rate is 0.5oC/min, ammonia flow are 40 mL/min.Obtain the CoFe of N doping2O4Nano-powder.
Step 3: N doping CoFe2O4Nano-powder electrolysis water application
1. weighing the CoFe of 5 mg N dopings2O4Nano-powder, be added to 1mL ethyl alcohol and water in the mixed solvent (ethyl alcohol with The volume ratio of water is 3: 7), while 50 μ L Nafion solutions is added, 1 h of ultrasound obtains black even dispersion liquid.Take 4 μ L Above-mentioned dispersion liquid, drop coating is in glassy carbon electrode surface, and wherein glass-carbon electrode diameter is 3 mm, naturally dry.
2. using three-electrode system, electrocatalytic decomposition aquatic products oxygen performance is carried out on occasion China 660E electrochemical workstation and is surveyed Examination.To be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, is to electrode, Ag/AgCl electricity with platinum electrode Extremely reference electrode.Using 1 mol/L potassium hydroxide solution as electrolyte, using H-type glass electrolytic cell as reaction unit.
3. to be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, is carried out in three-electrode system Cyclic voltammetry activates sample.Cyclic voltammetry voltage range is 0 ~ 0.8 V(with respect to Ag/AgCl electrode), highest 0.8 V of current 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.Between sampling It is divided into 0.001 V, time of repose is 2 s, and scanning number of segment is 500.
4. after cyclic voltammetry, to be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, Linear voltage sweep test is carried out in three-electrode system, voltage range is 0 ~ 0.8 V(with respect to Ag/AgCl electrode).Initial electricity Position is 0 V, and termination current potential is 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 CoFe of N doping2O4The glass-carbon electrode of nano-powder is working electrode, is exchanged catalyst Testing impedance, to carry out kinetic Process Analysis.Parameter setting is as follows, and initial potential is 0.6 V(with respect to Ag/AgCl electrode), High frequency is 100000 Hz, low frequency 0.1Hz.Amplitude is 0.005 V, and quiescent time is 2 s.After data processing and calculating, nitrogen The CoFe of doping2O4It is being applied to OER excellent effect, the overpotential that catalysis water electrolysis produces oxygen is 0.282 V(relative standard's hydrogen Electrode), Tafel slope is 40 mV/dec, and charge transfer resistance is 30 Ω.
Embodiment 4
Step 1: taking 50 mL hydrothermal reaction kettles, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner.Take 4 mL second Glycol, 8 mL glycerine, 28 mL isopropanols are added in 50 mL polytetrafluoroethylliner liners, and six hydrations three are sequentially added under stirring Iron chloride (0.8650 g, 3.2 mmol), cobaltous sulfate (0.4498 g, 1.6 mmol) are put into the magneton stirring 2 of suitable size H is then transferred in polytetrafluoroethylliner liner.155 °C of baking oven inside holding 22 is placed it in after sealing hydrothermal reaction kettle h.After natural cooling, black CoFe is obtained for several times, after vacuum drying with dehydrated alcohol centrifuge washing2O4Nano-powder.
Step 2: taking 50 mg CoFe2O4Nano-powder is placed in tube furnace, 400 under ammonia atmosphereoC calcines 5 h heating Rate is 0.5oC/min, ammonia flow are 30 mL/min.Obtain the CoFe of N doping2O4Nano-powder.
Step 3: N doping CoFe2O4Nano-powder electrolysis water application
1. weighing the CoFe of 5 mg N dopings2O4Nano-powder, be added to 1mL ethyl alcohol and water in the mixed solvent (ethyl alcohol with The volume ratio of water is 3: 7), while 50 μ L Nafion solutions is added, 1 h of ultrasound obtains black even dispersion liquid.Take 4 μ L Above-mentioned dispersion liquid, drop coating is in glassy carbon electrode surface, and wherein glass-carbon electrode diameter is 3 mm, naturally dry.
2. using three-electrode system, electrocatalytic decomposition aquatic products oxygen performance is carried out on occasion China 660E electrochemical workstation and is surveyed Examination.To be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, is to electrode, Ag/AgCl electricity with platinum electrode Extremely reference electrode.Using 1 mol/L potassium hydroxide solution as electrolyte, using H-type glass electrolytic cell as reaction unit.
3. to be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, is carried out in three-electrode system Cyclic voltammetry activates sample.Cyclic voltammetry voltage range is 0 ~ 0.8 V(with respect to Ag/AgCl electrode), highest 0.8 V of current 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.Between sampling It is divided into 0.001 V, time of repose is 2 s, and scanning number of segment is 500.
4. after cyclic voltammetry, to be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, Linear voltage sweep test is carried out in three-electrode system, voltage range is 0 ~ 0.8 V(with respect to Ag/AgCl electrode).Initial electricity Position is 0 V, and termination current potential is 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 CoFe of N doping2O4The glass-carbon electrode of nano-powder is working electrode, is exchanged catalyst Testing impedance, to carry out kinetic Process Analysis.Parameter setting is as follows, and initial potential is 0.6 V(with respect to Ag/AgCl electrode), High frequency is 100000 Hz, low frequency 0.1Hz.Amplitude is 0.005 V, and quiescent time is 2 s.After data processing and calculating, nitrogen The CoFe of doping2O4It is being applied to OER excellent effect, the overpotential that catalysis water electrolysis produces oxygen is 0.284 V(relative standard's hydrogen Electrode), Tafel slope is 42 mV/dec, and charge transfer resistance is 31 Ω.
Embodiment 5
Step 1: taking 50 mL hydrothermal reaction kettles, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner.Take 8 mL second Glycol, 16 mL glycerine, 16 mL isopropanols are added in 50 mL polytetrafluoroethylliner liners, sequentially add ferric sulfate under stirring (0.1599 g, 0.4 mmol), cobalt acetate (0.0708 g, 0.4 mmol), the magneton for being put into suitable size stir 2 h, then It transfers them in polytetrafluoroethylliner liner.140 °C of 19 h of baking oven inside holding is placed it in after sealing hydrothermal reaction kettle.From So after cooling, black CoFe is obtained for several times, after vacuum drying with dehydrated alcohol centrifuge washing2O4Nano-powder.
Step 2: taking 50 mg CoFe2O4Nano-powder is placed in tube furnace, 450 under ammonia atmosphereoC calcines 1 h heating Rate is 0.5oC/min, ammonia flow are 20 mL/min.Obtain the CoFe of N doping2O4Nano-powder.
Step 3: N doping CoFe2O4Nano-powder electrolysis water application
1. weighing the CoFe of 5 mg N dopings2O4Nano-powder, be added to 1mL ethyl alcohol and water in the mixed solvent (ethyl alcohol with The volume ratio of water is 3: 7), while 50 μ L Nafion solutions is added, 1 h of ultrasound obtains black even dispersion liquid.Take 4 μ L Above-mentioned dispersion liquid, drop coating is in glassy carbon electrode surface, and wherein glass-carbon electrode diameter is 3 mm, naturally dry.
2. using three-electrode system, electrocatalytic decomposition aquatic products oxygen performance is carried out on occasion China 660E electrochemical workstation and is surveyed Examination.To be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, is to electrode, Ag/AgCl electricity with platinum electrode Extremely reference electrode.Using 1 mol/L potassium hydroxide solution as electrolyte, using H-type glass electrolytic cell as reaction unit.
3. to be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, is carried out in three-electrode system Cyclic voltammetry activates sample.Cyclic voltammetry voltage range is 0 ~ 0.8 V(with respect to Ag/AgCl electrode), highest 0.8 V of current 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.Between sampling It is divided into 0.001 V, time of repose is 2 s, and scanning number of segment is 500.
4. after cyclic voltammetry, to be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, Linear voltage sweep test is carried out in three-electrode system, voltage range is 0 ~ 0.8 V(with respect to Ag/AgCl electrode).Initial electricity Position is 0 V, and termination current potential is 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 CoFe of N doping2O4The glass-carbon electrode of nano-powder is working electrode, is exchanged catalyst Testing impedance, to carry out kinetic Process Analysis.Parameter setting is as follows, and initial potential is 0.6 V(with respect to Ag/AgCl electrode), High frequency is 100000 Hz, low frequency 0.1Hz.Amplitude is 0.005 V, and quiescent time is 2 s.After data processing and calculating, nitrogen The CoFe of doping2O4It is being applied to OER excellent effect, the overpotential that catalysis water electrolysis produces oxygen is 0.285 V(relative standard's hydrogen Electrode), Tafel slope is 43 mV/dec, and charge transfer resistance is 35 Ω.

Claims (7)

1. a kind of N doping CoFe2O4The preparation method of nano-powder, which is characterized in that preparation step is as follows: (1) special The obtained ferro-cobalt pre-reaction liquid of addition cobalt, source of iron in reaction solution, 2 h of stirring, heating pre-reaction liquid certain time, natural cooling, Washing collects and obtains CoFe2O4Nano-powder；(2) by CoFe2O4Nano-powder is placed in tube furnace, fixed in ammonia atmosphere Temperature calcination certain time obtains N doping CoFe2O4Nano-powder.
2. a kind of N doping CoFe according to claim 12O4The preparation method of nano-powder, which is characterized in that the step Suddenly in (1), reaction solution be ethylene glycol, glycerine, isopropanol with volume ratio be 1 ~ 2: 1 ~ 2: 2 ~ 9 ratio mixing It forms.
3. a kind of N doping CoFe according to claim 12O4The preparation method of nano-powder, which is characterized in that the step Suddenly in (1), source of iron is six ferric sulfate hydrate ammoniums, Fe(NO3)39H2O, Iron(III) chloride hexahydrate, ferric sulfate, FeOOH, three Two iron, ferroso-ferric oxide, ferric acetate are aoxidized, the concentration of source of iron solution is 0.01 ~ 0.10 mol/L；Cobalt source is six nitric hydrates Cobalt, cobaltous sulfate, cobalt acetate, acetylacetone cobalt, cobalt chloride hexahydrate, cobalt sesquioxide, cobaltosic oxide, the concentration of cobalt source solution For 0.01 ~ 0.04 mol/L；Wherein, the molar ratio of cobalt source and source of iron is 1 ~ 2: 2 ~ 4.
4. a kind of N doping CoFe according to claim 12O4The preparation method of nano-powder, which is characterized in that the step Suddenly in (1), by gained ferro-cobalt pre-reaction liquid 130oC ~ 160 oHeating reaction 18 ~ 30 hours under C.
5. a kind of N doping CoFe according to claim 12O4The preparation method of nano-powder, which is characterized in that the step Suddenly in (2), gas required for calcining is ammonia, and gas flow rate is 20 ~ 50 mL/min.
6. a kind of N doping CoFe according to claim 12O4The preparation method of nano-powder, which is characterized in that the step Suddenly in (2), calcination temperature 300oC ~ 450 oC, calcination time are 1 ~ 6 h, heating rate 0.5oC/min。
7. a kind of N doping CoFe2O4The simple preparation and electro-catalysis application of nano-powder, which is characterized in that use three electrode systems System is tested, and carries out the oxygen performance test of electrocatalytic decomposition aquatic products, on electrochemical workstation to be coated with N doping CoFe2O4The glass-carbon electrode of nano-powder is working electrode, is to electrode, using Ag/AgCl electrode as reference electrode with platinum electrode； Using 1 mol/L potassium hydroxide solution as electrolyte；Using H-type glass electrolytic cell as electrolysis reaction device.
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CN110342586A (en) * 2019-08-30 2019-10-18 济南大学 A kind of defective phosphorus doping CoFe of tool2O4The preparation and electro-catalysis application of nano-powder
CN113106484A (en) * 2021-04-07 2021-07-13 西南大学 Hydrothermal preparation method of novel photo-anode based on alpha-type iron oxide vermicular nano-structure array, product and application thereof

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CN106082349A (en) * 2016-06-20 2016-11-09 济南大学 A kind of spinel-type sulfur doping Co ferrite Nano powder and preparation method
CN108906056A (en) * 2018-06-28 2018-11-30 济南大学 A kind of preparation of inverse spinel structure Co ferrite Nano powder and electro-catalysis application with oxygen defect

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CN101829590A (en) * 2010-05-06 2010-09-15 东华大学 Preparation method of easily-recovered nitrogen-doped core-shell ZnO/TiO2 visible light photocatalyst
CN106082349A (en) * 2016-06-20 2016-11-09 济南大学 A kind of spinel-type sulfur doping Co ferrite Nano powder and preparation method
CN108906056A (en) * 2018-06-28 2018-11-30 济南大学 A kind of preparation of inverse spinel structure Co ferrite Nano powder and electro-catalysis application with oxygen defect

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110342586A (en) * 2019-08-30 2019-10-18 济南大学 A kind of defective phosphorus doping CoFe of tool2O4The preparation and electro-catalysis application of nano-powder
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