CN107871875A - A kind of oxygen evolution reaction elctro-catalyst, its preparation method and application - Google Patents
A kind of oxygen evolution reaction elctro-catalyst, its preparation method and application Download PDFInfo
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- CN107871875A CN107871875A CN201610851613.5A CN201610851613A CN107871875A CN 107871875 A CN107871875 A CN 107871875A CN 201610851613 A CN201610851613 A CN 201610851613A CN 107871875 A CN107871875 A CN 107871875A
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- ferronickel
- salting liquid
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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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
- Y02E60/50—Fuel cells
Abstract
The present invention relates to a kind of oxygen evolution reaction elctro-catalyst, its preparation method and application, methods described includes the mixed system of ferronickel salting liquid and aqueous slkali being exposed to the step of reacting in oxidizing atmosphere；Described ferronickel salting liquid is that soluble ferrite and soluble nickel salt are dissolved in water and uniformly mix resulting solution；Described soluble ferrite is selected from ferrous sulfate, frerrous chloride or ferrous acetate；Described soluble nickel salt is selected from nickel sulfate, nickel chloride or nickel acetate.Simple using equipment needed for the method production OER catalyst of the present invention, easy to operate, cost is low.Prepared Fe simultaneously3+The β Ni (OH) of doping2Nano bar-shape microscopic pattern is presented in catalyst, has a good OER activity, and activity and stability are superior to the layer of NiFe shape double-hydroxide reported before and the best IrO of current performance2.Therefore can be as the elctro-catalyst in the fields such as regeneratable fuel cell, rechargeable metal, electrolysis water.
Description
Technical field
The invention belongs to the preparation field of electrochemical catalyst, is related to a kind of Fe that can be used for catalysis oxygen evolution reaction (OER)3+
β-the Ni (OH) of doping2The preparation method of nanometer rods.
Background technology
In modern society, the clothing, food, lodging and transportion -- basic necessities of life of people are all tightly associated with energy supply and consumption, such as make a fire and cook, take
Warm, illumination, communications and transportation, industrial production etc. all be unable to do without the energy.It can be said that just there is no modern civilization without energy industry.This
Outside, fossil fuel is the unholiness energy, while people's overwhelming majority energy demand is met, has also been discharged greatly to nature
The waste water,waste gas and industrial residue of amount, it is complete to cause acid rain harm, greenhouse effects, depletion of the ozone layer and threat of Chemical Time Bomb etc.
Ball environmental problem.In 21 century, with the sustainable development of global economy, particularly its fossil energy relied on, oil, coal
Charcoal, natural gas etc. are faced with serious resource exhaustion problem, economize on resources, efficiently utilize existing resource, exploitation clear energy sources
It is the theme of 21 century world energy sources science and technology with new technology.And metal-air battery has abundant raw materials, safety and environmental protection, energy
The advantages that density is high, it is referred to as " new green power geared to the 21st century ".The anode of metal-air battery be active metal (such as
Mg, Al and Zn etc.), during electric discharge metal M be oxidized to corresponding metal ions M+；It is reduced into accordingly for metal ion during charging
Metal.Cathode active material is the oxygen in air, O during electric discharge2It is reduced into OH-；OH- is oxidized O during charging2Separate out.Metal
The fuel metal M and oxidant O of air-fuel battery2It can be able to " regenerate " by charging process, play accumulation of energy effect.
Yet with the slow dynamic process of oxygen evolution reaction, oxygen evolution required voltage is significantly larger than thermodynamics electricity
Gesture, seriously limit the application of rechargeable metal.Up to the present, IrO2It is the performance and stably in alkaline system
Property best OER catalyst, it is expensive but because its content on earth is rare, it is commercialized to greatly limit them
Using.Therefore cheap, stability and high efficiency OER catalyst is developed to have great importance.
Except noble metal, the oxide containing ferronickel or hydroxide in alkaline medium there is higher analysis oxygen to urge simultaneously
Change activity.It is interesting that single nickel hydroxide and ferriferous oxide catalysis OER poor performance, but compound ferronickel hydrogen-oxygen
Compound just shows excellent OER performances.2014, Boettcher et al. prepared Ni by electrochemical in-situ method1- xFexOOH films, for oxygen evolution, it is found that the Fe of incorporation not only improves the electric conductivity of film and further promotes Ni Partial charge
Transferance, so as to significantly improve OER performances.2015, Dai et al. utilized the high conductivity of CNT, by Ni-Fe layers
Shape double-hydroxide is (with α-Ni (OH)2Structure is similar) with CNT is compound obtains high performance OER catalyst, and sent out
Table exists《Journal of the American Chemical Society》On.2016, Yan et al. existed
《Electrochemistry Communications》Report the Ni-Fe stratiforms pair that nano-sheet is made by hydrothermal method
Hydroxide is used to be catalyzed OER.But research main sides before focus on the γ-NiOOH of the Fe2O3 doping of electrochemical in-situ generation
With Ni-Fe layered double-hydroxides.In addition compared to commercialized IrO2, it is poor that these catalyst still have stability, catalysis
The problems such as agent synthesis is complicated.
The content of the invention
It is contemplated that being directed to, existing OER catalyst is expensive, catalytic current density is low, overpotential is high, stability is poor,
Synthetic method challenge, propose solution.A kind of oxygen evolution reaction elctro-catalyst, its preparation are provided for this present system
Method and application.
First, the preparation method of oxygen evolution reaction (OER) elctro-catalyst of the present invention is included ferronickel salting liquid and alkali
The mixed system of solution is exposed to the step of being reacted in oxidizing atmosphere；Described ferronickel salting liquid is soluble ferrite and can
Insoluble nickel salt is dissolved in water and uniformly mixes resulting solution；Described soluble ferrite be selected from ferrous sulfate, frerrous chloride or
Ferrous acetate；Described soluble nickel salt is selected from nickel sulfate, nickel chloride or nickel acetate.
Equipment needed for the synthetic method is simple, easy to operate, and cost is low.On the other hand, it is prepared by the above method
Be Fe3+β-the Ni (OH) of doping2.It is the oxygen evolution reaction elctro-catalyst with nanometer rods microstructure, possesses very excellent
OER activity.Tafel slopes can reach 32mV dec-1, current density is 10mA cm when overpotential is 0.26V-2, and activity
Layer of NiFe shape double-hydroxide reported in prior art and the best IrO of current performance are superior to stability2.Can be used as can
The elctro-catalyst in the fields such as regenerative fuel cell, rechargeable metal, electrolysis water.
Based on this, the purpose of further aspect of the present invention is the Fe for providing the invention described above3+β-the Ni (OH) of doping2Analysing
Application in oxygen reaction (OER).Especially it is used as OER catalyst in the basic conditions.
Simple using equipment needed for the method production OER catalyst of the present invention, easy to operate, cost is low.Institute simultaneously
The Fe of preparation3+β-the Ni (OH) of doping2Nano bar-shape microscopic pattern is presented in catalyst, has good OER active, Tafel is oblique
Rate reaches 32mV dec-1, current density is 10mA cm when overpotential is 0.26V-2, and activity and before stability is superior to
The layer of NiFe shape double-hydroxide of report and the best IrO of current performance2.Therefore Fe3+β-the Ni (OH) of doping2Nanometer rods can be made
For the elctro-catalyst in the fields such as regeneratable fuel cell, rechargeable metal, electrolysis water.
Brief description of the drawings
The width of accompanying drawing 2 of the present invention:
Fig. 1 is Fe in embodiment 43+β-the Ni (OH) of doping2The transmission electron microscope picture of material；
Fig. 2 is Fe prepared in embodiment 1~93+β-the Ni (OH) of doping2X-ray diffraction (XRD) spectrogram of material.
Embodiment
The present invention provides a kind of preparation method of oxygen evolution reaction elctro-catalyst, and the catalyst being thus prepared.Should
The oxygen evolution reaction elctro-catalyst is Fe3+β-the Ni (OH) of doping2。
The present invention's provides a kind of preparation method of oxygen evolution reaction elctro-catalyst first, and the present invention is based on improved atom level
Other topochemistry conversion method, under inert gas shielding, generation divalence Fe is reacted with aqueous slkali with Ni and Fe salting liquids and mixed
Miscellaneous β-Ni (OH)2, generation trivalent is then oxidized in oxidizing atmosphere using the topochemistry conversion method of atomic level
β-the Ni (OH) of Fe doping2Catalyst.
The above method of the present invention includes mixing ferronickel salting liquid with aqueous slkali, and the mixed system is exposed to
Step in oxidizing atmosphere.
Wherein, ferronickel salting liquid is soluble ferrite and soluble nickel salt is dissolved in water and uniformly mixes resulting solution；
Described soluble ferrite is selected from ferrous sulfate, frerrous chloride or ferrous acetate；Preferably sulfuric acid is ferrous；Described soluble nickel
Salt is selected from nickel sulfate, nickel chloride or nickel acetate；Preferably sulfuric acid nickel.It is further preferred that described ferronickel concentration of salt solution (according to
The concentration summation of nickel ion and iron ion in solution) it is 0.1~2mol/L.In preferred real technical scheme, described ferronickel
In salting liquid, the mol ratio of ferrous salt and nickel salt is 0.05~0.6.
In the method for the invention described above, described aqueous slkali refers to routinely understand according to this area, available for providing hydrogen-oxygen
The solution of radical ion, it can be selected but be not limited to potassium hydroxide aqueous solution, sodium hydroxide or ammoniacal liquor.Wherein particularly preferred potassium hydroxide
The aqueous solution.It is more highly preferred to, in the aqueous slkali, according to OH-Meter, its concentration is 0.1~5mol/L.The dosage of aqueous slkali can be with
According to OH-The amount of material calculated for 2~30 times of nickel ion and iron ion total moles.
In embodiment, process that the ferronickel salting liquid mixes with aqueous slkali is to add ferronickel salting liquid dropwise
Enter aqueous slkali and mixed system is made, the fierce side effect that may be occurred with control reaction.The speed of dropwise addition is 0.5~4mL/
min；It is preferred that 1mL/min.
In another specific embodiment, the preparation of the ferronickel salting liquid and its inert gas is blended in aqueous slkali
Carried out under protective condition.The inert gas routinely understands selection according to this area.
In the method for the invention described above, the mixed system of ferronickel salting liquid and aqueous slkali is exposed in oxidizing atmosphere, mesh
Be aoxidize divalent Fe be trivalent, the oxidizing atmosphere described in it is air, oxygen or ozone；It is preferred that air.Reaction temperature is
20-90℃.It is preferred that 80 DEG C.Reaction time is 4~6 hours.
According to foregoing description, the combination of preferred feature can obtain the optimal technical scheme of preparation method of the present invention, this
Class optimal technical scheme can be exemplified below, but be not limited to this.
In preferable technical scheme, preparation method of the present invention comprises the following steps：
(1) under inert atmosphere protection, soluble ferrite and soluble nickel salt are dissolved in water and well mixed preparation concentration
For 0.1~2mol/L ferronickel salting liquid；
(2) under inert atmosphere protection, by the ferronickel salting liquid prepared by step (1) according to 1mL/min speed dropwise
It is in 0.1~5mol/L potassium hydroxide aqueous solutions to add to concentration；
(3) mixed system for preparing step (2) is exposed in oxidizing atmosphere, the stirring reaction under the conditions of 20~90 DEG C
4~6h；Gained sediment is first washed with deionized to pH=7, then is washed 3 times with absolute ethyl alcohol, is distributed to after centrifugation
In ethanol, frozen drying.
By being Fe made from the above method3+β-the Ni (OH) of doping2.With excellent OER activity, can be applied to analyse oxygen
Especially it is used as OER catalyst in the basic conditions in reaction (OER).
The present invention further provides totally 9 embodiments of embodiment 1~9, to oxygen evolution reaction electro-catalysis of the present invention
The preparation method of agent, preparation-obtained product and its application are described further.
Test of the preparation-obtained dusty material through XRD in the embodiment of the present invention, shows identical feature：Sweeping
When to retouch angle of diffraction be 10-90, diffraction maximum is respectively 20 degree, 34 degree, 39 degree, 53 degree, 61 degree and 71 degree, control β-Ni (OH)2
Standard PDF cards find, just correspond to corresponding 001 crystal face diffraction (19.258 degree), 100 crystal face diffraction (33.064 degree),
101 crystal face diffraction (38.541 degree), 102 crystal face diffraction (52.100 degree), 003 crystal face diffraction (60.240 degree) and 103 crystal faces spread out
Penetrate (70.478 degree).Show the structures of β-Ni (OH) 2 that nanometer rods are hexagonal phase.Diffraction maximum relative standard slide calliper rule move to right a bit be by
In the less Fe of ionic radius3+(55pm) occupies β-Ni (OH)2The larger Ni of phase Ionic Radius2+Caused by (69pm).Inspection
Survey result as shown in Figure 2.
Oxygen precipitation (OER) activity rating further is carried out to the product obtained by the embodiment of the present invention, method is as follows：
(1) preparation of catalyst pulp：By a certain amount of Fe3+The nanometer rods of β-Ni (OH) 2 and XC-72 of doping are distributed to different
In propyl alcohol, then appropriate Nafion solution (5w.t.%) is added thereto, then ultrasonic vibration makes it be uniformly dispersed to obtain catalyst
Slurry.
(2) prepared by electrode：The catalyst pulp of above-mentioned preparation is pipetted with pipette it is a certain amount of in rotating disk electrode (r.d.e),
Spontaneously dried in air.
(3) test of electrode activity：The electrode prepared is attached on rotating circular disk device and tested.Test process is such as
Under：
1) electro-chemical test system is that (catalyst-loaded glass-carbon electrode is working electrode, platinum filament or platinum to three-electrode system
Piece is that saturated calomel electrode (SCE) is reference electrode to electrode), electrolyte is 0.1mol/L KOH solution.
2) O before test, is led into reactor2To saturation, oxygen is also ceaselessly led in test process.
3) evaluate oxygen and separate out (OER) activity, carry out polarization curve test (LSV), voltage scan range is 0~0.8V, is swept
It is 10mvs to retouch speed-1, rotary speed 1600rpm.
As a comparison, to the best IrO of current commercialized catalysis OER performances2(purchased from Johnson Matthey companies
Buy) carry out oxygen precipitation evaluation.Weigh commercialized IrO2It is dispersed in each 5mg of XC-72 in 2mL isopropanol, adds 50 μ L
Nafion (5w.t.%) solution, ultrasonic vibration 30min, which makes to be well mixed, obtains catalyst pulp.Then 20 μ L catalyst are pipetted
Slurry spontaneously dries in a diameter of 5mm rotating disk electrode (r.d.e) in air.Obtained electrode is according in the above content of the invention
Electrode testing procedure carries out oxygen precipitation (OER) activity rating.Test result is shown, when analysis oxygen current density is 10mA/cm2When,
Overpotential is 0.34V；When analysis oxygen current density is 20mA/cm2When, overpotential 0.38V.
Embodiment 1
Weigh 2.7801 grams of nickel sulfate hexahydrates to be dissolved in 20 milliliters of water, concentration of nickel sulfate is 0.5 mole every liter.In nitrogen gas
20mL 0.5mol/L nickel sulfate solution is added dropwise to dropwise in 80mL 1.25mol/L potassium hydroxide solution under atmosphere protection,
20min is added dropwise, 80 DEG C of reaction temperature.Then by turbid system exposure in atmosphere, 5h is reacted.Finally first it is washed with water to
PH=7, then centrifuged after washing 3 times with absolute ethyl alcohol.Product is distributed in ethanol, freeze drier cryogenic vacuum is done
It is dry.Obtain green powder.Weigh obtained green powder and each 5mg of XC-72 are dispersed in 2mL isopropanol, add 50 μ L
Nafion (5%) solution, ultrasonic vibration 30min, which makes to be well mixed, obtains catalyst pulp.Then the 20 above-mentioned catalyst of μ L are pipetted
Slurry spontaneously dries in a diameter of 5mm rotating disk electrode (r.d.e) in air.Obtained electrode is according in the above content of the invention
Electrode testing procedure carries out oxygen precipitation (OER) activity rating.Test result is shown, when analysis oxygen current density is 10mA/cm2When,
Overpotential is 0.42V.
Embodiment 2
Weigh 0.2628 gram of green vitriol and 2.5021 grams of nickel sulfate hexahydrates are dissolved in 20 milliliters of water, ferrous sulfate
It it is 0.5 mole every liter with nickel sulfate total concentration.20mL 0.5mol/L nickel sulfate solution is dripped dropwise under nitrogen atmosphere protection
Add in 80mL 1.25mol/L potassium hydroxide solution, 20min is added dropwise, 80 DEG C of reaction temperature.Then by turbid system
Exposure in atmosphere, reacts 5h.PH=7 is first finally washed with water to, then is centrifuged after washing 3 times with absolute ethyl alcohol.Will production
Product are distributed in ethanol, freeze drier low-temperature vacuum drying.Obtain yellowish-brown powder.Weigh obtained yellowish-brown powder and
Each 5mg of XC-72 are dispersed in 2mL isopropanol, add 50 μ L Nafion (5%) solution, and ultrasonic vibration 30min makes mixing
Uniformly obtain catalyst pulp.Then 20 μ L catalyst pulps are pipetted in a diameter of 5mm rotating disk electrode (r.d.e), in air from
So dry.Obtained electrode carries out oxygen precipitation (OER) activity rating according to the electrode testing procedure in the above content of the invention.Test
As a result show, when analysis oxygen current density is 10mA/cm2When, overpotential 0.33V.
Embodiment 3
Weigh 0.7886 gram of green vitriol and 1.9461 grams of nickel sulfate hexahydrates are dissolved in 20 milliliters of water, ferrous sulfate
It it is 0.5 mole every liter with nickel sulfate total concentration.20mL 0.5mol/L nickel sulfate solution is dripped dropwise under nitrogen atmosphere protection
Add in 80mL 1.25mol/L potassium hydroxide solution, 20min is added dropwise, 80 DEG C of reaction temperature.Then by turbid system
Exposure in atmosphere, reacts 5h.PH=7 is first finally washed with water to, then is centrifuged after washing 3 times with absolute ethyl alcohol.Will production
Product are distributed in ethanol, freeze drier low-temperature vacuum drying.Obtain yellowish-brown powder.Weigh obtained yellowish-brown powder and
Each 5mg of XC-72 are dispersed in 2mL isopropanol, add 50 μ L Nafion (5%) solution, and ultrasonic vibration 30min makes mixing
Uniformly obtain catalyst pulp.Then 20 μ L catalyst pulps are pipetted in a diameter of 5mm rotating disk electrode (r.d.e), in air from
So dry.Obtained electrode carries out oxygen precipitation (OER) activity rating according to the electrode testing procedure in the above content of the invention.Test
As a result show, when analysis oxygen current density is 10mA/cm2When, overpotential 0.27V.
Embodiment 4
Weigh 1.3143 grams of green vitriols and 1.3901 grams of nickel sulfate hexahydrates are dissolved in 20 milliliters of water, ferrous sulfate
It it is 0.5 mole every liter with nickel sulfate total concentration.20mL 0.5mol/L nickel sulfate solution is dripped dropwise under nitrogen atmosphere protection
Add in 80mL 1.25mol/L potassium hydroxide solution, 20min is added dropwise, 80 DEG C of reaction temperature.Then by turbid system
Exposure in atmosphere, reacts 5h.PH=7 is first finally washed with water to, then is centrifuged after washing 3 times with absolute ethyl alcohol.Will production
Product are distributed in ethanol, freeze drier low-temperature vacuum drying.Obtain yellowish-brown powder.Transmission electron microscope photo is as shown in Figure 1.Claim
Each 5mg of yellowish-brown powder and XC-72 obtained is dispersed in 2mL isopropanol, adds 50 μ L Nafion (5%) solution,
Ultrasonic vibration 30min, which makes to be well mixed, obtains catalyst pulp.Then 20 μ L catalyst pulps are pipetted in a diameter of 5mm rotation
On disk electrode, spontaneously dried in air.Obtained electrode carries out oxygen analysis according to the electrode testing procedure in the above content of the invention
Go out (OER) activity rating.Test result is shown, when analysis oxygen current density is 10mA/cm2When, overpotential 0.26V.
Embodiment 5
Weigh 1.3143 grams of green vitriols and 1.3901 grams of nickel sulfate hexahydrates are dissolved in 20 milliliters of water, ferrous sulfate
It it is 0.5 mole every liter with nickel sulfate total concentration.20mL 0.5mol/L nickel sulfate solution is dripped dropwise under nitrogen atmosphere protection
Add in 80mL 1.25mol/L potassium hydroxide solution, 20min is added dropwise, 80 DEG C of reaction temperature.Then in turbid system
In lead to oxygen, react 5h.PH=7 is first finally washed with water to, then is centrifuged after washing 3 times with absolute ethyl alcohol.By product point
It is scattered in ethanol, freeze drier low-temperature vacuum drying.Obtain yellowish-brown powder.Weigh obtained yellowish-brown powder and XC-72
Each 5mg is dispersed in 2mL isopropanol, adds 50 μ L Nafion (5%) solution, and ultrasonic vibration 30min makes well mixed
To catalyst pulp.Then 20 μ L catalyst pulps are pipetted in a diameter of 5mm rotating disk electrode (r.d.e), are done naturally in air
It is dry.Obtained electrode carries out oxygen precipitation (OER) activity rating according to the electrode testing procedure in the above content of the invention.Test result
It has been shown that, when analysis oxygen current density is 10mA/cm2When, overpotential 0.27V.
Embodiment 6
Weigh 1.3143 grams of green vitriols and 1.3901 grams of nickel sulfate hexahydrates are dissolved in 20 milliliters of water, ferrous sulfate
It it is 0.5 mole every liter with nickel sulfate total concentration.20mL 0.5mol/L nickel sulfate solution is dripped dropwise under nitrogen atmosphere protection
Add in 80mL 1.25mol/L potassium hydroxide solution, 20min is added dropwise, 80 DEG C of reaction temperature.Then in turbid system
In lead to ozone, react 5h.PH=7 is first finally washed with water to, then is centrifuged after washing 3 times with absolute ethyl alcohol.By product point
It is scattered in ethanol, freeze drier low-temperature vacuum drying.Obtain yellowish-brown powder.Weigh obtained yellowish-brown powder and XC-72
Each 5mg is dispersed in 2mL isopropanol, adds 50 μ L Nafion (5%) solution, and ultrasonic vibration 30min makes well mixed
To catalyst pulp.Then 20 μ L catalyst pulps are pipetted in a diameter of 5mm rotating disk electrode (r.d.e), are done naturally in air
It is dry.Obtained electrode carries out oxygen precipitation (OER) activity rating according to the electrode testing procedure in the above content of the invention.Test result
It has been shown that, when analysis oxygen current density is 10mA/cm2When, overpotential 0.28V.
Embodiment 7
Weigh 1.3143 grams of green vitriols and 1.3901 grams of nickel sulfate hexahydrates are dissolved in 20 milliliters of water, ferrous sulfate
It it is 0.5 mole every liter with nickel sulfate total concentration.20mL 0.5mol/L nickel sulfate solution is dripped dropwise under nitrogen atmosphere protection
Add in 80mL 1.25mol/L potassium hydroxide solution, 20min is added dropwise, 60 DEG C of reaction temperature.Then in turbid system
In lead to ozone, react 5h.PH=7 is first finally washed with water to, then is centrifuged after washing 3 times with absolute ethyl alcohol.By product point
It is scattered in ethanol, freeze drier low-temperature vacuum drying.Obtain yellowish-brown powder.Weigh obtained yellowish-brown powder and XC-72
Each 5mg is dispersed in 2mL isopropanol, adds 50 μ L Nafion (5%) solution, and ultrasonic vibration 30min makes well mixed
To catalyst pulp.Then 20 μ L catalyst pulps are pipetted in a diameter of 5mm rotating disk electrode (r.d.e), are done naturally in air
It is dry.Obtained electrode carries out oxygen precipitation (OER) activity rating according to the electrode testing procedure in the above content of the invention.Test result
It has been shown that, when analysis oxygen current density is 10mA/cm2When, overpotential 0.27V.
Embodiment 8
Weigh 1.3143 grams of green vitriols and 1.3901 grams of nickel sulfate hexahydrates are dissolved in 20 milliliters of water, ferrous sulfate
It it is 0.5 mole every liter with nickel sulfate total concentration.20mL 0.5mol/L nickel sulfate solution is dripped dropwise under nitrogen atmosphere protection
Add in 80mL 1.25mol/L potassium hydroxide solution, 20min is added dropwise, 40 DEG C of reaction temperature.Then in turbid system
In lead to ozone, react 5h.PH=7 is first finally washed with water to, then is centrifuged after washing 3 times with absolute ethyl alcohol.By product point
It is scattered in ethanol, freeze drier low-temperature vacuum drying.Obtain yellowish-brown powder.Weigh obtained yellowish-brown powder and XC-72
Each 5mg is dispersed in 2mL isopropanol, adds 50 μ L Nafion (5%) solution, and ultrasonic vibration 30min makes well mixed
To catalyst pulp.Then 20 μ L catalyst pulps are pipetted in a diameter of 5mm rotating disk electrode (r.d.e), are done naturally in air
It is dry.Obtained electrode carries out oxygen precipitation (OER) activity rating according to the electrode testing procedure in the above content of the invention.Test result
It has been shown that, when analysis oxygen current density is 10mA/cm2When, overpotential 0.27V.
Embodiment 9
Weigh 1.3143 grams of green vitriols and 1.3901 grams of nickel sulfate hexahydrates are dissolved in 20 milliliters of water, ferrous sulfate
It it is 0.5 mole every liter with nickel sulfate total concentration.20mL 0.5mol/L nickel sulfate solution is dripped dropwise under nitrogen atmosphere protection
Add in 80mL 1.25mol/L potassium hydroxide solution, 20min is added dropwise, 80 DEG C of reaction temperature.Then in turbid system
In lead to ozone, react 5h.PH=7 is first finally washed with water to, then is centrifuged after washing 3 times with absolute ethyl alcohol.By product point
It is scattered in ethanol, freeze drier low-temperature vacuum drying.Obtain yellowish-brown powder.Weigh obtained yellowish-brown powder and XC-72
Each 5mg is dispersed in 2mL isopropanol, adds 50 μ L Nafion (5%) solution, and ultrasonic vibration 30min makes well mixed
To catalyst pulp.Then 20 μ L catalyst pulps are pipetted in a diameter of 5mm rotating disk electrode (r.d.e), are done naturally in air
It is dry.Obtained electrode carries out oxygen precipitation (OER) activity rating according to the electrode testing procedure in the above content of the invention.Test result
It has been shown that, when analysis oxygen current density is 10mA/cm2When, overpotential 0.29V.
Above-described embodiment can enumerate many, be proved from the substantial amounts of test data of applicant, using technical solution of the present invention
Involved preparation method, it can successfully synthesize Fe3+β-the Ni (OH) of doping2Nanometer rods, and show in the basic conditions
Excellent oxygen evolution reaction (OER) catalytic performance.
Claims (10)
1. a kind of preparation method of oxygen evolution reaction elctro-catalyst, methods described is included the mixture of ferronickel salting liquid and aqueous slkali
System is exposed to the step of being reacted in oxidizing atmosphere；
Described ferronickel salting liquid is that soluble ferrite and soluble nickel salt are dissolved in water and uniformly mix resulting solution；
Described soluble ferrite is selected from ferrous sulfate, frerrous chloride or ferrous acetate；
Described soluble nickel salt is selected from nickel sulfate, nickel chloride or nickel acetate.
2. according to the method for claim 1, it is characterised in that described aqueous slkali is selected from potassium hydroxide aqueous solution, hydrogen-oxygen
Change sodium or ammoniacal liquor.
3. according to the method for claim 1, it is characterised in that：
Described ferronickel concentration of salt solution is 0.1~2mol/L；
In described ferronickel salting liquid, the mol ratio of ferrous salt and nickel salt is 0.05~0.6.
4. according to the method for claim 1, it is characterised in that in the aqueous slkali, according to OH-Meter, the amount of its material is nickel
2~30 times of ion and iron ion total moles.
5. method according to claim 1, it is characterised in that aqueous slkali is added dropwise in ferronickel salting liquid mixture is made
System, the speed of dropwise addition is 0.5~4mL/min；It is preferred that 1mL/min.
6. method according to claim 1, it is characterised in that described mixed system is exposed to what is reacted in oxidizing atmosphere
Temperature is 20-90 DEG C.
7. according to the method for claim 1, comprise the following steps：
(1) under inert atmosphere protection, soluble ferrite and soluble nickel salt are dissolved in water and are well mixed and prepare concentration as 0.1
~2mol/L ferronickel salting liquid；
(2) under inert atmosphere protection, the ferronickel salting liquid prepared by step (1) is added dropwise according to 1mL/min speed
It is in 0.1~5mol/L potassium hydroxide aqueous solutions to concentration；
(3) by step (2) prepare mixed system be exposed to oxidizing atmosphere in, under the conditions of 20~90 DEG C stirring reaction 4~
6h；Gained sediment is first washed with deionized to pH=7, then is washed 3 times with absolute ethyl alcohol, and ethanol is distributed to after centrifugation
In, frozen drying.
8. the Fe that the method for claim 1 is prepared3+β-the Ni (OH) of doping2。
9. the Fe of claim 83+β-the Ni (OH) of doping2Application in oxygen evolution reaction (OER).
10. application according to claim 9, it is characterised in that described application is to be used as OER in the basic conditions to be catalyzed
Agent.
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