CN108511766A - A kind of bifunctional electrocatalyst and preparation method thereof - Google Patents
A kind of bifunctional electrocatalyst and preparation method thereof Download PDFInfo
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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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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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- 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
- H01M4/9041—Metals or alloys
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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
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- 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 discloses a kind of bifunctional electrocatalyst and preparation method thereof, and preparation method includes：Oligoacrylonitrile is added in solvent, hydroxylated multi-walled carbon nanotubes are then added, stirs 1 ~ 2 hour, obtains paste suspension；Metal salt solution is added while stirring into the paste suspension, after stirring 0.5 ~ 1.5 hour, is transferred in oil bath, 30 ~ 50oIt is stirred 2 ~ 5 hours under C atmosphere；The solvent in mixture obtained by above-mentioned steps is removed, solid mixture is obtained；By the solid mixture under inert atmosphere protection, 800 ~ 1000oIt is calcined 0.5 ~ 1.5 hour under C, obtains calcined product, the ground processing of calcined product obtains bifunctional electrocatalyst.The present invention is that raw material have synthesized high performance ORR and OER bifunctional electrocatalysts using carbon nanotube and oligoacrylonitrile.The synthetic method is simple, environmental-friendly and of low cost.
Description
Technical field
The present invention relates to catalyst technical fields more particularly to a kind of bifunctional electrocatalyst and preparation method thereof.
Background technology
In fuel cell and electrolytic water device, fuel battery negative pole oxygen reduction reaction（ORR）With electrolytic water device anode
Oxygen evolution reaction（OER）Slow and complicated oxygen electrode restrict their commercial applications.On the other hand, metal-sky
The cathode reaction in pneumoelectric pond is exactly mainly the reaction of oxygen, including oxygen when oxygen reduction reaction and battery charge when battery discharge
Evolution reaction.Since oxygen reaction process is in kinetically slower characteristic, the use of catalyst can be improved largely
The efficiency of oxygen reaction.
Present researcher is also not limited only to study single catalyst, finds ORR, OER of high quality and at a reasonable price
Bifunctional catalyst is to realizing that the incremental advances of metal-air battery have great significance.Existing precious metals pt catalyst
It can be reacted, but catalytic capability is very weak in oxygen evolution reaction, can not be answered as bifunctional catalyst with efficient catalytic oxidation-reduction
It uses in metal-air battery.
Therefore, the existing technology needs to be improved and developed.
Invention content
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of bifunctional electrocatalyst and its preparations
Method, it is intended to solve existing catalyst and cannot function as ORR, OER bifunctional catalyst to be applied to asking in metal-air battery
Topic.
Technical scheme is as follows：
A kind of preparation method of bifunctional electrocatalyst, wherein including：
Step A, oligoacrylonitrile is added in solvent, hydroxylated multi-walled carbon nanotubes is then added, stirred 1 ~ 2 hour, obtain
To paste suspension；
Step B, metal salt solution is added while stirring into the paste suspension, after stirring 0.5 ~ 1.5 hour, is transferred to
In oil bath, 30 ~ 50oIt is stirred 2 ~ 5 hours under C atmosphere；
Step C, the solvent in mixture obtained by removal step B, obtains solid mixture；
Step D, by the solid mixture under inert atmosphere protection, 800 ~ 1000oIt calcines 0.5 ~ 1.5 hour, obtains under C
To calcined product, the ground processing of calcined product obtains bifunctional electrocatalyst.
The preparation method of the bifunctional electrocatalyst, wherein in the step A, point of the oligoacrylonitrile
Son amount is between 200 ~ 700.
The preparation method of the bifunctional electrocatalyst, wherein in the step A, the oligoacrylonitrile and hydroxyl
The mass ratio of base multi-walled carbon nano-tube is 1 ~ 10.
The preparation method of the bifunctional electrocatalyst, wherein in the step B, metal salt is iron chloride, cobalt chloride
One or both of.
The preparation method of the bifunctional electrocatalyst, wherein in the step B, the hydroxylating multi-wall carbon nano-tube
The mass ratio of pipe and the metal ion in metal salt is 0.3 ~ 0.4.
The preparation method of the bifunctional electrocatalyst, wherein the step C includes：Mixture obtained by step B is set
In 70 ~ 90oUnder C oil bath atmosphere, magnetic force rotary evaporation removes most of solvent；It is then transferred in vacuum drying chamber, in 60 ~
80 oResidual solvent is evaporated at a temperature of C, obtains solid mixture.
The preparation method of the bifunctional electrocatalyst, wherein the time of the magnetic force rotary evaporation is 3 ~ 5 hours,
The vacuum drying time is 6 ~ 8 hours.
The preparation method of the bifunctional electrocatalyst, wherein in the step D, calcination process takes temperature programming
Mode carries out：First segment heating rate is 5oC·min~1, until 300oC keeps the temperature 20 minutes, and second segment heating rate is 2oC·
min~1, until 800 ~ 1000oC is calcined 0.5 ~ 1.5 hour.
The preparation method of the bifunctional electrocatalyst, wherein in the step D, 900oIt is calcined 1 hour under C,
Obtain the calcined product.
A kind of bifunctional electrocatalyst, wherein prepared using the preparation method of bifunctional electrocatalyst of the present invention
It obtains.
Advantageous effect：The present invention is that raw material have synthesized high property using hydroxylated multi-walled carbon nanotubes and oligoacrylonitrile
ORR the and OER bifunctional electrocatalysts of energy.The synthetic method is simple, environmental-friendly and of low cost.It is synthesized using this method
Catalyst, under alkaline condition, ORR activity is comparable with business Pt/C catalyst, OER activity be better than business IrO2,
With good application prospect.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for the catalyst that embodiment 1 obtains in the present invention.
Fig. 2 is the catalyst that embodiment 1 obtains in the present invention and business Pt/C catalyst in the KOH solution of 0.1 M
Oxygen reduction reaction LSV test charts.
Fig. 3 is the catalyst that embodiment 1 obtains in the present invention and business Pt/C catalyst in the KOH solution of 0.1 M
Oxygen evolution reaction LSV test charts.
Fig. 4 be in the present invention the obtained catalyst of embodiment 1 in O2In 0.1 M KOH solutions of saturation, in different rotating speeds
Under oxygen reduction reaction LSV test charts.
Fig. 5 be in the present invention the obtained catalyst of embodiment 1 in O2In 0.1 M KOH solutions of saturation, in different rotating speeds
The K-L of lower oxygen reduction reaction schemes.
The oxygen for the ANT-CNT-Fe catalyst and ANT-CNT-Co catalyst that Fig. 6 is prepared for the embodiment of the present invention 2,3 is also
Performance test figure is precipitated in original reaction and oxygen, schemes with business Pt/C COMPARATIVE CATALYSTs.
Specific implementation mode
The present invention provides a kind of bifunctional electrocatalyst and preparation method thereof, for make the purpose of the present invention, technical solution and
Effect is clearer, clear, and the present invention is described in more detail below.It should be appreciated that specific embodiment described herein
It is only used to explain the present invention, be not intended to limit the present invention.
The present invention provides a kind of preparation method of bifunctional electrocatalyst, wherein including：
Step A, oligoacrylonitrile is added in solvent, hydroxylated multi-walled carbon nanotubes is then added, stirred 1 ~ 2 hour, obtain
To paste suspension；
Step B, metal salt solution is added while stirring into the paste suspension, after stirring 0.5 ~ 1.5 hour, is transferred to
In oil bath, 30 ~ 50oIt is stirred 2 ~ 5 hours under C atmosphere；
Step C, the solvent in mixture obtained by removal step B, obtains solid mixture；
Step D, by the solid mixture under inert atmosphere protection, 800 ~ 1000oIt calcines 0.5 ~ 1.5 hour, obtains under C
To calcined product, the ground processing of calcined product obtains bifunctional electrocatalyst.
The present invention using hydroxylated multi-walled carbon nanotubes and oligoacrylonitrile be raw material synthesized high performance ORR and
OER bifunctional catalysts.The synthetic method is simple, environmental-friendly and of low cost.Using difunctional the urging of this method synthesis
Agent, under alkaline condition, ORR activity are comparable with business Pt/C catalyst, and OER activity is better than business IrO2, have
Good application prospect.
The step A is specifically included：Oligoacrylonitrile is dissolved into solvent first（Such as absolute ethyl alcohol）In, then it is added
Hydroxylated multi-walled carbon nanotubes stir 1 ~ 2 hour, obtain the paste suspension of black.In order to ensure preferable mixing effect, adopt
It is stirred with magnetic stirring apparatus, mixing speed is unsuitable too fast or excessively slow, is advisable with 200 ~ 500 rpm, preferred rotating speed is
300 rpm。
Oligoacrylonitrile of the present invention（ANT, Chinese patent CN102212965A）For a kind of polymer, at room temperature for
Weak yellow liquid is made by the method for free poly tone, and preparation method is simple, environmental-friendly.The oligoacrylonitrile
Inherently there is preferable ORR catalytic performances, using ANT as the advantage of dopant and liquid carbon matrix precursor after high temperature sintering
It is, the catalyst of N, S codope can be made with a step, and its distinctive liquidus behavior can be with hydroxylating multi-wall carbon nano-tube
Closely contact is generated between pipe and metal salt.Furthermore the high nitrogen content of ANT and graphited ability are also after calcining
ANT has one of the reason of preferable ORR catalytic performances.Therefore the liquid polymers are excellent carbon matrix precursors.Preferably, described
The molecular weight of oligoacrylonitrile is between 200 ~ 700.
Since carbon nano tube surface defect is few, it is unfavorable for depending on for other particles.After acidification, the hydroxyl of a part can be generated
The groups such as base, these surface groups are conducive to other species and are reacted with carbon nanotube, or directly as reactive group bottom.Therefore originally
Invention synthesizes bifunctional electrocatalyst using hydroxylated multi-walled carbon nanotubes as raw material.Preferably, hydroxylating of the present invention
The model XFM05 of multi-walled carbon nanotube, No. CAS is 1333-86-4, and purity is more than 95%, and length is 0.5 ~ 2 micron, hydroxyl
Change content is 5.58 wt%.
Preferably, the oligoacrylonitrile and the mass ratio of hydroxylated multi-walled carbon nanotubes are 1 ~ 10, it is highly preferred that matter
Amount is than being 1, the target product best performance being prepared under the ratio.
The step B is specifically included：By metal salt solution（Such as metal salt ethanol solution）It is outstanding that it is added drop-wise to paste while stirring
In turbid, it is stirred by ultrasonic 0.5 ~ 1.5 hour（Such as 1 hour）Later, it is transferred in oil bath, 30 ~ 50oC（Such as 40oC）It is stirred under atmosphere
It mixes 2 ~ 5 hours.
Preferably, the mass ratio of hydroxylated multi-walled carbon nanotubes and the metal ion in metal salt is 0.3 ~ 0.4.This be because
For on the one hand hydroxylated multi-walled carbon nanotubes are the carriers of active component, by polymer（That is oligoacrylonitrile）Package and
On the other hand embedded with metal particle is the electric conductivity for increasing catalyst.Metallic iron or cobalt are with iron chloride, cobalt chloride metal salt solution
Mode be added in above-mentioned paste suspension, when high-temperature calcination, the chlorine element of introducing can be volatilized in the form of gas molecules
It goes out, and pore structure is formed in the polymer surfaces of carbonization, play the role of pore-creating with the more active sites of exposure.Together
When, the metal salt of addition should not be excessive as active constituent, hydroxylated multi-walled carbon nanotubes and the metal ion in metal salt
Mass ratio is 0.3 ~ 0.4, it is preferred that the mass ratio of hydroxylated multi-walled carbon nanotubes and the metal ion in metal salt is 0.33
When, metal dispersity is good, is conducive to catalytic activity and efficiently plays.
In order to enable polymer and hydroxylated multi-walled carbon nanotubes covered effect are preferable, by polymer be transferred in oil bath in
30~50 oIt is stirred 2 ~ 5 hours under C atmosphere.The length of mixing time directly affects polymer overmold carbon nanotube in oil bath
Thickness, it is preferred that stirring 5 hours, polymer overmold carbon nanotube thickness is uniform, and property is stablized.
The step C is specifically included：Mixture obtained by step B is placed in 70 ~ 90oC（Such as 80oC）Under oil bath atmosphere, magnetic
Power rotary evaporation removes most of solvent；It is then transferred in vacuum drying chamber, in 60 ~ 80oC（Such as 80oC）At a temperature of will remain
Remaining solvent is evaporated, and obtains solid mixture.Preferably, the time of the magnetic force rotary evaporation is 3 ~ 5 hours, when vacuum drying
Between be 6 ~ 8 hours.
The step D is specifically included：The solid mixture of above-mentioned solvent evaporated is transferred in clean porcelain boat, and by institute
It states porcelain boat to be placed in tubular heater, be calcined under an inert atmosphere, calcination temperature is 800 ~ 1000oC（Such as 900oC）, forge
It is 0.5 ~ 1.5 hour to burn the time（Such as 1 hour）.The inertia protection gas is argon gas, is in order to avoid solid mixture is in high temperature
The side reactions such as oxidation occur in calcination process.Before starting calcining, tubular heater need to be evacuated to vacuum meter reading be ~
0.1 MPa or so, supplement inertia protect gas to 0 MPa, in triplicate.It forms inert protective atmosphere to enclose, prevents solid mixture
It is aoxidized in temperature-rise period.After high-temperature calcination, Temperature fall processing is carried out, when tubular heater temperature is less than 50oC
When, take out porcelain boat, be cooled to room temperature it is ground, sieving processing, obtain the bifunctional electrocatalyst.
Preferably, the calcination process is carried out using temperature-programmed mode：First segment heating rate is 5oC·min-1, until
300 oC keeps the temperature 20 minutes, and second segment heating rate is 2oC·min-1, until 800 ~ 1000（Such as 900oC）Calcining 0.5 ~ 1.5 is small
When（Such as 1 hour）.Using the method for temperature programming, solid mixture can be made further to be removed in conjunction in the molecule in low-temperature zone
Moisture, avoid being rapidly increased to higher temperature damaging the activity of catalyst.During being continuously heating to higher temperature,
The heating rate of use is lower, and this aspect is to prevent from temperature from increasing suddenly to cause active component to volatilize catalyst, another party
The time that face is to provide abundance chemically reacts for mixture, obtains structure, the more uniform bifunctional electrocatalyst of composition.
The present invention also provides a kind of bifunctional electrocatalysts, wherein using bifunctional electrocatalyst of the present invention
Preparation method is prepared.
Below by several embodiments, the present invention is described in detail.
Embodiment 1
First, 25mL absolute ethyl alcohols are measured in beaker, 0.1 g oligoacrylonitriles are added dropwise（Molecular weight is 500）, polymer is molten
Xie Hou weighs 0.1 g hydroxylated multi-walled carbon nanotubes（Model XFM05）It is added in same beaker.Magnetic agitation 1 hour, makes
It is uniformly mixed.Then 330 uL, 0.5 M iron chloride ethanol solutions, 440 uL, 0.375 M cobalt chloride second are added dropwise while stirring
Beaker is transferred to ultrasonic machine by alcoholic solution, and ultrasound keeps metal salt solution evenly dispersed in 1 hour.Later, transfer beaker is to oil bath,
40oIt is stirred 5 hours under C atmosphere, is warming up to 80oC evaporates solvent, evaporates about 3 hours solvent used times.It is black by what is obtained later
Color solid mixture is transferred to porcelain boat, is positioned over vacuum drying chamber, and 80oC is dried overnight.Finally, above-mentioned porcelain boat is placed in tubular type
In heating furnace, 900oHigh temperature sintering 1 hour under C argon atmospheres, by grinding to get ANT-CNT-FeCo catalyst.
ANT-CNT-FeCo catalyst manufactured in the present embodiment is scanned Electronic Speculum characterization, the results are shown in Figure 1.It can be with
Find out, coats a diameter of 32.3nm of all right carbon nanotube, about exposed carbon nanotube（Diameter is about 8 ~ 10 nm）
3 times.Simultaneously it can also be seen that cladding situation is not very uniformly that there are a part of carbon nanotubes not by polymer overmold.
It is electrolyte in 0.1 M KOH solutions by ANT-CNT-FeCo catalyst manufactured in the present embodiment, glass-carbon electrode,
Pt pieces and Ag/AgCl are respectively working electrode, to carrying out electro-chemical test in the electrolytic cell of electrode and reference electrode.Use permanent electricity
Position instrument and rotating disk electrode (r.d.e) device are tested.All electrode potentials are all directed to reversible hydrogen electrode (reversible
Hydrogen electrode, RHE).Test condition is：Catalyst loading is 0.5 mgcm-2；It is 10 mV to sweep the rate of hastening
s-1.Before RDE tests, 0 ~ 1 V, 50 mVs are carried out to catalyst first-1, 20 circle cyclic voltammetries, to remove surface
Pollutant.The linear volt-ampere ORR test conditions of RDE are 0.1 ~ 1.1V, are just sweeping 5 mVs-1；OER test conditions are 1.0 ~ 1.8 V.
RDE tests are prepared into from electrode to be repeated 3 times until data stabilization is to ensure reproducibility.As a result as shown in Figure 2 and Figure 3.From Fig. 2
As can be seen that low about 30 mV of ANT-CNT-FeCo catalyst take-off potential ratio Pt/C catalyst prepared by the present embodiment, half-wave
Current potential is suitable with Pt/C catalyst with carrying current., it is apparent that being 10 mAcm in current density from Fig. 3-2When,
Overpotential is 0.34 V.This data is better than common business IrO2Catalyst（0.39 V）.It can be said that the bifunctional catalyst
Better performances.
Another important parameter of characterization ORR performances is four electronic selections of catalyst, the reason is that oxygen passes through four electricity
Subprocess is directly reduced to water or OH-, more more efficient than being reduced into hydrogen peroxide by bielectron process.By the present embodiment system
Standby ANT-CNT-FeCo catalyst is electrolyte in 0.1 M KOH solutions, and glass-carbon electrode, Pt pieces and Ag/AgCl are respectively work
Make electrode, to carrying out electro-chemical test in the electrolytic cell of electrode and reference electrode.Four electronic selections of ANT-CNT-FeCo are
By testing ORR polarization curves under different rotating speeds（See Fig. 4）And do what K-L equation models obtained.From figure 5 it can be seen that
Good linear relationship is presented in the K-L figures of ANT-CNT-FeCo under all potentials, illustrates that its reaction is first order reaction, rate
It is directly proportional to oxygen concentration.Electron transfer number has 3.8 ~ 4.0 under high potential, illustrates the ORR on ANT-CNT-FeCo
Reaction is carried out according to four electronic channels.
Embodiment 2
First, 25 mL absolute ethyl alcohols are measured in beaker, 0.1 g oligoacrylonitriles are added dropwise（Molecular weight is 700）, polymer
After dissolving, 0.1 g hydroxylated multi-walled carbon nanotubes are weighed（Model XFM05）It is added in same beaker.Magnetic agitation 1 hour,
It is set to be uniformly mixed.Then 595 uL, 0.5 M iron chloride ethanol solutions are added dropwise while stirring, beaker is transferred to ultrasonic machine, surpass
Sound keeps metal salt solution evenly dispersed in 1 hour.Later, transfer beaker is to oil bath, 40oIt stirs 2 hours, is warming up under C atmosphere
80 oC evaporates solvent, evaporates about 3 hours solvent used times.Obtained black solid mixture is transferred to porcelain boat later, is positioned over
Vacuum drying chamber, 80oC is dried overnight.Finally, above-mentioned porcelain boat is placed in tubular heater, 900oIt is high under C argon atmospheres
Temperature sintering 1 hour, by grinding to get ANT-CNT-Fe catalyst.
Embodiment 3
First, 25 mL absolute ethyl alcohols are measured in beaker, 0.1 g oligoacrylonitriles are added dropwise（Molecular weight is 200）, polymer
After dissolving, 0.1 g hydroxylated multi-walled carbon nanotubes are weighed（Model XFM05）It is added in same beaker.Magnetic agitation 1 hour,
It is set to be uniformly mixed.Then 750 uL, 0.375 M cobalt chloride ethanol solutions are added dropwise while stirring, beaker is transferred to ultrasonic machine,
Ultrasound keeps metal salt solution evenly dispersed in 1 hour.Later, transfer beaker is to oil bath, 40oIt stirs 2 hours, heats up under C atmosphere
To 80 oCSolvent is evaporated, about 3 hours solvent used times are evaporated.Obtained black solid mixture is transferred to porcelain boat later, is placed
In vacuum drying chamber, 80oC is dried overnight.Finally, above-mentioned porcelain boat is placed in tubular heater, 900oUnder C argon atmospheres
High temperature sintering 1 hour, by grinding to get ANT-CNT-Co catalyst.
Fig. 6 is the hydrogen reduction of ANT-CNT-Fe catalyst and ANT-CNT-Co catalyst prepared by above-described embodiment 2,3
Performance test figure is precipitated in reaction and oxygen, schemes with business Pt/C COMPARATIVE CATALYSTs.
In conclusion the present invention provides a kind of bifunctional electrocatalysts and preparation method thereof.The present invention utilizes carbon nanometer
Pipe and oligoacrylonitrile are that raw material have synthesized high performance ORR and OER bifunctional electrocatalysts.The synthetic method is simple,
It is environmental-friendly and of low cost.The catalyst synthesized using this method, under alkaline condition, ORR activity is urged with business Pt/C
Agent is comparable, and OER activity is better than business IrO2, there is good application prospect.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of preparation method of bifunctional electrocatalyst, which is characterized in that including：
Step A, oligoacrylonitrile is added in solvent, hydroxylated multi-walled carbon nanotubes is then added, stirred 1 ~ 2 hour, obtain
To paste suspension；
Step B, metal salt solution is added while stirring into the paste suspension, after stirring 0.5 ~ 1.5 hour, is transferred to
In oil bath, 30 ~ 50oIt is stirred 2 ~ 5 hours under C atmosphere；
Step C, the solvent in mixture obtained by removal step B, obtains solid mixture；
Step D, by the solid mixture under inert atmosphere protection, 800 ~ 1000oIt calcines 0.5 ~ 1.5 hour, obtains under C
Calcined product, the ground processing of calcined product, obtains bifunctional electrocatalyst.
2. the preparation method of bifunctional electrocatalyst according to claim 1, which is characterized in that described in the step A
The molecular weight of oligoacrylonitrile is between 200 ~ 700.
3. the preparation method of bifunctional electrocatalyst according to claim 1, which is characterized in that described in the step A
Oligoacrylonitrile and the mass ratio of hydroxylated multi-walled carbon nanotubes are 1 ~ 10.
4. the preparation method of bifunctional electrocatalyst according to claim 1, which is characterized in that in the step B, metal
Salt is one or both of iron chloride, cobalt chloride.
5. the preparation method of bifunctional electrocatalyst according to claim 1, which is characterized in that described in the step B
The mass ratio of hydroxylated multi-walled carbon nanotubes and the metal ion in metal salt is 0.3 ~ 0.4.
6. the preparation method of bifunctional electrocatalyst according to claim 1, which is characterized in that the step C includes：It will
Mixture is placed in 70 ~ 90 obtained by step BoUnder C oil bath atmosphere, magnetic force rotary evaporation removes most of solvent；It is then transferred to true
In empty drying box, in 60 ~ 80oResidual solvent is evaporated at a temperature of C, obtains solid mixture.
7. the preparation method of bifunctional electrocatalyst according to claim 6, which is characterized in that the magnetic force rotary evaporation
Time be 3 ~ 5 hours, the vacuum drying time be 6 ~ 8 hours.
8. the preparation method of bifunctional electrocatalyst according to claim 1, which is characterized in that in the step D, calcining
Process takes temperature-programmed mode to carry out：First segment heating rate is 5oC·min-1, until 300oC keeps the temperature 20 minutes, second segment
Heating rate is 2oC·min-1, until 800 ~ 1000oC is calcined 0.5 ~ 1.5 hour.
9. the preparation method of bifunctional electrocatalyst according to claim 1, which is characterized in that in the step D,
900 oIt is calcined 1 hour under C, obtains the calcined product.
10. a kind of bifunctional electrocatalyst, which is characterized in that use the difunctional electro-catalysis of claim 1 ~ 9 any one of them
The preparation method of agent is prepared.
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| CN114649536A (en) * | 2022-03-21 | 2022-06-21 | 河北工业大学 | Rare earth oxide supported iron nanoparticle catalyst and preparation method and application thereof |
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